CA2653928A1 - Molecular sieve ssz-75 composition of matter and synthesis thereof - Google Patents
Molecular sieve ssz-75 composition of matter and synthesis thereof Download PDFInfo
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- CA2653928A1 CA2653928A1 CA002653928A CA2653928A CA2653928A1 CA 2653928 A1 CA2653928 A1 CA 2653928A1 CA 002653928 A CA002653928 A CA 002653928A CA 2653928 A CA2653928 A CA 2653928A CA 2653928 A1 CA2653928 A1 CA 2653928A1
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- oxide
- molecular sieve
- catalyst
- tetravalent element
- hydrocarbon
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The present invention relates to new crystalline molecular sieve SSZ-75 having STI topology prepared using a tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication as a structure-directing agent, methods for synthesizing SSZ-75, and uses for SSZ-75.
Description
2 PCT/US2007/070210 I MOLECULAR SIEVE SSZ-75 CC3MPOSiTIC)N OF MATTER
3
4 BACKGRC?UN~ OF THE lNVi~i`JT IOiei 6 Field of the lnventior-i 8 The present invention relates to new crystalline molecular sieve SSZ- 7 u,a 9 method for preparing SSZ75 using a tetramethy1ene=-1,4--bis-(N-riiethylpyrrolirtinit-Ãm) dication as a structure directing agerit ("SDA") and uses 11 tcar SSZ--75.
16 Because of their unique sieving characteristics, as well as their catalytic 16 proper-ties; crystalline moEecr:rlar sieves and zeolites are ~~pecially useful Ãn 17 applications such as hydrocarbori conversion, gas drying and separatÃon.
18 AlthoL,gh many different crystalline rnolecuiar sieves h:ave been disrl~~ed.
19 there is a continuing need for new molecular sieves with desirable properties for gas separation and dryÃng, hydrocarkaor? and cherniraal conversions, and 21 other applications, New molecular sieves may contain novel internal pore 22 architectures, providing erihanced selectivities in these processes.
26 The present invention is directed to a family of crystalline molecular sieves 27 with unique properties, referred to herein as"molecular- sieve SSZ 75,' or 28 simply "~~Z-75". SSZ-75 has the fr-ar-nework topology designated "STI" by 29 the~. IZA. Materials having the STI tcspology include naturally occurring stilbite and the zeniite designated T-NU-10: Stilbite is disclosed irR Breckr Zeolite 31 Molecular Sieves, 1984, Robert E. Kr:eger Publishing Company where it is 32 reported ttlat strlbfir~ has a typical sili ;afalun-r#na mole ratio of 5,2_ Tl'1U-10 is 33 reported in Hong et a~., J. AM. Ci-IEM, SOC. 2004, 126, 5817-5826 as having 34 a silica/alurriir-ra mole ratio of about 14. Wheri attp-rnpts were rriade to .-g-1 increase the sifÃca:raIurnina rri01e ratio in trie product; rrraterials ott7er than 2 'i'NU-10 were produced.
4 In accordance with the present invention there is provÃdeda crystalline molecular sieve having STI topology and having a mole ratio of at ieast 15 of 6 (`~) an oxide of a first tetravalent eIems-nnt to (2) an, oxide of a trivafent element, 7 pentavalent element, second tetravalent element which is different from said 8 first tetravalent element or MixtÃ.Ãre thereof. The SSZ-75 molecular sieve has, 9 after calcination., trse< Y-ray diffrac-tion lines of Table I'.I. It should be noted trla1 the phrase ' moIe ratio of at, least. 15' includes the case where there is no 11 oxide (2), Ã.e., the mole ratio of oxide t1i to oxide "2) is ir{tinity:. In that case t2 the mole-cuiar sieve is comprise~.t or essentially afl sificon oxide.
14 The present iriven#ioÃ) also provides aMstalline molecular sieve having STI
topology and tiavirig ~.~ rnole rafi#o of at least 15 of (1) silicon oxide to (2) an 16 oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide;
17 titanium oxide, indium oxide and mixtures thereof. The SSZ-75 moler}Lalar 18 sieve has, after calCÃnatian, the X-ray diffraction lit~~s of Table Il.
The present invention fuÃther, provides such acÃ-ystaliine molecular sieve 21 having a composition comprising, as synthesized and in the anhydrous state, 22 in terms of rnc:31e ratios the tolEritivirÃg:
24 SiO2 / XIO~ at least 15 (i,e., 15 -- infinity) SiOz 0-0. C]a 26 Q 1302 0.02 - 0.08 27 F f sioz 0:01--- 0.04 29 wherein X is aluminum, gaftium, iron, boron, titanium, indium and mixtures tiiereofr c is I or 2, d is 2 when c is 1(Ã.e., W is tetravalent) or d is 3 or awt=ien 31 c is 2 (i.e,, d is 3 when VV is trivalent or 5 wfieri 17V is perktaualent);
M is an 32 alkali metal cation, alkaline earth metal cation or mÃxtures tE;ereot, ri is the -1 valenc;e of M (Le;, 1 or 2); Q is a tetrarriethyierre-'i,4-bis-(N-niet.1-,yI
2 pyrralidÃniur;s) dieation and F is fluoride.
4 Also provided ir) accordance with the present in-ventÃon is a method of preparing a crystaffine material, said method comprising contacting under 6 crystallizatiors conditions a source{sJ of (1) silacon oxide, (2) a source(s) of 7 aIumÃntim oxide, gallium oxide, iron oxide, boron oxÃde, titanium oxide, indium 8 oxide and mixtures thereof, (3) fitiorÃ~e bns arrd (4) a 5tructtire directing agent 9 comprising a te,b:r.ame'thylene--1,4-bis--(N-methYiPyrrolidinÃurri) ciicatpon. Ti-le present Ãnventiori incftides srich a method wherein the cr-ystal?ir:e Ã~n~.ater4 has -`i 1 STI topology and wh:erein ttie moiecri1ar sieve has, after calcination, the X...ray 12 diffraction lines af'Fab1e !!.
14 The preserit invention inciudes such a method of preparing a crystalline material which Lrses a reaction rraixttir-e corriprising (in terms of mole ratios), 16 the foi:~.~wing:
18 Smt?2 1 x3o:; at least 15 (Ã.e;, 15 T infinity) 19 ON. rF SiO2 0.20-0.80 Q l Si02 0.20--= 0<8Q
21 M2;1 / Si02 0 - 0.04 22 t-i20 1 SÃ02 2-- 10 23 HF / SiO2 0.20 --- 0:80 wherein X is aluminum, gafliurii, iro-s~, boron, t;taniurn, irdium and mixtures 26 thf:rp-of, a is 1 or 2, b 3s 2 when a is 1 (i.e., W is. xetraualent); b is 3 wheri a is 2 27 (i.e,;W is trivalent), M is an aIicaIi metal cation, alkaline earlh metal cation or 28 mixtures thereot; n is tt~evaience of M ;i.e., I or 2}', and Q is a 29 tetrar~e"Lhvie ne--1;4--bisrt,N -rnefiiyl~y rrolad in iu r?n) dication, 31 ir~ accordance with the present inverrtior: them is provided a process for 32 .;onver`tÃng hydrocarbons comprising contacting a hydro; a;rk.onace<aus feed at 33 hydrocarbon converting conditions with a catalyst corrit-rr'lsarÃg a crystalline ^
.,,g ..
1 molecular sieve having STI topology and having a mole ratio of at least 15 of 2 (1) an oxide af a first tet~ava;ent element to (2) an oxide of a trivalent Clement, 3 pentavalerit element, second tet:~avaÃent elemer?; which is ~iffp-rent from said 4 f:rst tetravaient element or Ã'nixture thereot: SSZ-_'rz~ ~~~ ~fter ;
aIcination, k~e X..ray diffraction lines of 't=ab!e Il, la should be noted that the phÃase ;'Mol~
6 ratio of at least 1a" includes the case where there is no oxide (2), i.e., the 7 mole ratio of oxide~ (1) to oxide (2) is infinity. In that case the molecular si~ve, 8 i~ ~omprised of essentially alt silic ori oxide. The molecular sieve may be 9 predominantly in the hydrogen forrr,- It may also be 4ribstant:Ãally free of acidity.
12 1~i_rrl:hPr provided by the present invention is a hydrocracking process 13 comprising corrtactirig a hydrocarbon feeetstoci': under hydrocracking 14 conditions with a catalyst coÃnpr;sing the molecular sieve of this invention, preferably predominantly in the hydrogen forrn.
17 Also iriclLided iri this invention is a process for increasing the octaÃie of a 18 liydrocarbnn feedstock to produce a product having an increased aromatics 119 content comprming contacting a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range 21 above about 401G and less than about 2001,C. L,nder aromatic conversion 22 conditions with a catalyst comprising the molecular sieve of this invention 23 i-i-iar~~ substantially free of acidity by neutralizing said mol~cular sieve with a 24 basic rrietal. Also provided in this invention Ã~ such a process wherein the molecular sieve contains a GroÃ.;p VI1l metal component.
27 Also provided bythe present invention #sa catalytic cracking process 28 comprising contacting a hydrocarbon feedstock in ~-i rf.action zone under 29 catalytic cracking conditions in the absence of actded hydrogen with a catalyst cor r*pÃ:sÃnq the molect.Ãlar sieve of this invention, preferably predominantly in 31 thehydregen #orm. Also irrducled in this iÃiveiition is such a catalytic c,ackinq 32 process where4Ãi the catalyst ~dciitionall~ oorrip;Ãses a large pore crystaliline 33 cracking t,omponent.
2 This in;rentior, further provides an isomerization process for isomerizing Cd to 3 C7 hydrocarbons, compa-isÃn.g contacting ~.~ f~ed ti~.~vring norrnal and slightly 4 branched C4 tG' Cr hydrocarbons under isomerezir*g conditions with a catalyst campris3ng the r-riolecLÃIar sieve of this invention, preferably predorÃ-Ãinanfty in 6 the hydrogen form. The maÃec.u1ar sieve may bm impregnated with at least 7 one Gr~~~p Viif metai: preferably platirÃum. The ;~~tailyst may be- calcined in a 8 steam/a:Ã niixture at an elevated temperature after impregnation of the GrmÃp 9 JIII metal.
1 1 Also provided by the present Ãnventnn, is a process for alkylating ari aror7eaiic 1'a:.' hydrocarbon which comprises contacting under aiiÃyiation conditions at least a 13 molar excess of an aromatic hydrocarbon with a C? tO C20 oÃefÃn under at least 14 pa:-tial 3iquid phase conditions @nd in the preserace of a catalyst cos-nprising thp-molecular ~~~ve. of this invention, preferably predominantly in. the hydrogen 16 form, The olefin may be a C;; to C.4 o:efiÃ:Ã, and the aromatic hydrocarbon and 17 olefin may be present in a molar ratio of about 4:1 to aboLÃt 20:1, respectively.
18 The aromatic hydÃoc;arbor) may be selected from the group consisting of 19 ber~zeÃie, toluene, ethysbenxene< xylene, naphthalene, r~aphthaiene derivatives, dimethyBnaphfhaier:e or mixtures thereot.
22 Ftirther provided in accordance with ttiis invenfion is a process for 23 transaikylating an aromatic hydrocarbori which comprises coritactir~g under 24 transalkylating conditions an aromatic hydrocarbori with a poiyalkyE
arornatiu hydrocarborà under at least partial liquid phase condÃtioris and in the presence 26 of a catalyst comprising the molecular sieve of this nventiont preferably 27 predominantly in the hydrogen form. The arornafiic hydrocarbon and the 28 polyalkyl aromatic hydrocarbon may be preseÃit iri a molar ratio of from about 29 1:1 to about 25: 1, respectively.
31 The aromat;c hydrocarbon may be selected from the group co^sistirÃg of 32 benzene, i`ol:aene, ethyibenzene, xylene, or mixtures thereof, and the polyalkyl 33 a,-ornafic iiydrocarborà may be a dialkyÃ.ber-zenfiu.
_.,.-.
2 Further provided by this invention is a process to convert paraffins to ? aroriiatic;s which comprises coritacting paraffins under oondÃtioiis which cause 4 paraffins to convert to aromatics with a catalyst comprlsi;ig. the molecular sieve of this invention, said catalyst comprising galiium, zin:, or a corr~~oi'md 6 Of gaiieUM Or Zir'c<;
8 Ir; accordance with this invention there is also provided a pr-ocress for 9 wsomerizing olefins comprising contacting said olefin :,ender candi.sonswhich cause isc+mer3zation of the 6efin with aCat@iyr:~t COMpriSing ::hlw molecUlar 11 sieve of this invention, 14 Further provided ir, accordance with this #nventirrq ;:s a process for isomerizing 14 an Ã~~merizatEon feed comprising an aromatic G8 stream of xylene isomers or mi~ture~s of xylene isomers and othyfbenzene, wherein a more nearly 76 equiIibrium ratio of ar~~o-, rneta- aia-id para-xyier;e:; is obtained, saifl process 17 comprising coritactbng said feed utider isomerizaon conditions with a catalyst 18 comprising the molecular sieve of this invenbon.
Ttie present invention fu Ãlher :provides a process for oligomerizing oiefins 21 comprising contacting ar> olefir~ feed under oligcarnerizatiOn conditioi1s with a 22 catalyst comprising the molecular sieve of #riis irivention.
24 .1"his iriventioii also provides a process for cotiveri:3~~ ~xygen.ated hydrocarbons cornprisi~~g contacting said oxygenia:ed hydroc-arbu~l with ~.a 26 catalyst cornprising the moiecu1ar sieve of this,nrention under condrtions to 27 produce liquid products. The oxygenate~,d hydrocarbon riiay be a lower 28 alcohol.
Furttie,- provÃdc-d in accordance with the present invention is a process for ti=~p-31 producfio:i of liigher mo(ecu#ar wc-Ãgh'r hydrocarbons from lower rrioieca~~~at 32 weigtai: hydrocarbons ; omprisirig thc- steps of:
~ (a) introducing ifizo a reactio3i zone a lower molecular weight 2 i'-:ydroc:artyon-containing gas and contactirig said gas in said ~..~ zone rander C2h hydrocarbon synthesis conditions with the 4 catalyst and a metai or meiaI c,ompoÃjr7d ~apab6; of convertÃng the. lower moI~cWar weight hydrocarbon to a higher molecular 6 weight hydrocarbon; and 7 (b) withdrawing from said reaction zone a higher molecular weigilt 8 hydrocarbon-contairsÃng stream.
The present invention further provides a process for hydrogeriating a 11 hydrocarbon feed ~onita#ning unsaturated hydrocarboris, the ~~~oc~~~
12 comprising contacting the feed and hydrogen rinder wondations which ca;Ase 13 hydrogenation with a ca#Wysti comprising the molecular sieve af this invention.
14 The catalyst can also contain metals, salts or complexes wherp-in the metal is selected frc:m the group consisting of piatmnumJ paIfaditim, rhodiLim, irid;ufri or 16 com~iriatÃons thereof, or the group consisting of nic kel; molybdenum, Cobai:, 17 tungsten, titanium, chr'ocr3i.um, vasiadium, rhen3um, mariganes~ and 18 combinations thereof.
The present invention also provides a catalyst cCaiiiiaosÃticÃn for prornsatin;
21 polymer3zation of I-otf >iis, said composition cor~~ w.-_--.iT-q 22 (A) a cÃystailirie rriolecuiar sieve having a male ratio of at ieast 15 of 23 (1) an oxide of a first tetravalent element to (2) an oxide of a 24 trivalent eIement, pentavaleiit element, second tetravalent elerraer-ii whit ii ;s different from said first tetravalent element or 26 mixture thereo#' and i~awng, after calcination, the X-ray 27 diffraction lines of Table 11; and 29 (B) an orgaÃiotitanium or organochromium compound.
31 Also provided is a process for polymerizing 1 -alefins, which prorc-ss ;3 2 comprises contacting 1-olefin monomer with a catalytically effective amount of 33 a catalyst composition comprising 2 (A) a crystaiiii~e molecular sieve having a mole ratio of at ieast 15 of 3 ('11) aii oxide of a first tetravaie~,nt element to (2) an oxide of a 4 trivalent e_emerit, pentavaÃenf element, second tetravalent element ~~rvhr.,h is different from said first tetravalent element or 6 mÃx'tLsre thereof and having, after calcination, the X-ray 7 diffract>on lines of Table II; and 9 (B) ari organo-Aitaniurri or organochromium r_orripound.
1 I under polymerization conditions which include a temperature and pressure 12 suitabie, for iriitiating and promoting thÃ: polymerizafiior, rearation.
The 1-oIeftn 13 may be ethyierie.
~~~he present invention further provides a dewaxing process comprising 16 contacting a hydrocarbon feedstock under dewaxing conditions with a catalyst 17 comprising a crystalline molecular sieve having STI trapoiogy and a mole ratio 18 of at least abo.it 14 of (1) an oxide of a first tetravalent element to (2) an oxide 19 of a trivalent element, pentavaÃerit eferyierit5 second tetravalent element which is different from said first tetravalent element or mixtLire thereof. The 21 molecular sieve is preferably predominantly in the hydrogen form, 23 Also provided is a process for!:r~iprc,ving the viscosity index of a dewaxed 24 product of waxy hydrocarbon feeds comprising cotitac:iinc~ a waxy hydrocas-bory #e-ed under isomerization dewaxing conditions wÃti=i a catalyst 26 comprising a crystalline molecular sieve havisig S Yi topology and ~[I-Ioie ratio 2 r of at least about 14 of (1) an oxide of a first tetravalent elenient to (2) an oxide 28 of ~.~ trivalerjt eÃeÃnent; pentavalent eleÃiierit; second tetravalent element which 29 is differeint from said first tetravalent element or mixture thereof. The molecular sieve is preferably predominantly Ãn, the hydrogen form.
32 Further provided by the present invention is a pracess for producing aCf:).F
33 i~ibe oil from a ~ Gr olefin feed coÃnpr;sÃng isomerizing said olefin feed under ~..
1 isomerization cond#tions over a catalyst comprising a crystalline riiofectjiar 2 sieve i~aving STI topology and a tiiole ratio of at adast about 14 of (1) a,i oxide 3 of a first tetravalent eIernerit to (2) an oxide of a trivalent element, pentavalent 4 eieÃr~ent, second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve may be 6 predomindntly sn the hydrogen ton. The catalyst r~~y contain at least one 7 GroL- p 'v``i ! I metaÃ.
9 Also provided is a processtor cataiytis.al.y dewax#i~~~ a hydrocarbon Dii feedstock boiling above about 350`F ;1 17 C; and containing straqht chain 11 and s;ightly Nranched chain hydrocarbons comprising contacting said 12 hydrocarbon oil ti-eds#ock in the presence of zidded hydrogen gas at a 1'3 hydrogen pressLire of about 15-3000 psi i0.103-207 1LIE'a' urider dewaxing 14 ^onditions wFth a catalyst c;omprisiÃic~ a crystaliine molerLilar sieve hauÃng STI
topology aÃid a mofe ratio of at least abotifi 14 of (1) an oxide of a first 16 tetravaierit eIesY~ent to (2) ati oxide of a trivalent element, per~~ava?ent eierr3e-M, I f second tetravalent element which is different frorr, said first tetravalent 18 element or mixture thereof. The molecular sieve may be predominantly in the 19 hydrogeti form. 1_.he catalyst may contain at least one Grr,~~~p Vlli metal. The catalyst may ~omprÃse a combination comprising a tirst catalysi comprisinc~
21 the molecular si:ee+e and at least one GrOLjP ViII metal, and a secor2d catalyst 22 comprising an aiurnir3osilÃcate zeolite which is MOre'sha~~ ~~~ec#Ne than the 23 molecular sieve of said first catalyst.
The present :nvention further provides a pr-ocess tor preparing a Iubricating oil 26 which corr~p~:~:s`
~~
28 hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to 29 obtairi a;i effluent cGniprising a hydro:;racie:ed oil; and 31 catalytically dewaxing said effluent comprising hydrocracked D;l at a 32 teÃytperaYLire of at least aboLÃt 40WF (2Ã341C) and at a pressure of from about 33 15 psig to about 3000 psig (0, 103 to 20,7 MPa gauge) in t~oe presence of t added hydrogen gas with acatafyst comprising a crystalline molecular sieve 2 having STI tapo!oqy and a mole ratio of at le-ast about 14 of (1) arà oxide of a 3 first tetrasralent element to (2) an oxide of a fir#vaEe,-it eIe~men;, pentavalerrt 4 element, second tetravalent eÃeryietit which is ditferent: from said first tetravalent eierrient or mixture thereof. The molecular sieve may be 6 predomiiiantly in the hydrogen torm. The catalyst may contain, at least orie 7 Group Vii! metal.
9 Aisoprovided is a process for :~omeri7atior, ~dewaxing a raffinate comprising contacting said raffinate ir3 the presence of added hydrogen under 11 isomerization dewaxing conditions wÃth a catalyst cornprisirig acrystaElÃne 1:2 MOieWiar sievf; having STI tr?poir3gy and a mole ratio of at least about 14 of 13 ( 1) an oxide of a first tetravalent element to (2) an oxide of a trivalent elemerit, 14 pentavalent element, second tetravalent element which is different from said first tetravalent element or mixtLÃre ttrereof: The raffinate may be bright 16 stock, and it-ie i-riolecufar sieve may be predominantly in the hydrogen form.
17 The catalyst may coritain at least one Group VIII metal, 19 In ac,c;ardatice with the present invention there is provided an improved process for separating gasses using a membrane containing a molecular 21 saeve, the improvement comprising using as the molecular sieve a crystalline 22 molecular sieve havirig STI topology and taavirrg a mole ratio of at least 15 of 23 (1) an oxide of a first Ãetrauqierit element to (2) ara oxide of atrivalent element, 24 ~entava(ent element, second tetravalent element which is different from said first tetravalent element or mixture thereraf: The molecular sieve can have a 26 rnale ratio of at ieEiss 15 of (1) siÃicon oxide to (2) an oxide selected from 27 aluminum axide, galliurn oxide: irur-s oxide, borort oxide; titar::Ãum vY:de-, indium 28 oxide arld miKtures thereof, 1`he rnc?iec:ular sieve has, after ca(cination, the 29 X-ray diffraction lines of Table II.
31 In accordance with t;'~~ present invention there is ~,~rovicled aprocsesa for 32 producing mett;y(arnir;e or dimethylamine comprising reacting methanol, 33 dimethyl ether or a mixture thereof and ammonia in the gaseous Phase in thc-, ;0-1 presence of a catalyst COMprising a crystalline i-nolecular sieve ha'ving STI
2 topology and haviÃig aÃriole ratio of 15 and greater of (1) an o:<ide of a t:i'`st 3 tetravalent e;ernent to (2i an oxide of a trivales,t element, pe:iiava[e-nt element, 4 second tetravalent efemeiit which is diffeÃent from said firstteiravalergt element or mixture thp-reof. The molerLslar sieve cari ih;~ve a mole ratio of 6 and greater of (1) silic:on oxade, to (2) an oxide seIected tÃori3 a!uminuill ox3de, 7 gallium oxide, iron oxide, borari oxide~: titanium oxÃde., indium oxide and 8 mixtures thereot: The molectÃiar sieve has, afte3= ca.lcination; the X-ray 9 diffraction lines of Tabl'e~r Ef'..
11 In accordance with ttiis invention, there is provided a process for the reduction 12 of oxides of nitrogen contained m a gas stream wherein said process 13 comprises contacting the gas stÃea~~i with a cristaliine moieWlar 'saev~
having `r~ STI topology and havinq a mole ratio of at least 15 of (1) an oxide of a first tetravalent eieÃnent to (2) an oxide of a trivalent element, pentavalent e6err3e.an:t 16 second tetravalent eÃement which is different froÃyi said first tetravalent 17 ele~~~ner,Ã or mixture thereof. The ~~~~~ecLelar sieve can have a mole ratio of at 18 least 15 of ; l} silicon oxide to (2) asi oxide seIer-ted frorri alurriiium oxide, ~ 9 gallium oxide. iron oxide, boron oxirte, tianlEIM oxide, sndiurli oxide and rnixtLires thereot, Th:e molecular sieve has, after calcination, the X-ray 21 diffraetioÃi lines of Tabile U. The, molecular sieve rTiay contain a metal or me-tal 22 ions (such as cobalt, copper, platinum, iron, chromium, manganese, nickel, 23 zinc, ianthanurn, palladium, r~~~iurri or mixtures thereo~ capable of catalyzing 24 the redy.Ãction of the oxides of nitro-gen, arid the process Ãanay be C-ond uc#ed in the presence of aexcess of ox~gp-ri. Ir, a preferred 26 embodiment, the gas streaÃr, is the exhaust stream (-"f an internal camt3ustion 27 engir;e.
29 This inventiori generally relates to a process for treating an engirle exhaust strearR~~ and in particLi(ar to a process for minimizing emissions during the cold 31 start operatior) of an engine. Accordingly, the present invention provides a 32 ~.~rocess faà trea sng a t:,old-start engirae. exhaust gas strea-ri r:..on#ainÃng 33 hydrocarbons and other pollutants rcons;sting of flowing said er3girle exhaust -t.l-, 1 gas s1rearrà over a Ã7ic~~ecLiiar s;eve bed which preferentiafly adsorbs the 2 hydracarbons over water to provide a flrst ex;naust stream; and flowing the 3 first exhaust gas strear;n over a catalyst to convert any residual hydrocarbons 4 aÃid other pofEutants contained in the first exhaust gas ,,~tream to innocuous prodLicts and pÃov#de a treated exhaust stream and discharging the treated 6 exhaust stream into the atmosphere, the molecular sieve bed characterireti in 7 that it comprises a crystalline molecular sieve having STI topology arid 11-laving 8 a mole ratio of at Ãmct 15 of (1) an oxide of a first tetravalent element to (2) aÃ-i 9 oxide of a trivalent eIrament,. pentavalent element, second tetravalent element which is different from said first tetravalent eiemer~t or mixture ther~of.
'Th~
11 moIe-cuIar sieve can have a mole ratio cif at least 15 of (1) siflc,ori oxideto (2) 12 ari oxide selected from aluminum QxÃde., gallium oxide, iron oxide, bor-or;
13 oxide, trtar:Eurn oxide, indium oxide and rniXlurp-s thereof. T'he molecular sieve 14 has the STi fraÃiievuork topology. It has, after calcination, the X-ray diffraction Iir:es of Tabfc-, II.
17 The preseÃit ir-tveritlon further provides such a process wiiere;n the engine #'s 18 ari internal combustion engine, IncIudÃrig automobile eriglr3es; which can be 19 fL,eled by a hydrocarbonaceoÃ.is fuel, 21 Also provided by the present invention is such a prc~ce-ss wherein the 22 molecular sieve has deposited oÃ3 st a rnetao selected trot-o the group 23 consisting of pIatlnr.,m; palladium, rhudiurn, ruther"iium, and mixtures thereof.
The present invention relates to a process for th,e production of light o:ef~~s 26 comprising olefins having frorÃz 2 to 4 carbon atram;~ per molecule frorn a,-;
2.7 oxygenate feedstuck. The process comprises passing the oxygenate 28 feedstc~eX to an oxygenate conversion zone containing a molecular sÃ~ve.
29 catalyst to produce a lÃghi olefin stream.
31 :I.hus, in accordance with the present Ãr~verition there is provided a process for 32 the prodLiction of light olefins from a ft~edstock coÃTipi-isirag aRr oxygenate or 33 mixture of oxygenates, the proce,~5s comprising reactng the feedstock at.
n --1:~_ I effec..t?ve conditions over a catalyst c~n-liprp~ing a crystalline molecular sÃe"~e 2 having STI topology aAid havirig a P-nc}le ratio of at seasf 15 of (1) an oxide of a 3 first tetravalent element t-n (2) ar: ~~ide of a trivalent element, peritavaient 4 element, second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve can have a mole 6 ratio of at least 15 of (1) sÃiicon oxide to (2) an oxide selected from aÃurY~inurn 7 oxide, gallium oxide, iron oxide, boron, oxide, titanium oxide, indium oxide and 8 mixtures herec;f. The moIectilar sieve has, after calcination, the X-ray 9 diffraction liges of 'T'able Il.
DETAILED DESCRIPTION Gt=..(.HE INVENTION
13 The present invention comprises a moiecular sieve designated i3ereiii 14 "molectsiar sieve SSZ-75" or simply "SSZ.<75}r, i:=x 16 In preparing SSZ-75, a 17 dication is used as a structure directing agent ("SDA"), also known as a 18 crystallization template. The SDA useful for mzakifig SSZ-75 has the following 19 structure:
sr=
~ ... ~'~
~;' ~~. ({,.3'~ 2)4_-~__-__Ã~ ,~.
22 Tetra Ãt:eth,rier,e-9,4-bis-(N-metftyl pyrralidinium) dication 24 Thi~ SDA dication is ~~so)cÃat~d with anions (X-) which may be any anion that ;s riof detrimental to the forÃs~ate;,n oft~~ ~~Z-75. Representafive anions 26 mu;ude ha1ogen> e.g., fluoride, chloride, bromide and indide, hydroxide, 27 acetate, su3fate, tetraf~tior~~~orate, rõarbcaa;ylate, and the Iike.
Hydroxide is the 28 most preferred anion. The structure directing agent (~DA) may be used to 29 provide hydroxide ion. Thus, it :s beneficial to ion exchange, for exarr:ple, a haiide to hydroxide ion.
1 Thie tetra rnethylene-1;4-b is-(N-nnethyipyr:V id inÃu. rri) dicatior-i SDA
can be 2 prepared by a rnet.hod simi1ar to ttiat descÃibed in U.S. Patent No.
16 Because of their unique sieving characteristics, as well as their catalytic 16 proper-ties; crystalline moEecr:rlar sieves and zeolites are ~~pecially useful Ãn 17 applications such as hydrocarbori conversion, gas drying and separatÃon.
18 AlthoL,gh many different crystalline rnolecuiar sieves h:ave been disrl~~ed.
19 there is a continuing need for new molecular sieves with desirable properties for gas separation and dryÃng, hydrocarkaor? and cherniraal conversions, and 21 other applications, New molecular sieves may contain novel internal pore 22 architectures, providing erihanced selectivities in these processes.
26 The present invention is directed to a family of crystalline molecular sieves 27 with unique properties, referred to herein as"molecular- sieve SSZ 75,' or 28 simply "~~Z-75". SSZ-75 has the fr-ar-nework topology designated "STI" by 29 the~. IZA. Materials having the STI tcspology include naturally occurring stilbite and the zeniite designated T-NU-10: Stilbite is disclosed irR Breckr Zeolite 31 Molecular Sieves, 1984, Robert E. Kr:eger Publishing Company where it is 32 reported ttlat strlbfir~ has a typical sili ;afalun-r#na mole ratio of 5,2_ Tl'1U-10 is 33 reported in Hong et a~., J. AM. Ci-IEM, SOC. 2004, 126, 5817-5826 as having 34 a silica/alurriir-ra mole ratio of about 14. Wheri attp-rnpts were rriade to .-g-1 increase the sifÃca:raIurnina rri01e ratio in trie product; rrraterials ott7er than 2 'i'NU-10 were produced.
4 In accordance with the present invention there is provÃdeda crystalline molecular sieve having STI topology and having a mole ratio of at ieast 15 of 6 (`~) an oxide of a first tetravalent eIems-nnt to (2) an, oxide of a trivafent element, 7 pentavalent element, second tetravalent element which is different from said 8 first tetravalent element or MixtÃ.Ãre thereof. The SSZ-75 molecular sieve has, 9 after calcination., trse< Y-ray diffrac-tion lines of Table I'.I. It should be noted trla1 the phrase ' moIe ratio of at, least. 15' includes the case where there is no 11 oxide (2), Ã.e., the mole ratio of oxide t1i to oxide "2) is ir{tinity:. In that case t2 the mole-cuiar sieve is comprise~.t or essentially afl sificon oxide.
14 The present iriven#ioÃ) also provides aMstalline molecular sieve having STI
topology and tiavirig ~.~ rnole rafi#o of at least 15 of (1) silicon oxide to (2) an 16 oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide;
17 titanium oxide, indium oxide and mixtures thereof. The SSZ-75 moler}Lalar 18 sieve has, after calCÃnatian, the X-ray diffraction lit~~s of Table Il.
The present invention fuÃther, provides such acÃ-ystaliine molecular sieve 21 having a composition comprising, as synthesized and in the anhydrous state, 22 in terms of rnc:31e ratios the tolEritivirÃg:
24 SiO2 / XIO~ at least 15 (i,e., 15 -- infinity) SiOz 0-0. C]a 26 Q 1302 0.02 - 0.08 27 F f sioz 0:01--- 0.04 29 wherein X is aluminum, gaftium, iron, boron, titanium, indium and mixtures tiiereofr c is I or 2, d is 2 when c is 1(Ã.e., W is tetravalent) or d is 3 or awt=ien 31 c is 2 (i.e,, d is 3 when VV is trivalent or 5 wfieri 17V is perktaualent);
M is an 32 alkali metal cation, alkaline earth metal cation or mÃxtures tE;ereot, ri is the -1 valenc;e of M (Le;, 1 or 2); Q is a tetrarriethyierre-'i,4-bis-(N-niet.1-,yI
2 pyrralidÃniur;s) dieation and F is fluoride.
4 Also provided ir) accordance with the present in-ventÃon is a method of preparing a crystaffine material, said method comprising contacting under 6 crystallizatiors conditions a source{sJ of (1) silacon oxide, (2) a source(s) of 7 aIumÃntim oxide, gallium oxide, iron oxide, boron oxÃde, titanium oxide, indium 8 oxide and mixtures thereof, (3) fitiorÃ~e bns arrd (4) a 5tructtire directing agent 9 comprising a te,b:r.ame'thylene--1,4-bis--(N-methYiPyrrolidinÃurri) ciicatpon. Ti-le present Ãnventiori incftides srich a method wherein the cr-ystal?ir:e Ã~n~.ater4 has -`i 1 STI topology and wh:erein ttie moiecri1ar sieve has, after calcination, the X...ray 12 diffraction lines af'Fab1e !!.
14 The preserit invention inciudes such a method of preparing a crystalline material which Lrses a reaction rraixttir-e corriprising (in terms of mole ratios), 16 the foi:~.~wing:
18 Smt?2 1 x3o:; at least 15 (Ã.e;, 15 T infinity) 19 ON. rF SiO2 0.20-0.80 Q l Si02 0.20--= 0<8Q
21 M2;1 / Si02 0 - 0.04 22 t-i20 1 SÃ02 2-- 10 23 HF / SiO2 0.20 --- 0:80 wherein X is aluminum, gafliurii, iro-s~, boron, t;taniurn, irdium and mixtures 26 thf:rp-of, a is 1 or 2, b 3s 2 when a is 1 (i.e., W is. xetraualent); b is 3 wheri a is 2 27 (i.e,;W is trivalent), M is an aIicaIi metal cation, alkaline earlh metal cation or 28 mixtures thereot; n is tt~evaience of M ;i.e., I or 2}', and Q is a 29 tetrar~e"Lhvie ne--1;4--bisrt,N -rnefiiyl~y rrolad in iu r?n) dication, 31 ir~ accordance with the present inverrtior: them is provided a process for 32 .;onver`tÃng hydrocarbons comprising contacting a hydro; a;rk.onace<aus feed at 33 hydrocarbon converting conditions with a catalyst corrit-rr'lsarÃg a crystalline ^
.,,g ..
1 molecular sieve having STI topology and having a mole ratio of at least 15 of 2 (1) an oxide af a first tet~ava;ent element to (2) an oxide of a trivalent Clement, 3 pentavalerit element, second tet:~avaÃent elemer?; which is ~iffp-rent from said 4 f:rst tetravaient element or Ã'nixture thereot: SSZ-_'rz~ ~~~ ~fter ;
aIcination, k~e X..ray diffraction lines of 't=ab!e Il, la should be noted that the phÃase ;'Mol~
6 ratio of at least 1a" includes the case where there is no oxide (2), i.e., the 7 mole ratio of oxide~ (1) to oxide (2) is infinity. In that case the molecular si~ve, 8 i~ ~omprised of essentially alt silic ori oxide. The molecular sieve may be 9 predominantly in the hydrogen forrr,- It may also be 4ribstant:Ãally free of acidity.
12 1~i_rrl:hPr provided by the present invention is a hydrocracking process 13 comprising corrtactirig a hydrocarbon feeetstoci': under hydrocracking 14 conditions with a catalyst coÃnpr;sing the molecular sieve of this invention, preferably predominantly in the hydrogen forrn.
17 Also iriclLided iri this invention is a process for increasing the octaÃie of a 18 liydrocarbnn feedstock to produce a product having an increased aromatics 119 content comprming contacting a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range 21 above about 401G and less than about 2001,C. L,nder aromatic conversion 22 conditions with a catalyst comprising the molecular sieve of this invention 23 i-i-iar~~ substantially free of acidity by neutralizing said mol~cular sieve with a 24 basic rrietal. Also provided in this invention Ã~ such a process wherein the molecular sieve contains a GroÃ.;p VI1l metal component.
27 Also provided bythe present invention #sa catalytic cracking process 28 comprising contacting a hydrocarbon feedstock in ~-i rf.action zone under 29 catalytic cracking conditions in the absence of actded hydrogen with a catalyst cor r*pÃ:sÃnq the molect.Ãlar sieve of this invention, preferably predominantly in 31 thehydregen #orm. Also irrducled in this iÃiveiition is such a catalytic c,ackinq 32 process where4Ãi the catalyst ~dciitionall~ oorrip;Ãses a large pore crystaliline 33 cracking t,omponent.
2 This in;rentior, further provides an isomerization process for isomerizing Cd to 3 C7 hydrocarbons, compa-isÃn.g contacting ~.~ f~ed ti~.~vring norrnal and slightly 4 branched C4 tG' Cr hydrocarbons under isomerezir*g conditions with a catalyst campris3ng the r-riolecLÃIar sieve of this invention, preferably predorÃ-Ãinanfty in 6 the hydrogen form. The maÃec.u1ar sieve may bm impregnated with at least 7 one Gr~~~p Viif metai: preferably platirÃum. The ;~~tailyst may be- calcined in a 8 steam/a:Ã niixture at an elevated temperature after impregnation of the GrmÃp 9 JIII metal.
1 1 Also provided by the present Ãnventnn, is a process for alkylating ari aror7eaiic 1'a:.' hydrocarbon which comprises contacting under aiiÃyiation conditions at least a 13 molar excess of an aromatic hydrocarbon with a C? tO C20 oÃefÃn under at least 14 pa:-tial 3iquid phase conditions @nd in the preserace of a catalyst cos-nprising thp-molecular ~~~ve. of this invention, preferably predominantly in. the hydrogen 16 form, The olefin may be a C;; to C.4 o:efiÃ:Ã, and the aromatic hydrocarbon and 17 olefin may be present in a molar ratio of about 4:1 to aboLÃt 20:1, respectively.
18 The aromatic hydÃoc;arbor) may be selected from the group consisting of 19 ber~zeÃie, toluene, ethysbenxene< xylene, naphthalene, r~aphthaiene derivatives, dimethyBnaphfhaier:e or mixtures thereot.
22 Ftirther provided in accordance with ttiis invenfion is a process for 23 transaikylating an aromatic hydrocarbori which comprises coritactir~g under 24 transalkylating conditions an aromatic hydrocarbori with a poiyalkyE
arornatiu hydrocarborà under at least partial liquid phase condÃtioris and in the presence 26 of a catalyst comprising the molecular sieve of this nventiont preferably 27 predominantly in the hydrogen form. The arornafiic hydrocarbon and the 28 polyalkyl aromatic hydrocarbon may be preseÃit iri a molar ratio of from about 29 1:1 to about 25: 1, respectively.
31 The aromat;c hydrocarbon may be selected from the group co^sistirÃg of 32 benzene, i`ol:aene, ethyibenzene, xylene, or mixtures thereof, and the polyalkyl 33 a,-ornafic iiydrocarborà may be a dialkyÃ.ber-zenfiu.
_.,.-.
2 Further provided by this invention is a process to convert paraffins to ? aroriiatic;s which comprises coritacting paraffins under oondÃtioiis which cause 4 paraffins to convert to aromatics with a catalyst comprlsi;ig. the molecular sieve of this invention, said catalyst comprising galiium, zin:, or a corr~~oi'md 6 Of gaiieUM Or Zir'c<;
8 Ir; accordance with this invention there is also provided a pr-ocress for 9 wsomerizing olefins comprising contacting said olefin :,ender candi.sonswhich cause isc+mer3zation of the 6efin with aCat@iyr:~t COMpriSing ::hlw molecUlar 11 sieve of this invention, 14 Further provided ir, accordance with this #nventirrq ;:s a process for isomerizing 14 an Ã~~merizatEon feed comprising an aromatic G8 stream of xylene isomers or mi~ture~s of xylene isomers and othyfbenzene, wherein a more nearly 76 equiIibrium ratio of ar~~o-, rneta- aia-id para-xyier;e:; is obtained, saifl process 17 comprising coritactbng said feed utider isomerizaon conditions with a catalyst 18 comprising the molecular sieve of this invenbon.
Ttie present invention fu Ãlher :provides a process for oligomerizing oiefins 21 comprising contacting ar> olefir~ feed under oligcarnerizatiOn conditioi1s with a 22 catalyst comprising the molecular sieve of #riis irivention.
24 .1"his iriventioii also provides a process for cotiveri:3~~ ~xygen.ated hydrocarbons cornprisi~~g contacting said oxygenia:ed hydroc-arbu~l with ~.a 26 catalyst cornprising the moiecu1ar sieve of this,nrention under condrtions to 27 produce liquid products. The oxygenate~,d hydrocarbon riiay be a lower 28 alcohol.
Furttie,- provÃdc-d in accordance with the present invention is a process for ti=~p-31 producfio:i of liigher mo(ecu#ar wc-Ãgh'r hydrocarbons from lower rrioieca~~~at 32 weigtai: hydrocarbons ; omprisirig thc- steps of:
~ (a) introducing ifizo a reactio3i zone a lower molecular weight 2 i'-:ydroc:artyon-containing gas and contactirig said gas in said ~..~ zone rander C2h hydrocarbon synthesis conditions with the 4 catalyst and a metai or meiaI c,ompoÃjr7d ~apab6; of convertÃng the. lower moI~cWar weight hydrocarbon to a higher molecular 6 weight hydrocarbon; and 7 (b) withdrawing from said reaction zone a higher molecular weigilt 8 hydrocarbon-contairsÃng stream.
The present invention further provides a process for hydrogeriating a 11 hydrocarbon feed ~onita#ning unsaturated hydrocarboris, the ~~~oc~~~
12 comprising contacting the feed and hydrogen rinder wondations which ca;Ase 13 hydrogenation with a ca#Wysti comprising the molecular sieve af this invention.
14 The catalyst can also contain metals, salts or complexes wherp-in the metal is selected frc:m the group consisting of piatmnumJ paIfaditim, rhodiLim, irid;ufri or 16 com~iriatÃons thereof, or the group consisting of nic kel; molybdenum, Cobai:, 17 tungsten, titanium, chr'ocr3i.um, vasiadium, rhen3um, mariganes~ and 18 combinations thereof.
The present invention also provides a catalyst cCaiiiiaosÃticÃn for prornsatin;
21 polymer3zation of I-otf >iis, said composition cor~~ w.-_--.iT-q 22 (A) a cÃystailirie rriolecuiar sieve having a male ratio of at ieast 15 of 23 (1) an oxide of a first tetravalent element to (2) an oxide of a 24 trivalent eIement, pentavaleiit element, second tetravalent elerraer-ii whit ii ;s different from said first tetravalent element or 26 mixture thereo#' and i~awng, after calcination, the X-ray 27 diffraction lines of Table 11; and 29 (B) an orgaÃiotitanium or organochromium compound.
31 Also provided is a process for polymerizing 1 -alefins, which prorc-ss ;3 2 comprises contacting 1-olefin monomer with a catalytically effective amount of 33 a catalyst composition comprising 2 (A) a crystaiiii~e molecular sieve having a mole ratio of at ieast 15 of 3 ('11) aii oxide of a first tetravaie~,nt element to (2) an oxide of a 4 trivalent e_emerit, pentavaÃenf element, second tetravalent element ~~rvhr.,h is different from said first tetravalent element or 6 mÃx'tLsre thereof and having, after calcination, the X-ray 7 diffract>on lines of Table II; and 9 (B) ari organo-Aitaniurri or organochromium r_orripound.
1 I under polymerization conditions which include a temperature and pressure 12 suitabie, for iriitiating and promoting thÃ: polymerizafiior, rearation.
The 1-oIeftn 13 may be ethyierie.
~~~he present invention further provides a dewaxing process comprising 16 contacting a hydrocarbon feedstock under dewaxing conditions with a catalyst 17 comprising a crystalline molecular sieve having STI trapoiogy and a mole ratio 18 of at least abo.it 14 of (1) an oxide of a first tetravalent element to (2) an oxide 19 of a trivalent element, pentavaÃerit eferyierit5 second tetravalent element which is different from said first tetravalent element or mixtLire thereof. The 21 molecular sieve is preferably predominantly in the hydrogen form, 23 Also provided is a process for!:r~iprc,ving the viscosity index of a dewaxed 24 product of waxy hydrocarbon feeds comprising cotitac:iinc~ a waxy hydrocas-bory #e-ed under isomerization dewaxing conditions wÃti=i a catalyst 26 comprising a crystalline molecular sieve havisig S Yi topology and ~[I-Ioie ratio 2 r of at least about 14 of (1) an oxide of a first tetravalent elenient to (2) an oxide 28 of ~.~ trivalerjt eÃeÃnent; pentavalent eleÃiierit; second tetravalent element which 29 is differeint from said first tetravalent element or mixture thereof. The molecular sieve is preferably predominantly Ãn, the hydrogen form.
32 Further provided by the present invention is a pracess for producing aCf:).F
33 i~ibe oil from a ~ Gr olefin feed coÃnpr;sÃng isomerizing said olefin feed under ~..
1 isomerization cond#tions over a catalyst comprising a crystalline riiofectjiar 2 sieve i~aving STI topology and a tiiole ratio of at adast about 14 of (1) a,i oxide 3 of a first tetravalent eIernerit to (2) an oxide of a trivalent element, pentavalent 4 eieÃr~ent, second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve may be 6 predomindntly sn the hydrogen ton. The catalyst r~~y contain at least one 7 GroL- p 'v``i ! I metaÃ.
9 Also provided is a processtor cataiytis.al.y dewax#i~~~ a hydrocarbon Dii feedstock boiling above about 350`F ;1 17 C; and containing straqht chain 11 and s;ightly Nranched chain hydrocarbons comprising contacting said 12 hydrocarbon oil ti-eds#ock in the presence of zidded hydrogen gas at a 1'3 hydrogen pressLire of about 15-3000 psi i0.103-207 1LIE'a' urider dewaxing 14 ^onditions wFth a catalyst c;omprisiÃic~ a crystaliine molerLilar sieve hauÃng STI
topology aÃid a mofe ratio of at least abotifi 14 of (1) an oxide of a first 16 tetravaierit eIesY~ent to (2) ati oxide of a trivalent element, per~~ava?ent eierr3e-M, I f second tetravalent element which is different frorr, said first tetravalent 18 element or mixture thereof. The molecular sieve may be predominantly in the 19 hydrogeti form. 1_.he catalyst may contain at least one Grr,~~~p Vlli metal. The catalyst may ~omprÃse a combination comprising a tirst catalysi comprisinc~
21 the molecular si:ee+e and at least one GrOLjP ViII metal, and a secor2d catalyst 22 comprising an aiurnir3osilÃcate zeolite which is MOre'sha~~ ~~~ec#Ne than the 23 molecular sieve of said first catalyst.
The present :nvention further provides a pr-ocess tor preparing a Iubricating oil 26 which corr~p~:~:s`
~~
28 hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to 29 obtairi a;i effluent cGniprising a hydro:;racie:ed oil; and 31 catalytically dewaxing said effluent comprising hydrocracked D;l at a 32 teÃytperaYLire of at least aboLÃt 40WF (2Ã341C) and at a pressure of from about 33 15 psig to about 3000 psig (0, 103 to 20,7 MPa gauge) in t~oe presence of t added hydrogen gas with acatafyst comprising a crystalline molecular sieve 2 having STI tapo!oqy and a mole ratio of at le-ast about 14 of (1) arà oxide of a 3 first tetrasralent element to (2) an oxide of a fir#vaEe,-it eIe~men;, pentavalerrt 4 element, second tetravalent eÃeryietit which is ditferent: from said first tetravalent eierrient or mixture thereof. The molecular sieve may be 6 predomiiiantly in the hydrogen torm. The catalyst may contain, at least orie 7 Group Vii! metal.
9 Aisoprovided is a process for :~omeri7atior, ~dewaxing a raffinate comprising contacting said raffinate ir3 the presence of added hydrogen under 11 isomerization dewaxing conditions wÃth a catalyst cornprisirig acrystaElÃne 1:2 MOieWiar sievf; having STI tr?poir3gy and a mole ratio of at least about 14 of 13 ( 1) an oxide of a first tetravalent element to (2) an oxide of a trivalent elemerit, 14 pentavalent element, second tetravalent element which is different from said first tetravalent element or mixtLÃre ttrereof: The raffinate may be bright 16 stock, and it-ie i-riolecufar sieve may be predominantly in the hydrogen form.
17 The catalyst may coritain at least one Group VIII metal, 19 In ac,c;ardatice with the present invention there is provided an improved process for separating gasses using a membrane containing a molecular 21 saeve, the improvement comprising using as the molecular sieve a crystalline 22 molecular sieve havirig STI topology and taavirrg a mole ratio of at least 15 of 23 (1) an oxide of a first Ãetrauqierit element to (2) ara oxide of atrivalent element, 24 ~entava(ent element, second tetravalent element which is different from said first tetravalent element or mixture thereraf: The molecular sieve can have a 26 rnale ratio of at ieEiss 15 of (1) siÃicon oxide to (2) an oxide selected from 27 aluminum axide, galliurn oxide: irur-s oxide, borort oxide; titar::Ãum vY:de-, indium 28 oxide arld miKtures thereof, 1`he rnc?iec:ular sieve has, after ca(cination, the 29 X-ray diffraction lines of Table II.
31 In accordance with t;'~~ present invention there is ~,~rovicled aprocsesa for 32 producing mett;y(arnir;e or dimethylamine comprising reacting methanol, 33 dimethyl ether or a mixture thereof and ammonia in the gaseous Phase in thc-, ;0-1 presence of a catalyst COMprising a crystalline i-nolecular sieve ha'ving STI
2 topology and haviÃig aÃriole ratio of 15 and greater of (1) an o:<ide of a t:i'`st 3 tetravalent e;ernent to (2i an oxide of a trivales,t element, pe:iiava[e-nt element, 4 second tetravalent efemeiit which is diffeÃent from said firstteiravalergt element or mixture thp-reof. The molerLslar sieve cari ih;~ve a mole ratio of 6 and greater of (1) silic:on oxade, to (2) an oxide seIected tÃori3 a!uminuill ox3de, 7 gallium oxide, iron oxide, borari oxide~: titanium oxÃde., indium oxide and 8 mixtures thereot: The molectÃiar sieve has, afte3= ca.lcination; the X-ray 9 diffraction lines of Tabl'e~r Ef'..
11 In accordance with ttiis invention, there is provided a process for the reduction 12 of oxides of nitrogen contained m a gas stream wherein said process 13 comprises contacting the gas stÃea~~i with a cristaliine moieWlar 'saev~
having `r~ STI topology and havinq a mole ratio of at least 15 of (1) an oxide of a first tetravalent eieÃnent to (2) an oxide of a trivalent element, pentavalent e6err3e.an:t 16 second tetravalent eÃement which is different froÃyi said first tetravalent 17 ele~~~ner,Ã or mixture thereof. The ~~~~~ecLelar sieve can have a mole ratio of at 18 least 15 of ; l} silicon oxide to (2) asi oxide seIer-ted frorri alurriiium oxide, ~ 9 gallium oxide. iron oxide, boron oxirte, tianlEIM oxide, sndiurli oxide and rnixtLires thereot, Th:e molecular sieve has, after calcination, the X-ray 21 diffraetioÃi lines of Tabile U. The, molecular sieve rTiay contain a metal or me-tal 22 ions (such as cobalt, copper, platinum, iron, chromium, manganese, nickel, 23 zinc, ianthanurn, palladium, r~~~iurri or mixtures thereo~ capable of catalyzing 24 the redy.Ãction of the oxides of nitro-gen, arid the process Ãanay be C-ond uc#ed in the presence of aexcess of ox~gp-ri. Ir, a preferred 26 embodiment, the gas streaÃr, is the exhaust stream (-"f an internal camt3ustion 27 engir;e.
29 This inventiori generally relates to a process for treating an engirle exhaust strearR~~ and in particLi(ar to a process for minimizing emissions during the cold 31 start operatior) of an engine. Accordingly, the present invention provides a 32 ~.~rocess faà trea sng a t:,old-start engirae. exhaust gas strea-ri r:..on#ainÃng 33 hydrocarbons and other pollutants rcons;sting of flowing said er3girle exhaust -t.l-, 1 gas s1rearrà over a Ã7ic~~ecLiiar s;eve bed which preferentiafly adsorbs the 2 hydracarbons over water to provide a flrst ex;naust stream; and flowing the 3 first exhaust gas strear;n over a catalyst to convert any residual hydrocarbons 4 aÃid other pofEutants contained in the first exhaust gas ,,~tream to innocuous prodLicts and pÃov#de a treated exhaust stream and discharging the treated 6 exhaust stream into the atmosphere, the molecular sieve bed characterireti in 7 that it comprises a crystalline molecular sieve having STI topology arid 11-laving 8 a mole ratio of at Ãmct 15 of (1) an oxide of a first tetravalent element to (2) aÃ-i 9 oxide of a trivalent eIrament,. pentavalent element, second tetravalent element which is different from said first tetravalent eiemer~t or mixture ther~of.
'Th~
11 moIe-cuIar sieve can have a mole ratio cif at least 15 of (1) siflc,ori oxideto (2) 12 ari oxide selected from aluminum QxÃde., gallium oxide, iron oxide, bor-or;
13 oxide, trtar:Eurn oxide, indium oxide and rniXlurp-s thereof. T'he molecular sieve 14 has the STi fraÃiievuork topology. It has, after calcination, the X-ray diffraction Iir:es of Tabfc-, II.
17 The preseÃit ir-tveritlon further provides such a process wiiere;n the engine #'s 18 ari internal combustion engine, IncIudÃrig automobile eriglr3es; which can be 19 fL,eled by a hydrocarbonaceoÃ.is fuel, 21 Also provided by the present invention is such a prc~ce-ss wherein the 22 molecular sieve has deposited oÃ3 st a rnetao selected trot-o the group 23 consisting of pIatlnr.,m; palladium, rhudiurn, ruther"iium, and mixtures thereof.
The present invention relates to a process for th,e production of light o:ef~~s 26 comprising olefins having frorÃz 2 to 4 carbon atram;~ per molecule frorn a,-;
2.7 oxygenate feedstuck. The process comprises passing the oxygenate 28 feedstc~eX to an oxygenate conversion zone containing a molecular sÃ~ve.
29 catalyst to produce a lÃghi olefin stream.
31 :I.hus, in accordance with the present Ãr~verition there is provided a process for 32 the prodLiction of light olefins from a ft~edstock coÃTipi-isirag aRr oxygenate or 33 mixture of oxygenates, the proce,~5s comprising reactng the feedstock at.
n --1:~_ I effec..t?ve conditions over a catalyst c~n-liprp~ing a crystalline molecular sÃe"~e 2 having STI topology aAid havirig a P-nc}le ratio of at seasf 15 of (1) an oxide of a 3 first tetravalent element t-n (2) ar: ~~ide of a trivalent element, peritavaient 4 element, second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve can have a mole 6 ratio of at least 15 of (1) sÃiicon oxide to (2) an oxide selected from aÃurY~inurn 7 oxide, gallium oxide, iron oxide, boron, oxide, titanium oxide, indium oxide and 8 mixtures herec;f. The moIectilar sieve has, after calcination, the X-ray 9 diffraction liges of 'T'able Il.
DETAILED DESCRIPTION Gt=..(.HE INVENTION
13 The present invention comprises a moiecular sieve designated i3ereiii 14 "molectsiar sieve SSZ-75" or simply "SSZ.<75}r, i:=x 16 In preparing SSZ-75, a 17 dication is used as a structure directing agent ("SDA"), also known as a 18 crystallization template. The SDA useful for mzakifig SSZ-75 has the following 19 structure:
sr=
~ ... ~'~
~;' ~~. ({,.3'~ 2)4_-~__-__Ã~ ,~.
22 Tetra Ãt:eth,rier,e-9,4-bis-(N-metftyl pyrralidinium) dication 24 Thi~ SDA dication is ~~so)cÃat~d with anions (X-) which may be any anion that ;s riof detrimental to the forÃs~ate;,n oft~~ ~~Z-75. Representafive anions 26 mu;ude ha1ogen> e.g., fluoride, chloride, bromide and indide, hydroxide, 27 acetate, su3fate, tetraf~tior~~~orate, rõarbcaa;ylate, and the Iike.
Hydroxide is the 28 most preferred anion. The structure directing agent (~DA) may be used to 29 provide hydroxide ion. Thus, it :s beneficial to ion exchange, for exarr:ple, a haiide to hydroxide ion.
1 Thie tetra rnethylene-1;4-b is-(N-nnethyipyr:V id inÃu. rri) dicatior-i SDA
can be 2 prepared by a rnet.hod simi1ar to ttiat descÃibed in U.S. Patent No.
5,166,111, 3 issued NoveÃ~iber 24, 1992 to Zones et a1., which discloses a method for 4 preparing a bisi1,4-dÃa:zotiiabi{:,ycIo[2.2:2]alpha, omega alkane compoLind, or U.S. Patent No, 5,268,161, assued December 7, 1993, which discloses a
6 method for preparing 1,3,3,8,8-pentamethylN3-azor,,iabicycEo[3.2.1]octane
7 cation_ U.S. Patent No. 5,166;111 and U,S. Patent No. 5,268,161 are,
8 incorporated by reterencYe herein mti ttieiY entÃrety>
9 In general. SSZ-75 is prepared by contacting (1) an active source(s) cif sÃlac:on 11 oxide, and (2) an active source(s) of aluminum cjxide, gaÃliuii) oxide, iron 12 oxide, b:aroÃi -oxide, tilaÃ3iuÃri oxide, iÃ:c1iurn oxide and rnixtÃares thereof with tine 13 tetramethyEene-1,4-bis-(eti1LLmethylpyrrolidiÃiii-FÃr~) dicraiic~~~ SDA in the presence 14 of fluoride ion.
16 ~~~-75 is prepared from a re~action mix:ture comprising, Ãri terms of mole 17 ratios, the fc+ilowing:
ReactÃor, Mixture 22 Si02 , ' XaOb at &east 15 (i.e., 1 5 - intinity) 23 OH- / Si02 O:20 -- 0,80 24 Q/ Si02 0.20-0.80 ~~2.1ta 1Si02 0 --- 0.04 26 1120 ,+ Si02 2- 1 0 27 HF / Si02 0..20 w 0.80 29 where X is aluminum, gi@fhum, iron, boron, titanium, indium and ÃnÃxlures thereof, a is I vÃ, 2, b is 2 whesi. a is I {i.e., W is tet~avaierÃt}; b is 3 when a is 2 31 (Ã,e,, W is trivalent), NA is an alkali metal cation, alkaline earth metal cation or 32 nlixtLires thereof; n ii the va1er~~~ of M (i.e., 1or 2): Q:s a tetramethylene-1,4..
33 bis-(N-metr~,yipyrYolÃdiniurn) dication and F is fluoride.
1 As noted ~bove.; the &0, I XO4 moIe ratio in the reaction mixture is ~~ 15.
2 Th:is means that the SiO2 2 / X~O~, mole ratio carr, be Ãrwfimty, #.e,, there is Ã~~ ~,O,~
3 Ãrt the#-eaction m:xtÃ,Ãre. TtiÃs results in a version of SSZ-75 that is essentially 4 aIB silica. As~ 4:sed herein, "essentiaily a1Ã silic.om oxidetl or "essertia`iy a11_ siIb~a" Ãiiear#s that the molecular sieve's crystal szructt3re _s comprised of only 6 silicon oxide or :s comprised of sificon oxÃde ar;d only trace amourjts .t~
other ~F M;
7 oxides, such as aluminum { oxide, which # may be introduced as im#~#t#es in the 8 source of silicon oxide, ~
In practice, 5SZ-75 is -repared by a prncp5s compr;s3Ã~~~
~~
12 (~) prp-paring an aqueous solution containing (1) a soLir~~(~) of 1 s#IÃwo## oxide, (2) a source(s) of 4~l~arr~Erlurn oxide;
14 galiiL:#m oxide, iron oxide, boron oxide, fitanjum oxide, indiLim oxide asid mixtures thereof, (3) a source of fikioridc- ion and (411 a 16 tefrar-raet~~yleÃ-ie-1,4-bis-(N-- r~,~etliylpyrrolidir`ium) dication 17 having an anionic coLi#iterion which, is not detrimenta? tca the 18 formation of SSZ- 75;
19 (b) maintaining the aquec~Lis solution under conditions sufficient to form crystals of SSZ-75; and'.
21 (c) reC.overirig the crystal~ of ~~~-75.
23 The reactior, mixture is maintained at an elevated temperature Lin;il the 24 crystals of the SSZ-75 are formed. The hydrothermal crystallization is usually 2 15 conducted under autogenous pressure, at a temperature bettiueen "1 00"C
and 26 200*1C.'. Pref,;rabfy between 135'-~ and ~~~ C-, The crysttial4ixatior;
period ;S
27 typically greater than 1 day and preferably from about 3 days to about 28 20dayrs. The moleoula#, sieve may be prepared using miid stirring or 29 agitation.
31 Dtià Ãng the hydrothermal wrystaÃIizatÃon step, the., S5Z-75 c#^istals can be 32 allowed to r#tÃcIeate spontaneously from the reaction mrx#uro. The use of 33 SSZ-75 rr", tai~ ~~ seed mater#aI can be advanÃageous m decreasang the t#Ãlie j5..
1 r~ecessary for complete crystallization to occur. In addit.km, seeding Cai lead 2 to an Encreased ptÃr;ty o: tÃ~~ prodtact ob#a:r~ed by promoting the narleation 3 andior fo~~cTiation of SSZ-7 5 over- ar:y uridasir~d pÃ-,ases, When used as 4 seeds, SSZ-75 crystals are added ir, an arri:ount between 0. ~ and 10% of the weight of tÃ-ie first tetravalent element oxide, e.g. silica, used in the reaction 6 mixture.
r, 8 Once the molecular sieve crystals have fo~rmed, the solid product is separatecii 9 from the reaction mixture by standard mechanical separation techniques suchi as filtration, The Crystals are water-wastied and then dried, e.g., at 90 C to 11 1 5VC for from 8 to 24 hours, to obtain the as-synthesized SSZ-75 ;xrystals, 12 The drying step can be performz=:d at atmospheric pressure or ufider vacuum.
14 ~SZ-76 a:~~ prepared has the X-ray d?tracatÃor, lines of :-f-abia 1 t:1e$ow. SSZ-75 has a c:oriipossteon, as synthesized (Ã.eõ prior to ,emavall of the SDA from the, 16 SSZ--76) arid in the anhydrous state, comprising the foÃlowing iin term:s of 17 mole ratiosr:
19 sÃo:~,' X10i at Ãeast 15 (t.e., 119 - irifiFnÃty) m2;n ! sioy 0-0.0::3 21 Q 1 Si02 0.02 - 0.08 22 F / Si~`~z O_01 -- 0.04 24 wherein X is aÃumir~um; galfium, Ãrori, bori)rl, tita=iÃum, andium and mixtures thereof, c is 'j or 2-1 d is 2 whesi c is 1 (i.e., W is tetravalent) or d is 3 or 5 wher, 26 c is 2 l .e.; d is 3 when W is trivalent or 5 wtier; W is pentava3enti, M
is an 27 aikali metal cation, alkaline ea:-th nnetaà cation or rr;ixtures thereof; n is the 28 valence of M (i.e:; 'à or 2); Q is a tetramet(iylene-.1t4-bis-(,N-methyÃ-29 pyrrolmdir7ium) dicatioti a,id F is fluoride..
31 SSZ-75 (whekher iri the as synthesized or c.aÃcined versÃon) has a SiOz r X, Od 32 rnoÃe ratio of at least 15 (i.e,, 15 - infinity), for exaE-Ã3ple 20 -infinity or 40 33 infinity.
~?-2 SSZ-75 has the STI frar-reworÃ~ ~~po~~gy, It is charaoteri.~~~ by its X ÃaY
3 diffraction pattern. SSZ-75, as-synthesized, has a crystafline wtrur-ture whose 4 X =dy powdeÃ- diffraction pattern exhibits the characteristic lines sh:own in 'I'abIc- 1.
8 As-Synthesized SSZ-75 __ - -------- ---- ....._..--2 Theta d s acina (Angstroms Rezative . ....... . .....
Intensity - - - -------- ------ ....... .............------------------ -- -------
16 ~~~-75 is prepared from a re~action mix:ture comprising, Ãri terms of mole 17 ratios, the fc+ilowing:
ReactÃor, Mixture 22 Si02 , ' XaOb at &east 15 (i.e., 1 5 - intinity) 23 OH- / Si02 O:20 -- 0,80 24 Q/ Si02 0.20-0.80 ~~2.1ta 1Si02 0 --- 0.04 26 1120 ,+ Si02 2- 1 0 27 HF / Si02 0..20 w 0.80 29 where X is aluminum, gi@fhum, iron, boron, titanium, indium and ÃnÃxlures thereof, a is I vÃ, 2, b is 2 whesi. a is I {i.e., W is tet~avaierÃt}; b is 3 when a is 2 31 (Ã,e,, W is trivalent), NA is an alkali metal cation, alkaline earth metal cation or 32 nlixtLires thereof; n ii the va1er~~~ of M (i.e., 1or 2): Q:s a tetramethylene-1,4..
33 bis-(N-metr~,yipyrYolÃdiniurn) dication and F is fluoride.
1 As noted ~bove.; the &0, I XO4 moIe ratio in the reaction mixture is ~~ 15.
2 Th:is means that the SiO2 2 / X~O~, mole ratio carr, be Ãrwfimty, #.e,, there is Ã~~ ~,O,~
3 Ãrt the#-eaction m:xtÃ,Ãre. TtiÃs results in a version of SSZ-75 that is essentially 4 aIB silica. As~ 4:sed herein, "essentiaily a1Ã silic.om oxidetl or "essertia`iy a11_ siIb~a" Ãiiear#s that the molecular sieve's crystal szructt3re _s comprised of only 6 silicon oxide or :s comprised of sificon oxÃde ar;d only trace amourjts .t~
other ~F M;
7 oxides, such as aluminum { oxide, which # may be introduced as im#~#t#es in the 8 source of silicon oxide, ~
In practice, 5SZ-75 is -repared by a prncp5s compr;s3Ã~~~
~~
12 (~) prp-paring an aqueous solution containing (1) a soLir~~(~) of 1 s#IÃwo## oxide, (2) a source(s) of 4~l~arr~Erlurn oxide;
14 galiiL:#m oxide, iron oxide, boron oxide, fitanjum oxide, indiLim oxide asid mixtures thereof, (3) a source of fikioridc- ion and (411 a 16 tefrar-raet~~yleÃ-ie-1,4-bis-(N-- r~,~etliylpyrrolidir`ium) dication 17 having an anionic coLi#iterion which, is not detrimenta? tca the 18 formation of SSZ- 75;
19 (b) maintaining the aquec~Lis solution under conditions sufficient to form crystals of SSZ-75; and'.
21 (c) reC.overirig the crystal~ of ~~~-75.
23 The reactior, mixture is maintained at an elevated temperature Lin;il the 24 crystals of the SSZ-75 are formed. The hydrothermal crystallization is usually 2 15 conducted under autogenous pressure, at a temperature bettiueen "1 00"C
and 26 200*1C.'. Pref,;rabfy between 135'-~ and ~~~ C-, The crysttial4ixatior;
period ;S
27 typically greater than 1 day and preferably from about 3 days to about 28 20dayrs. The moleoula#, sieve may be prepared using miid stirring or 29 agitation.
31 Dtià Ãng the hydrothermal wrystaÃIizatÃon step, the., S5Z-75 c#^istals can be 32 allowed to r#tÃcIeate spontaneously from the reaction mrx#uro. The use of 33 SSZ-75 rr", tai~ ~~ seed mater#aI can be advanÃageous m decreasang the t#Ãlie j5..
1 r~ecessary for complete crystallization to occur. In addit.km, seeding Cai lead 2 to an Encreased ptÃr;ty o: tÃ~~ prodtact ob#a:r~ed by promoting the narleation 3 andior fo~~cTiation of SSZ-7 5 over- ar:y uridasir~d pÃ-,ases, When used as 4 seeds, SSZ-75 crystals are added ir, an arri:ount between 0. ~ and 10% of the weight of tÃ-ie first tetravalent element oxide, e.g. silica, used in the reaction 6 mixture.
r, 8 Once the molecular sieve crystals have fo~rmed, the solid product is separatecii 9 from the reaction mixture by standard mechanical separation techniques suchi as filtration, The Crystals are water-wastied and then dried, e.g., at 90 C to 11 1 5VC for from 8 to 24 hours, to obtain the as-synthesized SSZ-75 ;xrystals, 12 The drying step can be performz=:d at atmospheric pressure or ufider vacuum.
14 ~SZ-76 a:~~ prepared has the X-ray d?tracatÃor, lines of :-f-abia 1 t:1e$ow. SSZ-75 has a c:oriipossteon, as synthesized (Ã.eõ prior to ,emavall of the SDA from the, 16 SSZ--76) arid in the anhydrous state, comprising the foÃlowing iin term:s of 17 mole ratiosr:
19 sÃo:~,' X10i at Ãeast 15 (t.e., 119 - irifiFnÃty) m2;n ! sioy 0-0.0::3 21 Q 1 Si02 0.02 - 0.08 22 F / Si~`~z O_01 -- 0.04 24 wherein X is aÃumir~um; galfium, Ãrori, bori)rl, tita=iÃum, andium and mixtures thereof, c is 'j or 2-1 d is 2 whesi c is 1 (i.e., W is tetravalent) or d is 3 or 5 wher, 26 c is 2 l .e.; d is 3 when W is trivalent or 5 wtier; W is pentava3enti, M
is an 27 aikali metal cation, alkaline ea:-th nnetaà cation or rr;ixtures thereof; n is the 28 valence of M (i.e:; 'à or 2); Q is a tetramet(iylene-.1t4-bis-(,N-methyÃ-29 pyrrolmdir7ium) dicatioti a,id F is fluoride..
31 SSZ-75 (whekher iri the as synthesized or c.aÃcined versÃon) has a SiOz r X, Od 32 rnoÃe ratio of at least 15 (i.e,, 15 - infinity), for exaE-Ã3ple 20 -infinity or 40 33 infinity.
~?-2 SSZ-75 has the STI frar-reworÃ~ ~~po~~gy, It is charaoteri.~~~ by its X ÃaY
3 diffraction pattern. SSZ-75, as-synthesized, has a crystafline wtrur-ture whose 4 X =dy powdeÃ- diffraction pattern exhibits the characteristic lines sh:own in 'I'abIc- 1.
8 As-Synthesized SSZ-75 __ - -------- ---- ....._..--2 Theta d s acina (Angstroms Rezative . ....... . .....
Intensity - - - -------- ------ ....... .............------------------ -- -------
10.04 ~~~O .~~..._ ------------------------------------------------------------- - -------- --:_-----..~ ................... _ -------- f 1,?. 15.1 6 ~~
---------------------------------- ------- - --------19.44 4.56 s ~ ................
-----.... ................ ____________ --------iV ~'~
2'1. 13 4.20 ---------------------------- --------22.36 3.97 tfs .......... ---- __- ~ .................. - ..._...
,~2.4~ ~ 3. 9~ C1f3 ............ ....___ ___ ___ .......................... __ -- ;
24. 19 3,68 w __ .....------------------------- .........
2~.=~.61 ~.35 w -- ---------------- --- --- _________ ...---3,13 w 28,49 ...------------- ......... ..... .__ --.
3U0 __ -------- 2~~ ~
___ _ _______________ ~__._........... __ Ã......
- 0: 1 13 The X-ray pa##ers-is provided are based or, a reiative intensity -scale i~n 14 which the strongest line in the X-ray paftern is assigned a vaIue of 1 W
VV(w,reak) is less than 20; M(medium) is ~~ehmeen 20 arid 40; S(strong) 16 is between 40 and 60; VS(very strong) is greater than 60.
1`r 18 Tabfe IA belawshows the X-ray powder r~iffÃ~~~~~~~t, lines for as-synthesized 19 SSZ--75 ÃriclLrdirig aciua; r-c-latdve iniensÃt#es, TABLE IA
2 As-Synthesized SSZ-75 --- ..... -----. _ ._.. ____- ----- _____________ Relative int~carated 2 Theta tr~~..stroms 'y ....................... l#?tenslt - ---------------------=
-------------------8.98 7 9.84 10.04 Ã3. t30 100 1`~;~..24 6.68 7 1419 6.24 4 17.17 5.16 13 19.44 4:56 47 20,01 4A3 2 20.17 4.40 7 21,13 4.20 2111 22.36 3.97 84 22.49 3.95 38 24.19 3.68 12 26:13 3.41 7 ~ ~
26.61 3,:35 28.49 3.13 18 29.31 3.04 10 30.20 30 30.30 2.95 7 31,94 2.80 2 32.12 2.78 1 32.61 2.74 3 33,13 2.70 4 33,59 2.37 6 :34.86 2.57 7 35.13 2.55 5 35.75 2.51 6 C,15 2.46 2 36,69 2.45 1 37.19 2A2 .~
...... .... , ....... .....~
*
7 After caicination, the K--Ã~~ powder d;ttract=on patierÃi for SSZ-75 exhÃbmts the 8 charac.teristic lines sh~owri :n Table il beIow.
~
2 `i~~BLE li 3 Ca#caned SS~-75 ................. ---------------- --------------------- -- -------------- ---------dS acang jAngstroms Relative_fnfiegrated ~ Theta , . .
. .
, = . t . =
lnten~rtY~
>--- -_ ---- ---------- . ........ _____ 9.64 9,17 w .....
- ___--- -----.....- ............. ---9,95 &~8 vs -- _ ---- .......
~ . 7~~ ~
.............. ------ -- ..........
1 0; 06 ............... ..... ----- - ________ ---- ----1 3.'I4 6.~3 w __ - .... ----- -------- ......_.... ___ ....
4.58 w _______ ______ _ 2`t .t~3 4,22 ~~
~.. ----- - ------------------------------___________ ------------------------------------------------ _ _________ .............------------22.35 3.97 Kri-S
....... . . ......._-- ....______,- ------ --------......._-__ ----- --------24.1 9 3,68 w ________ -_ . ------ ---- -------- __ ~ ........
28.37 3.14 ~
-__,30,16 ................... --------- _-______ - ------- - - _________ 2.96 w --------------- ______ _ ....---~
6 `a'+0.1 a 8 Table IIA beEow shows the X-ray , rsbvder dififracticrti lines for calcined 9 iric(udirig actual relative inÃer'sities', I '~ TABLE iiA
12 Calcined SSZ-75 ~ ---- ........ .... ------- ------ ........ -_ 2 Th~t~ s~a~~r~~ f~ristr~r~~), Reiatsve ~r~t~,~rated -----...
Intensit %.' __ - .....___ ...____ ---- ..... - ----- ----- ----------------- ___=-____ -- ---- --- .
------- ~~- --- - ..:
9.64 9.17 8 9.9r- 8.88 10.06 8.79 24 13.14 6.73 7 14.17 6..25 2 1:7,13 5.17 2 17.25 5.14 3 19.38 4.58 15 20;23 4.39 1 21.03 4.22 10 12:35 3.97 39 h;
22,54 3,94 24,19 16i3 7 25.24 3.53 6 26.08 3.41 2 26.48 3.36 6 ~
,...-- = ......____. = -----------. t~~
.....................................................................
................. --~_____________________-- -_________ , 28:37 3.14 7 29,25 3.05 3 30.16 L96 13 30:32 2.95 2 ~
32,18 2,78 J.3,S.laõ . 2.1 E 2 33.54 M7 ~
34.57 2.59 1 34. 94 2. 57 ~.' 35.09 2,56 1 35.68 2.51'. 2 36.58 2.45 1 3TO7 2.42 1 _______________________1 -_ ....... ..................... .._..__ __ ~
4 The X-ray pcsw~er diffraction patterns were determined by standard ;.~ tec}hr~~ques, The rad tiors was CuKa:pha radiation. The peak heights and the 6 positions, as a function of 20 where 0 is the Bragg angle, were. read from the 7 reI:atEve. intensities of the peaks, and d, the- interplanar spacing in Angstroms 8 corresponding to the recorded Ãiries, can be caicuiated, The arar3atie}n, in the scattering angfe, (two theta) measurements, due to
---------------------------------- ------- - --------19.44 4.56 s ~ ................
-----.... ................ ____________ --------iV ~'~
2'1. 13 4.20 ---------------------------- --------22.36 3.97 tfs .......... ---- __- ~ .................. - ..._...
,~2.4~ ~ 3. 9~ C1f3 ............ ....___ ___ ___ .......................... __ -- ;
24. 19 3,68 w __ .....------------------------- .........
2~.=~.61 ~.35 w -- ---------------- --- --- _________ ...---3,13 w 28,49 ...------------- ......... ..... .__ --.
3U0 __ -------- 2~~ ~
___ _ _______________ ~__._........... __ Ã......
- 0: 1 13 The X-ray pa##ers-is provided are based or, a reiative intensity -scale i~n 14 which the strongest line in the X-ray paftern is assigned a vaIue of 1 W
VV(w,reak) is less than 20; M(medium) is ~~ehmeen 20 arid 40; S(strong) 16 is between 40 and 60; VS(very strong) is greater than 60.
1`r 18 Tabfe IA belawshows the X-ray powder r~iffÃ~~~~~~~t, lines for as-synthesized 19 SSZ--75 ÃriclLrdirig aciua; r-c-latdve iniensÃt#es, TABLE IA
2 As-Synthesized SSZ-75 --- ..... -----. _ ._.. ____- ----- _____________ Relative int~carated 2 Theta tr~~..stroms 'y ....................... l#?tenslt - ---------------------=
-------------------8.98 7 9.84 10.04 Ã3. t30 100 1`~;~..24 6.68 7 1419 6.24 4 17.17 5.16 13 19.44 4:56 47 20,01 4A3 2 20.17 4.40 7 21,13 4.20 2111 22.36 3.97 84 22.49 3.95 38 24.19 3.68 12 26:13 3.41 7 ~ ~
26.61 3,:35 28.49 3.13 18 29.31 3.04 10 30.20 30 30.30 2.95 7 31,94 2.80 2 32.12 2.78 1 32.61 2.74 3 33,13 2.70 4 33,59 2.37 6 :34.86 2.57 7 35.13 2.55 5 35.75 2.51 6 C,15 2.46 2 36,69 2.45 1 37.19 2A2 .~
...... .... , ....... .....~
*
7 After caicination, the K--Ã~~ powder d;ttract=on patierÃi for SSZ-75 exhÃbmts the 8 charac.teristic lines sh~owri :n Table il beIow.
~
2 `i~~BLE li 3 Ca#caned SS~-75 ................. ---------------- --------------------- -- -------------- ---------dS acang jAngstroms Relative_fnfiegrated ~ Theta , . .
. .
, = . t . =
lnten~rtY~
>--- -_ ---- ---------- . ........ _____ 9.64 9,17 w .....
- ___--- -----.....- ............. ---9,95 &~8 vs -- _ ---- .......
~ . 7~~ ~
.............. ------ -- ..........
1 0; 06 ............... ..... ----- - ________ ---- ----1 3.'I4 6.~3 w __ - .... ----- -------- ......_.... ___ ....
4.58 w _______ ______ _ 2`t .t~3 4,22 ~~
~.. ----- - ------------------------------___________ ------------------------------------------------ _ _________ .............------------22.35 3.97 Kri-S
....... . . ......._-- ....______,- ------ --------......._-__ ----- --------24.1 9 3,68 w ________ -_ . ------ ---- -------- __ ~ ........
28.37 3.14 ~
-__,30,16 ................... --------- _-______ - ------- - - _________ 2.96 w --------------- ______ _ ....---~
6 `a'+0.1 a 8 Table IIA beEow shows the X-ray , rsbvder dififracticrti lines for calcined 9 iric(udirig actual relative inÃer'sities', I '~ TABLE iiA
12 Calcined SSZ-75 ~ ---- ........ .... ------- ------ ........ -_ 2 Th~t~ s~a~~r~~ f~ristr~r~~), Reiatsve ~r~t~,~rated -----...
Intensit %.' __ - .....___ ...____ ---- ..... - ----- ----- ----------------- ___=-____ -- ---- --- .
------- ~~- --- - ..:
9.64 9.17 8 9.9r- 8.88 10.06 8.79 24 13.14 6.73 7 14.17 6..25 2 1:7,13 5.17 2 17.25 5.14 3 19.38 4.58 15 20;23 4.39 1 21.03 4.22 10 12:35 3.97 39 h;
22,54 3,94 24,19 16i3 7 25.24 3.53 6 26.08 3.41 2 26.48 3.36 6 ~
,...-- = ......____. = -----------. t~~
.....................................................................
................. --~_____________________-- -_________ , 28:37 3.14 7 29,25 3.05 3 30.16 L96 13 30:32 2.95 2 ~
32,18 2,78 J.3,S.laõ . 2.1 E 2 33.54 M7 ~
34.57 2.59 1 34. 94 2. 57 ~.' 35.09 2,56 1 35.68 2.51'. 2 36.58 2.45 1 3TO7 2.42 1 _______________________1 -_ ....... ..................... .._..__ __ ~
4 The X-ray pcsw~er diffraction patterns were determined by standard ;.~ tec}hr~~ques, The rad tiors was CuKa:pha radiation. The peak heights and the 6 positions, as a function of 20 where 0 is the Bragg angle, were. read from the 7 reI:atEve. intensities of the peaks, and d, the- interplanar spacing in Angstroms 8 corresponding to the recorded Ãiries, can be caicuiated, The arar3atie}n, in the scattering angfe, (two theta) measurements, due to
11 instrument error and to differences between irtdivÃdu~~ samples, Ãs estimated
12 att 0,1 degrees.
13
14 Representative peaks from the X-ray diffraction pattern of asYsynthesized 16 SSZ-75 are shown in Tab1e i. CaÃcinationcan ~~sLiit in changes in the 16 Ãnten's#ties of the peaks as compared to patterns of the ;.as-syÃ~thesized,>
17 material, a-q well as minor shifts in the diff ractmon. pattern.
19 CrVstaÃiÃt~~ SS;~~~~ ~ can be used as-synthesized, but prei'erak,ly will be thermally tr~.ated (caÃciÃzed): Usually, it is desirable to remove t'ie aÃkaiimetaÃ
21 cation (if aily) by ion excharige ar~~ replace it.with hydragen; ammonium, nr 22 any desired r-nefiai ion. CaÃcÃnect SSZ-i 5 has an r`-~exarse adsorption capacity 23 of ak~oLit 0.15 cts/q.
;{3w 1 SSZ-75 can be formed into a wÃdÃ~> varaetyt of physical sP~~pels. Generally 2 speah9nq ; the i-nolecuÃar sieve cari be in the form of a powder, a granule;
or a 3 moaded product; ~uch as extrudate t;aving a partide si~~ sufficient to pass 4 through a 2-mesh Ã-l"yleri screen and be retaÃned on a 440:_rnesr} (Tyler) scr~en, fr, ccases where the catalyst is moided, sLÃch as by extrusion with an 6 organic binder, the SSZ-75 caii be extruded. before drying, or, dried or 7 partially dried and then extruded.
9 SSZ- 75 can be ~~n-ipc:sited with other materials resistant tc) ;he, temperattires and other conditions employed in organic conversÃori processes. SiAch matrix 11 materiaÃs include active and inactive materials and syritheaic or natu~'ally 12 occurri~~g zealite-, as well a,s inorganic materials such as Claya, siiÃca and 13 mefial' oxides. Examples of sucFi materials and the manner in which they can 14 be tised are disclosed i~i US, Patent No. 4,910,006, isstaed May 20: 1:990 to Zones c;t al., and US. Patent No. 5,316,753, . issued May 31, 1994 to 16 Nakagawa, both of which are incorporated by rerrrreaice hereir, in their 17 entirety.
19 H, ~~rocarbon Conversion Pr~~e-5 21 SSZ--r ~.~ molecular sieves are usefLil in hydrocarbon coriuersÃc,n reactions.
22 Hydrocarbon conversion reactions are ehern4cal and catalytic~ prace5ses an 23 which carbon containing c.campvurids are changed to different carbon 24 containing compounds. Examples of rsydrocarbon conversion reactions in which ~SZ-:r ~'~ is expected to be usefui inc:utÃe hydrocracking, dewaxirig, 26 catalytic crackiÃ~~ and olefiti and aromatics fwrmation reactions. The Catalyst~
27 are also ~~~ected't~ be useful in other petroleum, refining and hydrocarbon 28 roiiversics3-i reactions such as isarrerizir~g n-paraffiÃis and r~~phthenes, 29 polyÃrier;zing arid oligomerizing olefinic or acetylenic compounds such as ;~abLi1yIene and bute:ie-1, poÃynierÃzatgon of 1-olefins (e,q.; ethylene), 31 retiorrnÃng, isomerizing poÃyal'Kyl substituted aromatics (e.g.; m-xylene), and 32 disproportionatÃng aromatics (e,g., toluene) to provide mixtu:es of benzene, 33 xylenes and higher rnethyÃbenzerie5 and rWxidat~~n reaetÃons. Also included .:,lw I are rearr~.ar;gpment reactions to make various naphthalene ~.~erivatives, and 2 forming higher moiecul:ar weigt,f hydrocarbons trtvm lower -n-i~~~cula#
we#ght 3 hydrocarbons (e,:g., methane upgrading).
~`i The SSZ-75 catalysts Ã-fiay have high selectivity, and under hydrouar~on, 6 conversion conditÃoris can provide a high percentage of desired products 7 relative to total producxs.
9 For high catalytic activity, the ~SZ-75 Ãnoteor.rlar sieve should be predominantly in its hydrogen ion form, ~.~eneraf1y, the molecular sieve is 11 converted to its hydrogen form by arnrr onium exchange followed by 12 calcination. If the molecular sxeve, is synthesized with a high enough rati~,.} of 13 SDA cation to sodium ion, calcÃnatio#i a9one may be sufficient. It is preferred 14 that, after oatcinatioÃ7, at.1east 80% of the cation sites are occupied by hydrogen Ãosis and/or rare earth ions. As used hcrein, "predoriianatitly in the 16 hydrogen torm: means tFiat, after t:,alciÃiatian, at least 80% of the, cation s;tes 17 are occupied by hydrogen ions andtor rare earlh moris.
19 ~~~-75 molecular sieves c ar~ be Lr~ed in processing hydrc.rarboraaceaus feedstocks. Hydrocarbonaceous feedstocks contain carbori compounds and 21 cari be frorn r-nany different sources, such as virgin petroletirii fractions, 22 recycle pegroleurii fractions, shale oil, liquefied coal, tar sand oil, synthetic 23 paraffins from NAO, recycled plastic feedstocks. Other feeds include 24 synthetic feeds, such as those derived from a FÃscher 'l ropacfi process, ;ncludÃrrg ar, oRygenate-cont:aining Fis~~~er Trop'sch process boili-rg below 26 about 371'G L700 F), IÃ~ ~eneeal, the feed ~an;be any carbon containing 27 feedstock susceptible to zeolitic,:ata(y#ic reactions. Depending on the type of 28 processing the hydrocarbonaceous feed is to undergo, the 1'eed can co>-#tain 29 metal or be free of metals, it can also have high or low nitrogen or sa:,ltur impurities. It can be appreciated, howe-vrer, that in general processing wili be 31 more efficient (and the catalyst more active) the lower the metal, nitrogen, and 32 sÃaifur content of tl-ie fe-edstock, :>~
1 The conversion of ~ydrocarbon@cecaus feeds can take place Jzi ariy carivenient 2 mode, for example, in fluis~iizeÃ~ bed, rÃ-tcv:ng bed, or fixed bed reactors 3 depending crà the types of pfocc-ss des;Ã-ed. The fornnulafion of the catalyst 4 particles Mf vary ~ependirxg an the conversicÃi process and method of operation.
7 Other reactions which can be performed using the c~~~~~yst of this iravenfion 8 corltaÃnÃng a r-fiefai, e.g., a GÃ"ou~,.~ tfifà Ãiietal such platÃnLÃm, includp-9 hydroge nation-dehydroge nation reactions, denÃtr.oge nation and desufftirÃzaiior~
reactions.
12 'Fhe following faNe indi:.qfos typical reaction c~ndÃfiorts whic,i-Ã Ãilay be 13 employed when using catalysts comprising SSZ-75 in the f~ydrocarbon 14 coriversÃon reactions of this iriver9tion. Preferred coÃiditions are indicated in parentheses.
~?N
Temp. `C Presstire SV
t-iydroerackÃng 175.-485 0.5-350 bar ---------=--------------- ""-~ ....- -- ---------D~;a~a;~ia~ g 200-475 15-3000 psÃ+~, 01-`~Q
(2 50<~4,90) 0.103-20.7 Mpa (0.2-10) ga ge (200-3000, 11.38..
20- 7 Mpa gauge) ------- -------- ------------ r----------- ------"" -"--"-"_"
_-" __--___ -__________ ~
fr~r~~a~'jon (480-55M
- - -- - - ------------ -Cat: Ã racÃsinq A
atni. ) -- --_____ _ -,7--------------- - --_______---t7Ãic~or~~erizat;or~ 2:~2-649A ~a: 1 -50 atta~ (1,2 -,5 10-232" OM-2.
(27.-204)4' --------- { -____~.
~ar~~ins to 100-700 0-1000 psig arornatics - ----- ------ --- -------- --------- -- -------- ------ ____-_- -Corideiisation ot 2b.~-1000 psÃg, 0.5-50 -aÃcoÃ-iois = 0.00345-6.89 Mpa gauge --------- ------------------------ - ~" ------------" --_ ____ __ Ãsomerizatior~ 93-538 50-1000 psig, 1-10 #'204-3153 0.345--&89 Mpa (1-4) gauge ------------------------------------------ ----_-XyÃ~ne.
isoÃiaerizatior~ ...26O-593 ~'i~~ ~t~i~ (0.6-50), ,..
a8-3tf1.r 1-200 atm.4 ~ 15 - -5 '`~
~----------- _ -------------- "------------ - --------.-----""----_____"_~~ -. ----- ...... ~
2 ~evera4 hundred ;~~~~~~spÃietes 3 ` Gas phase rea~.~tion 4 ' Fiydrtsc:arboa-i partial ~~~~sune " Liquid phase reaction ~ 6 wÃ-isv 7 Other reaction cordi õ~~ons and parameters are proyridUd beÃow.
'14 ~
2 ~ ~~ocrackinq 4 Usmg a catalyst which comprises SSZ-75, preferably predom,nant:ly+ in the hydrogen form, and a hyciroger t>on pror-noter, heavy petroleum residual 6 teedstoi;ks, cyciÃcstoc;~~ and other hydrocrackate charge 'stocks can be 7 hydrocracked using the process conditions and catalyst components 8 dlscbsed in the atore P-nent3oned U.S. Patent No. 4,910,006 and U.S. Paterit 9 Nca. 5,316,753, 11 The hydrocracking catalysts corÃtain, an effectwe amount of at ieast one 12 hydrogenation cc#rnponent of the type ;:ommon3y employed in hydrocracking 13 catatysts. The hydrogenation component is generally selected from the, grcrÃ,Ãp 14 of hydrogenation catalysts consisting of one of more metals of Group VIB ar-~~
Group ;,t'iil. inci~idirig the saits, complexes arid solutions containing such. 'T`he 16 hydrogertakmori catalyst is preferai,;ly selected from the group of metals, salts 17 and cOmpiexes t~ef-eof of tt3e group consisting of at least one of platinum, 18 palladium, rhodiÃ.im, iridium, ruthenium and mixtures thereof or the group 19 s_.orisisting of at least one of nickeir molybdenum, cobalt, tLingsten, titanium, chromium and rnlxlures thereof, RetereÃ-ice to the catalytically active metal or 21 B-netals is BnterÃded to. encompass such metal or metals in the elemental state 22 or in some form such as an oxide, sLÃIfide, halide, carboxylate and the like.
23 The hydrogenatiosi catalyst is present iri ari effective amount to provide the 24 h}rdrogenationfuÃ`Ãction otti^ie hydrocracking catalyst, and prefarabiy in the rarige of from 0.05 to 25% by weight.
27 Dewaxing 29 For dewaxing processes, the catalyst comprises arnolecular sieve having STi tpology and hav;rig a Ãn6e ratio of at Ãeast 15 of (1) an oxide of a first 31 tetravalent element to (2) an oxide of a tF'#valarit element, pentavalee-.t element, 32 secoE'id tetravalent element which is different from said tirst te.trava[enT
33 eIement or mixture thereof. Thus, the molecular sieve may be SSZ-75 or-''~-1 TNU-10, preterainly predomÃnantly in the hydrogen torm, The catalyst can o.~
2 used to dewax hydrocaribar>aceous feeds by selectively removing straight 3 chain paraffÃm-s; Typically, the viscosity Ãradex of the dewaced product is 4 improved (eompared to the waxy t~~~) when the waxy feed is contacted with S SZ-75 or T'NU-10 urider isornerization i~ewaxÃrkg concÃiti~.~ns.
7 The catalytic dewaxing conditions are c~ependeait ir, large measure on the 8 feed used and upon the desired pour point. Hydrogen is preferably present in 9 the reaction zone during thp- catalytic ~ewaxing: process. The hydrogen to feed ratio is typir,a11y k~~~~~~~ about 500 and about 30,000 ~~F/bbi (standaru 11 cubic feet per barrel) (0.089 to 5.34 SCM/liter ;standard cLibic mete rsr`i:te r)), -12 preferab1~ about 1000 to abo~at 20,000 SC:;FF`bb! (0.178 to 3.56 SCM/iiter)~
13 Generally, hydrogen wii[ be separated from the product and recycled to the 14 reaction zoa-ae, Typical reedstor;ks include light gas oil, heavy gas oi~~
and reduced crudes boiling above aboui~501'i" L'177,C;.
17 ~"a typical dewaxing process is the catalytic dewaxing of a hydrocarbon oil 18 feedstock boilir~~ above about 350UF (17; ,"C) and containirig straighL
chain 19 and sl ;!htly branched chain hydrocarbons by contacting the hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pr~~sure of 21 about 15-3000 psi (0.103-20.7 Mpa) with a catalyst comprising SSZ-75 and at 22 least orie Group VIià metal, 24 The SSZ--75 or TNU-10 hydrodewaxing catalyst may optionally contain a hydrageriatÃon component of the type commonIy employed wn dewaxing 26 catalysts. See the, aforementioned U.S. Patent No. 4,910,006 and U.S.
27 i`'aketit No. 5,3416;753 f~.?r exaÃ~ip1es of ti'=~~~ehydrogenation Ct3rr,ponents.
29 The hydrogenation component is preseiit in an effect;ve arnu:ant to provide an.-effective hydrodewaxing and hydroisonierization catalyst preferably in the 31 range of from about 0.05 to 5% by weight. The catalyst Ã-nL~y be run in such a 32 mode to increase isomerization c~ewaxing at the expense of cracking 33 reactions.
2 The teaci may be hydroCra.cked, foll~~vp-d by dewaxing. This type of two stage 3 process and typical hydr~cracking condations are described #n U.S. Patent 4 No, 4,921,594, issuec9 :May 1, 1990 to Miller, wt7icti is incorporated herein by reference in its enkir-eiy.
7 S5Z-75 or 't-i=3U--10 may also be utÃfized as a cor-iib:riataor? of catalysts. That 8 is, the cataiyst comprises acombinatior-~ comprising rrioiectjlar sieve SSZ
f5 9 or TNir1-10 and atleast orie Group Viil rneta,~, and a second catalyst comprising an aiummosiiicate zeolite vvrtich. is more shape selective than 11 mcslecLilar sieve SSZ- l5 or TNLt 10. The combination may be comprised of 12 1ayers. The LÃse of layered catalysts is disclosed in U.S. Patent 13 Na. 5, 149,421, issued Septer~ber 22, 1992 to Miller, which is incorporated by 14 reference herein in its entirety. The layering may also include abect of SSZ-75 or TNU=10 layered withi a r:or-Ã-zeolÃtic component deslgF-.ed for eÃt(ier 16 hydrocrac;kir~g or liyrtrofiriishing.
18 S5Z-75 or 1'NU-10 may also be used to dewax raffriates, irtcludisig t3rlght 19 stock, Lsnder conditions sE~~~~ as. those cilsef.ase(i in U. S. Patent No. 4,181,598, Ã~stied January 1, 1980 to Gillespie et ai., which is 21 incorporated by reference herein in its entirety.
23 It is otter-r desirab!e to use mild hydrogariat#on (sometimes referred to as 24 hydrofinÃsh:iig) to produce more stable dewaxed products. The hydrotinishirg step can be performed either before or after the dewaxing step, and 26 preferably attes-. H, drotinÃshing is typicairy cond~~~~ed at tempera.tures ranging 27 from about 19VC to about 340 C atipreSsur-Ã:s from about 400 psiva to about 28 3000 psig (2.76 to 20.7 Mpa gatige) at space veItac3ties tLHSV; be'tbq~~~~
29 abcsrJt 0.1 anti 20 and a hydrogen recycle r ate of about 400 to 1500 SCiFlbl~+i (0.071 to 0.27 SCM/liter). The hydrogenation cafalvst employed must be 31 aative eraough riot only to hydrogenate the olefins, dioEetins and color bodÃ~~
32 which may be present, but afso to reduce the ararnati;; content, gLrltabIe.
33 hydrogeriat;or catalyst are discl~~e(J ;n U. S. Patent No. 4,92.111a594, isSiUed .,.~
1 May 1, 1090 to Miller, ,whic:h is #ncarpoÃated by reference herein in its entÃrety:
2 Thehydrofin;shing step is beneficial in prapanng an acceptably stable product 3 (e:g;, a lL,bric.atirag oil) sir~~~ ~ewaxed: products prepared froÃii hydrocracked 4 stocks tend to ~p- uristabfe to air and !Ãght aiid terid to form sludges spontaneously and quickly.
7 Lube oil may be prepared using SSZ-7 5 or TNU-1 0. For exampEe, a C20_> lube 8 oil may be rr,ac#~ by isornerizing a~~0, oIefÃn feed over a 4ata(yst compr`ssing 9 SSL-,75 or TNU-10 in the hydrogen form and at least one Group Vill metal.
Alternatively, the lubricating oil may be made by hydrocracking in a 11 hydrocracking zone a hydrocarbonaceous feedstock to obtain an efffuentt.
1'y.' comprising a hydrocracked o#i, and catalytically dewaxing the effluent at a 13 temperature of at feast about 4WF (204 C) and at apressÃare of from abotÃt 14 15 psig to about 3000 psig (0.1031-201 Mpa gauge) in the presen:ce of added hydrogen gas with a cataiyst comprising SSZ-75 or TNU- 1OF in the hydrogeri 16 form and at least one Group Vill metal.
18 Aromatics Formation SSZ-75 cran be used to convert light straightrLan naphthas and similar 21 mixtures to highly aromatic Ãnixtutes, Thus, normal ar7d slightly branched 22 chained hydrOcarbans, preferably t ving ababiiÃig range above about 4Ã3 t;
23 and less than about 200"C, can be converted to prodEaCt~ having ~substantsaf 24 higher octane aromatics content by contacting the hydrocarbon feed with a catalyst comprising SSZ-75. It is also possible to conveat heavier feeds into 26 B'T-X or riaphthaler-e dei-ivatives of vaiÃ.:e using a catalyst comprisiÃ~g SSZ-75.
28 T~~~ ~onversion catalyst preferabiy contains aGrs~~~p VIII mp-tal compound to 2 9 have sufficient activity for commercial use. By Group VIII iiieta&
~~~~lpauÃkd as used he--eiÃi is meaÃit the metal itself or a cctmpoLir;d thereof. The Group Vlll 31 noble metals and their compounds, piatisium, palladau:m, and irictiurTi, or 32 combinations thereof caÃi be cised. Rhenium or tin or a mixture thereof may 33 also be used ;n corijuÃictiori with, the Group ViIl iiiet~t compouFnd and _._'~
I prt-farab(y a noble metai compound. The most preferredr.r~Ãetal is piaiÃnurn.
2 The amoLint of Grcatsp Vlil metal preseÃit in the conversion catalyst should t~~
3 within the normal range of use in reforÃ-ni-tsg catalysts, from about 0.05 to 4 . 2.0 weight percent, preferably 0.2 to 0.8 weight perceÃ7t.
6 It is crrt~cal to thie selective production of aromatic$ in tiseful qtiantities that the 7 conversion catalyst be sLibstantiail~ free of aaidity, for exarrÃple, by 8 ne tra(izing the molecular sieve with a basic metal, e.g., a(kals metal, 9 compound_ Methods for rendering the catalyst free of acidity are knownÃr:
the art. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Paterit 11 No. 5,316,753 for a description of sr.:ch mettiods.
13 The preferred alkali metals are sodium, potassium, rubidiurn and casium;
The 14 moÃecular sieve itself can be substar<fialiy free of acidityj only at ver)r higt) si!Ãca:alurziÃna mole ratios.
17 Catalytic _ QracliÃ~~c 19 Hydrocarbon cracking stocks can be catalytically cra cked in the absence of hydrogen using SSZ-75r preferably predominantly in the hydrogen form.
22 When SSZ-75 is used as a catalytic cracking catalyst iÃi tiie absence of 23 hydres<;eÃt, the catalyst may be employed in conjunction wÃtti traditional 24 craek,inQ~ cataiysts, e;g., any aIurninosiiica~.te heretofore empIoyed as a component in cracking catalysts. "i ypically, i:t~~se ai-e lar:~~ pore, crystailine 20- awtamÃr#asificates. Exampies of these tra,ditioriai cr~cking catalysts are 27 disclosed in the, atorer?ierytior.ed U.S. Patent No, 4,910,006 and U.S.
Patent 28 No 5.316,753. W~en a traditionaC cracking cataiyst (TC) corrrporient Ãs 29 employed, #tie Ãelative weight ratio of the TC tc) the SSZ-75 is generally bertvVeer) about 1 : 10 and about 500:1, desirably between aboÃÃt t :'s'. C
and 31 about 200:1, pre#erabiyf betvveen about 1:2 and abo:it 50:1, and most 32 preferably is bet~*reen about I :1 and about 20: 1. 'T'he novel molecular sieve .~:t~~
1 and/cxÃ- the traditional cracki~~9 coii1ponent may be further ion exchanged with 2 rare earih: ions tonnod:fy selectivity, 4 The cracking catalysts are typicai'ly empb~~(i with an inorganic oxide matrix component. See the aforementioned U.S. Patent No. 4,910;006 and US.
5 Patent No. 5.316,753 for examples of such matrix components.
a isor~er#zatiot) ( t~~ present catalyst is highly active and highly selective for isornerrzRr3gC4 to 11 C-7 hydroGaÃ-batis, Theac>tivity means that the catalyst can operat~ at 1:2 relatively low temperature which thet'modynamically favors highly branched 1:3 pat-~.~ffins, ~._oÃ-~~equeritly, t~~e catWyst can produce a high octane profjLjct..
14 The high selectivity means that a relatively hig.hi liquid yield can be achieued when the +~,@ta!yst is rusi at ah;gi~ actane.
17 The present process comprises contacting the isomc-tÃzation catalyst, i.e., a 18 cataiy5t comprising SSZ-75 in the Ãiydr~~en form, with ~~~~~~rocar=bon feed 19 r_ander isomerlzation conditions. T1'ap, feed is preferably a 1Ãgtit straight r-tit~
fraction, boiling within the range of 30'F to 250'1:=- ~--1IC to ~~~'C) and 21 ~re-ferably from 60'F to 240"~ (16 C to 93 'C). Preierably, the hydrocarbon 22 feed for the pi'c-scess comprises a substantial ainount of C.j to C;
nor'rnaI and 23 slightly tararictied low octane h7ydr-ocar-tYc.r-is, riiare preferably CE, arid C6 24 hydrocarborss:
2~'?
26 It is preferable to ~~~~ out the isomerization reaction ir, tlle presence of 27 hydrogen. Preferably, hydrogen :s added to give a hydrogen to hydrocarbon 28 ratio (~2,41C) of 'r?et'weet) 0.5 and 10 112r'1-IC, more preferably between I and 29 8 H21HC. See the aforementioiied L.J.S. Patent No. 4,910,006 and U.S.
Patent No. 5,316,753 for a tr.irther dÃsc;Ãssicap, of isomerization process conditions.
32 A 'loYv sulfur feed is especially preferred in the pre'sent process. The feed 33 pi-eter-ably contains less tharb 10 ppryi, -nore preferably less than I
:xipm, af:d 1 most preferably less than 0 . 1 ppm sulfur. Iri the case of a feed which is not 2 already low in sulfur, acceptable levels car: be reached by hydrogenating the 3 feed in a presaturation zone with a hydrogenating catalyst which is r-esistar-t to 4 suIfuÃ- poisoning; See the aforementioned U.S. Patent No, 4,910,006 and U.S. Patent No. 5;3167753 for a further dÃskusuia~ of this hydrodesulfurÃzation, 6 process.
8 It is ~~eferable to!Ãm!t the nitrogen level and the water content of the feed 9 Catalysts and processes which are suitable f{Drfhese purposes arp- known to those skilled in the art.
12 After a period of operation, the catalyst can becsime deactivated by sÃ.ÃiÃur or 13 ~ok.e. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent 14 No. 5;316,753 for a #uÃ-ther discussion of methods of removing tHs su3fur arid coke, and of regeneratirig the catalyst.
17 The conversion catalyst preferably coritaÃrss a Group Vill r~ietal compound to 18 E~ave sufficient activity for comniercÃai use, By Gr~~~p Vlli metal compound as 19 used herein is meant the metal itself or a compound thereof. The Group VIII
noble metals aand their compounds, platinum, paI[adiurn, and iridium, or 21 corrrtiiaiatÃorrs thereof can be used. Rhenium and tin may also be used in 22 conjunction with the noble metal. The most prefe-rred liietal is platlnum.
The 23 amo~int of Group VIli rnetal present in the conversion catalyst shotild be withi;l 24 the normal range of use in isornerizing catalysts, from about 0.06 to 2.0 weight percent, preferabiy 0.2 to 0.8 weight percent.
27 Alkylatior~ ~~d.TransalkyLation 29 SSZ-75 c:~.~Ã~ be used in a process for the alkylation or transalkylation of ar~
arc-ma#3c hydrocarbon. The process coiiiprises contacting the aromatic 431 hydrocarbon with a C2 tO 0<6 OIetin aIlcylating agent or a polyalkyl aromatic 32 hydrocarbon transalkylating agent, ~~~rAer at least partial liquid phase 33 conditions, and in the presence of a catalyst comprising SSZ-75.
-3t-2 SSZ--75 cari also be tised for rernoving benxerae frorn gasoline by ~ikyiating 3 th:e benzene as described above and removing the alkylated prodtict from the 4 gaso1ine,, 6 For high r:atalytic activity, t#ie, SSZ-75 rno(ecuiar sieve should be 7 predominantly En its hydrogen ion forrn. It ispreter~~ed that, afte-r calcination, at 8 luast 80% of the cation sites are occupied by hydrogen ior7~ andlor rare earth 9 ions.
11 Examples of suitaWe aromatic hydrocarbon feedstocks which may be 12 alkylated or transaikyEated by the prc~~~ss, of 5he, invention ;ne:;ude, aromatic 13 compounds such as benzene, toluene and x-v(ene. The preferred aromatic 14 hyrir'ocarbor is benz.eille. There may be occasions where naphthalene or t~aphtr#aferie derivatives sticr'h as clRmethyIpaphthalene may be desirabte.
16 Mixtures of aromatic Frydrocar-bor3s may also be employed.
18 Suitab1e olefins for the alkylation of the aromatic hydr'ccarbor, are those 19 contairiinr.~ 2 to 20, preferably Z to 4, carbon atoms, %Ac h as ethylene, propylene, buter:ze-I ; trans-butene-Z and cis-bGitene-2; or rnixtures therenf.
21 There may be instances where pentenes are desirable, -rhe preferred olefins 22 are ethylene and propylene. Lor~goar chain alpha r11efins may be used ~s well.
24 When tran-saiky?ation is desired, the transalkylatirig agent is ~polyalky;
arornatic. hydrocarbon :.ontaining two or more alkyl groL,ps ttiat each may 26 have from 2 to about 4 carbon atorrs: For example, suitable polya~kyi 27 aromatic hydrocarbons include di--õ trÃ- and ietfa-alkyl aromatic hydrocarbons, 28 suchi as dieti^>y1benzene, triethyÃbenzene; dÃethy;methylber~~ene 29 (diethyltoluene), di-isopru~~lbt>;r~~~ne, di-isopropyltoluene, dibutylbenzene, and the like. Preferred po9yalkyl ararnatic hydrocarbons are the dialky;
31 benzer-tes> A par-~~cuIariy preferred pofyalky~ aromatic hydrocarbon, is 32 dkisopropylberzzene.
::.. , ~:..
1 When aIkylatiori is the process conducted, re~.~..c;tiort conditions are as follows, 2 The aromatic hydrocarf~on feed should be present Ãn sto#chiometric excess.
It `~ is preferred that molar ratio of arornatics to oIefir-s be greater than four-tc--ore 4 to prevent rapid catalyst foulirrg. The reaction temperatLrre rnay; rarige from 100'F to 600~~ (38 C to 31YC), preferably 250"f" to 450''F (1''~1 C tr~ ~
~~CC).
6 The reaction pressure should be sufficient to maÃntairi at least a partial liquid 7 phase in order to retard catalyst fouiing. 'f`Ns is typically 550 psig to 1000 psig 8 (0.345 tt-, 6.89:Mpa gauge) depending on the feedstock and reaction 9 teniperature, Contact time may range from 10 seconds to 10 hours, but r~
usuaiiy from 5 m;inutes to an hour. The weight hourly space vefc+city~ (WHSV), 11 in terÃnu of grams (pounds) of aromatxr: hydrocaÃbon and olefin per gram 12 (pound) of catalyst per hour, is generally witfiiri the range of about 0,5 to 60.
14 When transalkylation is the process conducted, the molar ratio of aromatic ~1 5 hydrocarbon wÃ1Ã generally rar:ge froÃ~~ about 1:1 to 25;1, and preferably froÃ-n 16 about 2:1 to 20:1. The reactiori temperature may rangra from about 1006 Fto 17 640`F= (380C to ~~ 50C), but it is preferably about 250s F to 450'F=" ~ 121 FC to 18 232cC}. The reaction pressure should be sufficient to maintain at least a 19 partiai liqfiid pf3ase: typicaq(y in the range of abc~~~~ 50 psig to 1000 psig (0.345 to 6.89 Mpa ~auge), preferably 300 psig to 600 psig (2,07 to 4.14 Mpa 21 ~~~ge): The weight hourly space velocity vvEll range from about 0.1 to 10.
22 U.S. Patent No. 5,082,990 issued on January 21, 1992 to f-isÃeti, et al.
23 ciesf;sibes such processes and is incorporated herein by refer'ence, Conversion of Paraffins to AroÃnatic-,, , paraffins to higher moI~cLilar 27 SSZ 7 5 can be tised to convert lig l-it gas C2 Cr 28 weiglRf hydrocarbons including aromatic compounds. Preferably, the 29 molecrj3ar sieve will contain a catalyst metal or metal oxide wherein said metal is selected from the gÃoup consisting of Groups 18, I18, VÃfl and IIIA of the :31 Periodic Table: Preferably, the metal is gallium, niobiurn, ~tidirim ot' zinc irl the 32 range of fsoÃn about 0.06 to 5,1/o by aveight.
r;3 ,,..
1 fsomerization of Olefins ~.
3 SSZ-75 r:ar, be used to isomerize oletir:s. The feed stream is a hydrocarbon 4 stream containing at Eeast orÃeGr-~, O1efio., preferably a C~ F, normal 6e#wn, more preferably normal butene. Normal buter:~ as used in this specification means 6 all forms of normal buterie, e.g., 1-butene, cis-2..butene, and trarls-2-buter,e.
7 'Typlcally, hydrocarbons other than normal butene or other '4 ~ normal olefins 8 will be presergt in the feed stream,. These other hydrocarbons may include, 9 e.g., alkaries, other olefins, aromatics, hy.droger-1, and inert gases.
11 'T'he feed stream typqcaEly may be the eftlueÃif frorn a fluid catalytic cracking 12 urrit or a methyl-t:ert-bu#yI ether uriit. A fluid cat~lytic, cracking ullit effluent 13 typically contaxris aboLAt 40-60 weight percent normal butenes. A
14 methy:-tertNbu#yl ethereingt e-ffluent ty+~.~Ãcally contains 40-100 weight percent normal buterre, The feed stream preferably contains at least about 40 weight 16 percent normal butene, more preferably at ieast about 65 weight percent 17 normal btitene. The terms isovolefar~ and rnethy+! branched iso-oÃefin may be 18 used interchangeably Ãp this specificatÃon.
The prof-ess is carried out under isomerlratiora corrditi:aris. The hydrocarbon 21 feed is contacted ~r%, a vapor phase wi'th a catalyst waniprlslÃig the ~SZ-i -5.
22 The process may be carried out generally at a temperature froÃ-Ãi about 625 '~
23 to about 950u~ (329-510UC), for butenU s, preferably from aboLFt 700uF to 24 about 900"F (37a-482`C); and about 360'F to about 650+ (1 f 7-343"C) fur pentenes and fiexenes. The pressure ranges from sr.rõatrnospherac to about 26 200 ps;g ; 1.~8 Mpa ~auge)> preferably froril abc rst 15 psig tr) about 200 psig 27 ( Ø 103 to 1.38 Mpa gauge), and more preterably troni about ~ ps-1g to about 28 150 psig (0.00689 to 1.03 1Vipa gauge).
Tiie liquid hourly space velocity during contacting is generally from about 0.
31 to about 50 hr '.; based or, the hydrocarbon teed, preferably from about 0.1 to 32 about 20 hr', more preferably frc1r;~ ~~OLst 0.2 to abou#. 10 hr"i, ntost preferably 33 from about I to abutit 5 I'-ir". A hydrogen/hydrocarbon molar ratiois v34., 1 mairitaEr-ied from about 0 to about 30 or higher> 'T'he hydrogen can be added 2 dErect@y to k},e feed stream or directly ta the isomerÃzatiar) zone. The reaction, 3 is prefera~ly substantiaHy free of water, typically tess than abaL,t two weigtzt 4 percent based on the fr~ed. The process can be carried out 3n a packed C~ed rp-actor; a fixed bed, fELiidszed bed reactor, or amovir-rg bed reactor: The bed 6 of the ; atalyst can rr:ove upward or dowr3ward. The r?-ioI~ percent conversion 7 of, e:g., rrarmal br,aierze to iso-butene is at least 10: preferably at least 25, and 8 more preferaNy at least 35.
~. I~~~~~~ornerirats~r, 1'1 12 ~SZ-75 may also be u,5etul in a process for asomarizir~g one or more xylene 13 isomers. in aCa aromatic t~ed to obtain ortt3o-, meta--, ar:d para-xylene in a 14 ratio approaching the equilÃbriLim vaiue. In particular, xylene isomerization is used in conjunction with a separate proce<ss, tt) marrufactL3re para-xylene:
For 16 example, a portior, oof the para-xylene in a mixed Ca aromatics straarii may be 17 rer:overed by erystaflization and centrifugatican. `~he, mother liquor trom the 18 crystallizer is then reacted under xylene isomerization conditions to restore 19 ortho-, meta- and pa-a-xyieries to a near equilibrium ratio. At the same time, part of the ethylber~~ene in the mother liquor is converted to xyfer~es, or to 21 products whÃch are easiiy separated by fi1tration. -rhe isomerate is blended 22 with fresh feed and ttie cgombiÃied stream is distilled to remove heavy as-id light 23 bv_praducts. The resuÃtar3t Ca aromatics stream is then sent to the crystallizer 24 to repeat the cy1cle:
26 Optiorially; isomerization in the vapor phase is conducted in the presence of 27 3.0 to 30,0 moles of hydrogen per mole of alkylberizetie (e:g.;
ethy;benxene), 28 If hydrogen is used, the catalyst should comprise about 0.1 to 2.0 VA.% of a 29 h:ydrogenatm:orr'dehvdroqp-natsorw componerii selected from ~`~ror,~~~ VilI
(of the Periodic 1abie) metal component, especially platinum or nickel. By Grou;p VIII
31 metal cor~ponerit Ãs meant the metWs and their compounds such as oxides 32 and s1.3lf4C$es.
1 Optionally, the isornerizatioÃ, feed rnay contairi IQ to 90 wt. of a diluent such 2 as folrione, trimethylbenzene: naphthenes or paÃ-affiiis.
r~
u 4 'Oligomerization 6 it iz,-, expected that SSZ 75 can also be used to oligomerÃze straight a-ld 7 bran&ed chair~ olefins having from about 2 to 21 and preferably 2-5 ~arbon 8 atams. ` The oIÃgomers which are the. prodricts of the process are mediurn to 9 heavy olefins wh~ch are useful for both fuels, i.e., gasoline or a c~asso1 me blending stock and ctiemicals:
12 The o;igomerixatiorà process c:orY7wri~~s, contacting the olefin #eedstock in the 13 gaseous or liquid phase with a catalyst comprising SSZ--75.
The n~~~ol~cuÃar sieve can have the original cations associated therewith 16 replaced by a wide variety of other cations according to tÃ~~chniqr_r~s well 17 known in the art, Typical cations would include hydrogen, ~~nmonit-im and 18 metal cations incii.iding mÃxlures of the same. Of the replacing irieta113~
19 cations, particular preference is given tc3 cations of met~l~s such as rare earth metals, manganese, calcium, as well as metals of Group li of the Periodic 21 Table, e.g., zinc, and Group VIII oÃthe Periodic Table, e.q., r3ickei, One of the 22 prirne requisites is that the molecular sieve have a fairly low aromatization 23 activity, i.e., in which the amoiant of r.~rorr'ati~s produced is not more than 24 about 20% by weight. This is accamplistied by using a molecular sieve with controlled acid activity aspizz~ va3iie' of from about 0.1 to about 120;
preferably 26 from about 0. 1 to about 100, as rÃ~~~~ured by its ability to crack r0hexane.
28 Alpha vaiue; are defiried by a standard test known in the art, as sf?obvri 29 in U.S. Patent No. 3,960:978 issued on June 1, 1976 to Givens et al. which is incorporated totally herein by reference. -f required, such molecular sieves 31 may be obtained by steam:ng, by use in a conversrori process or by any other 32 rr~~thod which may occurtc. one skilled inthis art.
'~ r~..
I Condensation of Alcohols 3 SSZ-75 can be used to condense lbwer aliphatic aico+iols haviiig 1 to 4 10 carbon atoÃns to a gasol;rÃe boiling point hydrocarbori pioduct coÃnprising mixed aliphatic and aromatic hydrocarbon. The process disclosed iri U,S.
6 Patent N'o. 3,894,107, issued July 8, 1975 to BcÃttei-et aIõ describes the 7 process conditions used in this process, 'ii1'hi~h patent is i:'1corp:}~"'ated totally 8 herein by reference:
E_, The catalyst may be in the ~~~rr-)ger3 form or may be base exchanged or 11 impregnated to contain ammonium or a metal catioci complement, prefierabEy 12 in the : ange of from about 0,05 to 5% by weight. The metal cations that may 13 be present incRude any of the metals of the Groraps I through VIl1 of the 14 Periodic Table, However, in Yhe- case of GrouF? IA metals, the ca;iori rontent ~~ould in no case be so large as to effectively iÃiactivate the catalyst, nor 16 should the exchange be such as to eliminate all acsdity, There may be cithei-17 processes invo1virig treatment of oxygenated substrates where a basic 18 catalyst is desired.
Mthaiap_Q~adÃnc~
22 Higher moiecula weight Iiydrocarbons can be formed from lower mal~cuiaÃ2.3 weight hydror.arbor~s by contacting the lower molecular weight hydrocarbon 24 with a catalyst comprising SSZ-75 and a meta4 or metaE compourid capable of converting the lower nio1ecLÃlar wesght hydrocarbon to a higher molecular 26 weight t-Ãydrocart3on, Examples of *,uch reactions Ãr-icitÃde the conversion of 27 Ã-nethane to G, , hydrocarbons such as ethylene or ~~nzeÃie ot both:
28 Exam,,1es, of useful mei~~~ ~tid metal c-oÃiipourids include ~anttaarlid~
w',d or 29 actinide metals or metal corr;pozinds:
31 The-se reactions, the metals or rrie'tal compoLind~ employed and the 32 conditions Linder which they can be run are disclosed in U.S. Paten:ts No, 33 4.734s537, issued March 29, 1988 to Devries e; al. 4,939 .31 1 Ysswed July 3"
-.:=y:7...
1 1990 to W~~~~~heck et al., 4,962,261: IsSUed October 9, 1990 to Abrevaya et 2 aI.: 5,095.1 61, issued March 10, 1992 to Abrevaya et aL; 5,105,044, issued 3 Aprii 14, 1992 to Han et al,; 5,105,046, issued Aprif 14, 1992to Washecheck;
4 5,238,698, issued August 24, 1993 to Han et a1.; 5,321,185, issued June 14, 1994 to van der Vaart; and 5.336;825, issLied August 9, 1994 to ChoLadhaÃy et 6 al., each of which is #r3cf3''pCtra:'~~d herein by reference in its entir'ety;
fy 8 Poly#'ne9Ezat3on vf 1-0leÃans The molecular sieve of the pr~sent. irivnnÃÃon may be used in a catalyst for the 11 poIymerizatiori of '#role#Ãns, e:g., the polymerization of ethylerle. -Fo #orm. the 12 olefin poIyryierizatÃon catalyst, the mo'ecular sieve as hereinbefore described 13 is reacted with a particular type of csrganomeÃai1ic cornpotind.
Organametaflif.
14 t: mpous-tds useful in forming the polymei-ixaÃion catalyst inCfude trivalent and tetravalent orgarioÃÃÃanium and organoc,lii-omÃum compounds having ilkyÃ
16 moaeÃÃes and, optionally, lialo moieties. 1>i the context of the preserit invention 17 the term "alkyi" ificiudes both straight and bran:cE~~d chain alkyl, cycloalkyl arld 18 a1karyi groups sr"rch as benzyl.
Examp:es of trivalent and tetravalerit argar-roch rOMir_ini and cj~ganotifaniGrrn 21 : ornpraunds are disclosed in U. S. Patent No. 4,376, 722, issued March 15, 22 1983 to Chester et ai,, U. S. Patent No. 4,37 7,49?, issued March 22, 1983 to 23 Chester ent aÃ.; U. S. Patent No. 4,446,243, issued May 't ; 1984 to ~`,;
hester et 24 a1., and U. S. Patent No. 4,526,942, issued Jufy 2, 1985 to Chester et al.
The disc"osure of the aforementioned patents are. incorporated herein by reference 26 in their enÃÃreby..
:...' 7 28 ExainpÃes of the organorrretalk compounds r:ised to form the polymerization 29 catalyst iric:IL~de, but are not iimited to, compourids corresponding to the general #om)u1a,;
32 MY,Xf,,:, -. .>
~>., I wherein M is a metal selected frun-, titanium and chrorriium; Y is aiky1; X
is 2 iialoger# (e,.g,, CÃ or Br); n is 1-4; aizd ni is greater th~~~~ or equal to r, and is 3 3 or 4.
Exam.ples of organotitanium and organoGFiromiurn compounds encompassed t by such a formula compounds of the Iffirmula CrY4, CrY:, CrY5X, 7 CrY2X, Cry=,X2, Cr"YXr; C rYX;, TiY4, TX3, TiY3K l"iY2X, `T'iY?X, TiYX.::, TiYXv :
8 wherein X can be CÃ or Br and Y can be methyl, ethyl, propyl, isopropyl, butyl, 9 isob;:Ãfyl, sec-butyl, teÃ-trbutyl, perifyl, #sopentyi, ne,+penty+l, hexyl, isohexyl:
neohexyl, 2-ethybutyl, octyl, 2--ethgrlhexy&, 2,2-d:ethylbuty(; 2-i~~~~~pyÃ-3~
~ 1 methyÃbutyl, etc:, cye ohexylallcyl~ such as, for example, cyclo he:xyim ethyl, 2-1 21 cyclohexylefhyl, 3-wycly hexyÃp ropyl, 4-cyc#ohexylbutyÃ,* and the t,oÃ-responding 13 a#kyl-substktuted cyclohexyl radicals as, for example, 14-14 methyleyclahexyl)mekhyl; neophyl, i;e., beta, heta-dimethyl--phenethyl, benzyl..
ethylbenzyl, and p--ise~.~ropylbenzyd. l"'referre~ exaimples of Y include C;--5 alkyl, 16 especÃaily htityl.
'~
18 The organotitaniurn and organochromium fTlaterials employed in the catalyst 19 can be prepared by techniques well known iri the ad. See, for example th<.
aforementioned Chester et aI, patents.
22 The organotitanluÃ~i or organochromium compouricfs c-asi, be with ttie 23 molecular sieve of the present irweni;on, such as by reactir-ig the 24 orgar o metalI Ãc compound and the molecular sieve, in order to form the oiefÃÃ-i polymerization catalyst. Generally, such a reaction takes place in the samp-26 reaction med~~im used to prepare the organ ometaiiic compound under 27 conditions which prornote formation of such a reaction prc~~uct. The 28 molecular sieve eari: simply be added to the reaction mixture after formation of 29 the oÃgartofnetallic compound has been completed. Molecular sieve is added 3 () in ari amount sufficient to provide fr~~ about0,'i to 10 parts by weight, 31 preferably from about 0.5 to 5 parts by weigl-jt, of organametallic compound in u2 the reaction mediuni per 100 parts by weiglit of molecular saeve.
.. !.~}_.:
2 Ternperature of the reaction mec'aum durÃng r~action ot orgenvmetaili~
3 compoL;nd with rnafecu;ar sieve is also maintained at a level which is low 4 enough to er ssure, the stability of thip, organometallic reactar#t. Thus, terflperatures in the range of froni about -150 C, to 50" C., pa-eferabiy from 6 about --8W C, to O" C. can be usefully employed. Reaction times of from 7 about 0.0 1 to '&C, hours, more preferably frorn- about 0.1 to 1 hour, can be, 8 employed in reacting the organotitanium or organor:hrorr3>um Wors?paund with 9 the molecu(ar, sieve_ 11 Upon completion of the reacticn. the catalyst mater~al so formed Ãrlay be 12 recovered and tirA~d by evaporating the reaction medii._,m solvent under a 13 nitrogen atmosphere. Alternat#vc-ly, olefÃti poIyrrserizatiori r-~actions can be 14 conducted in this sarrie solvent based reaction mediuryi useci to forrri the catalyst.
'16 .
17 The polyi-nerÃzation catalyst r:~~~ be used to catalyze polymerizat{oel of1 -IS olefins. The polymers produced r:ising thecatalysts of this inventiori are 19 normallyso4ad polymers of at least one mon,a-l-oletin coritair;irrg from 2 to 8 f-arborr, atoms per moiecuie. T~~~c- polymers are normally solid 2-1 homopolymers of ethylene or cc?poiyrTiers of ethylene wiÃra another rnono-l-.
22 olefin coriLtaining 3 to 8 carbon atoiiis per mo~~~~..sile. Exemplary copcalymer6 23 iii;..;iude ttiose of ettiylenelprapylene, ethylene/1-butenÃ:, ethylene:111-hexane, 24 and ethykes~e/i -o+;ter3e and the iike. The major portior~ of such copolymers is derived fro$r, ~thy3ene afid generally consists of about 80-99, preferably 95-26 mole percent of ethylene. These palymers are well suited for eAr,.rsion;
blow 27 mofdirig, injection molding and the ~~ke.
29 Thip, polymerization reaction can be cotiduCtec~ by confactdng monomer or monomers, e.g., eti7ylene, alor~e or with one c-t rriore other oiefÃr;s, and in the 31 substarstial absence of cafaiyst poisons such as moisture and air, with a 32 catalytic a3rtiaurrt of the supported organometwIl,c caia:ysi at a temperature 33 and at a pressure sufficient to 3riitiate the polymerization re-actiorl, If desired, _:_l==0 1 ari iraert organic soivent may be used as a diluent an{ to facilitate materÃa!s 2 handling if tt~e polymerization reaction is {:,or,dur:ted' with the re-actants in the 3 liquid phase, e.g. in a particle form (slurry) or soiu#>on process. The reaction 4 Ãyiay also be conducted with reactants in the vapor phase, e:g:, in a tluid':zed bed arrangement in the abser3cp- of a sc.lvetit but, if desired, in the presence of 6 an inert gas such as nitrogen.
;f 8 Thp- polymerization reaction is carried out at temperatures of frcarr, abotit 30`
9 C. or less, tip to about 200" C. or rnore; depeslding to a great extent on the operating pressure, the pressure of ti-se o'etjri monomers, and the particulaB'.
11 catalyst being used and its concentration. Naturally, the selected operating 12 temperature is also depeÃider?t upon the desired polymer melt index since 13 temperature is definitely a tactor iÃ) ad,iusiing the molecular weigtit of the 1,4 polymer. i~'referably, the temperature Lrsed is from about 30" C. to about 00' C. in a cor;vention',.-A slurry or "particle forming" process or from 10~.r"
C. tO
16 150' C. in, a "soIut;ori forming" process. A ternperature of from about 70' C to 17 11 D" C. can be emplayr:d for fluidized bed processes.
19 ~I-te pressure to be used in the polymerization reactions can be any pressure sufficient to initiate the poIymerizatioÃi of the moriomer(s) to high molecular 21 weight pralyÃ~er. The pre5sure, ttterefore, can range from subatmospheric 22 prp-ssures, using arà inert gas as diluent, to ~uperatmc~~~hf-rÃ~, pressLires of up 23 tc, about 30,000 psig or mare. The preferred pressure is from atmospheric (0 24 psig) up to about 1000 psig. As a ggeneral ruie, a pressure of 20 to 800 psig is most pr~fe-rred.
27 The selectiori of an inert orgariic solvent mediuÃ~n to be employed in the 28 so#Litian or slurry process embodiments of this invention is not too critical, but 29 the ;oives-it should be ineil to the supported organometallic catalyst and olefin polymer produced, and be stabÃe. at the reaction temperature used. It is not 31 necessary, t~~ow~.~ver, that t.iie inert organic solvent medium also serv'p-as a 32 solvent for the. poiymer to be tarod~iced. Among the i>;ert organic soivents 33 applicable for stich purposes rriav bc mentioned saturated aliphatic -4-1, `I hydrocarbons having from aboarPt 3 kc) 12 car-taon atoms per rno1~cuie such as 2 hexane, heptane, pentane, #sooctane, parmf,ed kerosene arid the like;
3 sat4araied cyicica'~~~haÃic hydrocarbons having from a~.~oL,t 5 to 12 carbor?
4 asorTss per rrFole,:~le such as cyclohexane, cyclopentane, dimethylcyclopentane and methyIoyclohexane and the l;ka and aromitas;
6 hydr"ocarbor'is having from about 6 to 12 carbon atoms per mralecuÃe such as 7 benzene, toluene, xylene, and the like. PartÃctilarly preferred soIveFit ri-iedia 8 are cycbhexane, peritane, hexane and heptane.
Hydrogen ~.an be.sntrodUced into the polymerization reaction zone in order to 11 decrease the molecular wetgFat of the polyrners producaci k1l.e.. give a much 12 higher Melt 1nd;:x, M1). PartEaE pressure of hydrogen when hydrogen is used 13 car~ be withi;n the rarige of 5 to 100 psig, preferably 25 to 75 psig. The mel':t 14 indices o#the, polymeÃ-s pr~ducedÃrr aceordaÃice with the instant invt.ntion can range frorri aboLit 0.1 to about 70 or even higher.
x~
1More detailed descrlption of suitable poAymerÃzatior, Ã,oÃiditÃons irieludmn~
18 exarxipl~s of particle form, solution and fluidized bed polymerization 19 arrangements are #or.:nd in Karapiraka; U.S. Pat. Rlo. 3.709,853, Issued Jan. 9, 1973 and Karol et al; U.S. Pat. I*to. 4,086,408; Issued Apr. 215, 1978. Both of 21 these patents are incorporated herein by r=e-fererice.
23 ~ +c~ iÃ~r~tr:an SSZ-75 f:aÃ) be used in a catalyst to catalyze hydrogenation of a hydr=ocarbor~
2 f 3 feed containing unsaturated hydrocarbons. The unsaturated hydrocarbons 27 c ~n, comprise. olefins, dienes, polyenes, aromatic compounds and the like.
29 Hydrogenation is accomplished by contacting the hydrocarbon feed containing wnsaturated hydrocarbons with hydrogen in the prewence of a 31 catalyst comprising SSZ- 75. The catalyst car; also coÃitaan one or more 32 ,-netals ofi Group VIB and Gror~p VIII, including salts, complexes and solutions 33 thereof, Reference to these catalytically active metals rss gntentled to -4.2-1 encompass such metals rjr meta$s in the elemental state or in sÃ?nre roÃ-ÃYl such 2 as an oxide, sulfide, tiaf#de, carboxylate and the leke: Exarnples of suvh, 3 metals include metals, salts or r:oÃ~~~~~~~58 wherein ti-ie nrtetai is selected from 4 the gr-aiip consisting of platinum, palladium, rhodium, iridium or combinations tfiereof; or the grou:p consisting of riickel, moiybder-rurn; cobalt, tungsten, 6 fitani;.r9-n, cttron7ium, vanadium, rhenium, manganese and comb#rations 7 thereof.
9 "(_he hydrogenation component of tt~~ catalyst (i.e., th -0 at:rarementi~..~ned rr#et,al) is pÃeserit #r, an amount effective to provide the- hydrogenation function of the 1.1 catalyst, preferably in. the range of from 0.05 to 25% by v~eight.
13 Hydrogenation conditions, sr_icti as tr:mperats:Ãre., iaressure, space veiowities, 14 contact time and the like are weIE known Ãri tlio-, art.
16 ~SZ-75 is usefuo as aÃi adsorbent tor gas separations (owing to its hÃqh pore 17 voiut-Tie wh,ile maintaining difftision control arid hydrophot}icity). SSZ-75 can 18 also be used ir~ a catalyst for converting oxygenates (such as metnaÃzoi) to 19 olefins, and for r-ciakirag small amines, SSZw7 5 can be used to reduce oxides of nitrogen in gas streams (such as automotive ex~~L3st) . SSZ-71: can aliso be 21 used ~~ a cold start hydrocarbon trap Ãri coz-rTbt_istiorr engine polfu.ivl3 control 22 syster-rTs. S5Z-75 is particularly useful for tÃappiÃig G; fragr-nenis.
24 T'he molecular ~~p-ve of the preser3t. invention can be used to separate ~~ss'es.
For example, it cari be used to separate carbon dioxide from natural gas.
26 T1{pieaiiy, the molecular sieve is Ãised as a cornponent in a memdrane, that is 27 used to separate the gasses. Examples of such membranes are disclosed in 28 U. S. Patent No. 6,508,86Qs ,ssa~red January 21 , 2003 to Kulkarni et a1., which 29 i!~ incorporated by re-fereÃi;e herein in its entirety.
31 The molecular sieve of the present inventaor, c.ar3 be used in aca¾aiyst to 32 prepare methylamine or dÃmethyEarliirre. DÃmethytamisRe is generally prepared 33 in EÃtdtÃstrial quantities bw ~ontinuo "; r~act:on of methanol (andior "I dirr;ethÃyIeifieÃ-j and ammonia in the preserÃce of a siÃica~-aluE-nina c.atalyst. The 2 reactants are typic~.ai9y combined in the vapor phase, at temperatures in the 3 range of 300"C; to 500'0, and at elevated pressures. Such a process is 4 disc:'Ioaed in U. S. Patent No. 4737,592, issued April 12, 1988 to Abrams et aL> wh_ch?s incorporated by reference in its entirety.
7 The catalyst is i-Ãsed ir: its acid form. Acid forms of moEecularsieves can be 8 prepared by a variety of tecfir;iq(jes. Preferably, the molecular sieve used to 9 prepare dimethylamine will be in tt~ehydrogen forÃY),, or have an alkali or a,kafinw earth metal, such as Na, K, W or Cs, ic:n-exchanged into it.
.z.t 12 The process of the present invention involves reactnc~ m eth~=I o>,:
133 dimethylether or a mixture thereof and ammonia in amotAnts siaff icient to 14 provide a c~arbon/nitrc~~en. "CIN} ratio from about 0.2 to about -1.5j preferably about 0,5 to aboÃ.it 1.2. The r~actior~ ~s conducted at a temperatt#i-e from 16 about 2a0t'~.:~ to about 450 G, preferably about 300 C to about ~`~00"C..
17 Reaction pressL:res can vary from about T-7000 kPa ( 1 -1000 psi), preferably 18 about 70-3000 kPa (10-~500 psi). A methanol and1oà d=ÃnethyletheÃspace time 19 of about 0.01-80 :~ours, preferably 0,10-1.5 hours, is typically used. ThÃs space time is calculated as the mass of cataÃyst divided by the mass flow rate 21 of rne}hano!rFdsrnethylether introduced into the reactor.
23 SSZ-75 may be t_Ãsed f{ar the cataiyk~c. reduction of the oxides of nitrogen in a 24 gas stream. Typically, the gas strearp, also contains oxygen, often a stoichiometric exz: ess t1-3ereaf; Also, the molecular ~~eve may contain a metal 26 ar, metal ioà s of on it which are cva~aWe of catalyzing the reduction of 27 the raitÃ-agen: oxides. Examples of such rneta14 or metal ions include cobalt, 28 coppeÃ-, platinum, iron, chrommm, mangai~aese, raickol, zinc, ;an}har;~urn, 29 palladium, rhodiuiri and mixtures thereof.
31 Orie example of such a process for the catalytic reduction of oxides of 32 nifrc,geÃ) in the ~reseÃice of a zeo1-tc ,s dascfosud !M US. Patent No.
4,297,328;
33 issued October 27, 1981 to Pitsctze-- et al., which is incorporated by reference -44.-1 tiereirl. There, the catalytic process is iiie coriabustioÃi of c;arbo-i m~.~rloxsd~
2 2 ' aÃtd hydrocaÃboris and the catalyt{c redÃ.FctÃon of the oxides of riitroger, 3 contained in a gas stream, such as the exhaust gas from an interr;al 4 combLÃstion engine. The zeoiite used is metal ion-exchanged, doped e.~r5 loaded sufficiently so as to provide an effective amoukit of catalytic copper 6 metal or copper ions withiÃi or on the zeolite. IÃi addition, the process is 7 condLicted in an excess of oxidant, e.g., oxygeri 9 Gaseous waste products resulting from the combustion of hydrocarbonaceous fuels, such as gasoline and fuel oils, comprise carbor, mar*axide;
11 ~ydrracark;=s and nitrogen oxides a5 cTroducts of tõornbust:c~n cir incomplete 12 combustion, and pose ~.~ serious health problem with respect to poElÃat:onof the 13 atmosphere, While exhaust gases from other carbcanac~eotis fuel-burning 14 soL,rces, such as stationary engines, iradustrial furnaces, etu:, contribute substantially to air pollotiori, the exhaust gases from aLrtcma}ive e~,ngines are a 16 principal source of pollutiorÃ. Bo-caLise of these bealtr7 problem concerns, ttie 17 Environmental Protection Agency (EPA) ~~~s promulgated strict controls on 18 the amouÃits of carbor, monoxide, hydrocarbons and Ãiitrogen oxides which 19 aritomobiic:s can emit. The implementation of these controls has resulted in the Lese of catalytic converters to reduce the amount of pollutants ernifted from 21 automobiles.
23 In order to achieve the simultaneous conversion of ~arbori n-Ãonoxide, 24 hydrocarbon and nitr~geti oxide pOilufasits, st has becoÃi3e the practice to employ catalysts in conjLxÃir;tic.ri with a=r-ro-tuel ratio control nnearÃs.
which 26 functions in response to a feedback signal from an oxygen sensor in the 27 engine exhaust system. Although these three component control cataly~~~~
28 work quite well after they have reached operating temperature of about 300V
29 C., at lower temperatures they are. not able to convert substantial amoLirit~ of the pollutants. What this rrÃeans- is that when an engine and in partccu#ar ar~
31 automobile engine is started up, the three compoÃ;eit control catalyst is not 32 able to convert the hydrr3c;arbon5 aÃid other pollutants to 3nnocuoLis 33 , ompoÃar,cfs.
_45._ 2 Adsorbent beds have beer~ used to adsorb the hydrocarbons during the wold':
3 start portion of the engine. Although the process typicaily w;I~ be used with 4 hydrocarbon fLÃe1s, th:e instant invention cari aw:~o be taseci to treat exhaust streams from alcohol fueled erÃgirres. The adsorbent bed is, iypically placed 6 immediately before the catalyst. Thus, the exhaust stream is first flowed 7 through the adsorberit bed and then through the Cataiyst. The adsorbent bed 8 preferentially adsorbs hydrocarbons over water under the conditions ~.~,resent 9 in the exhaust st:ream. After a certain arriount of tirne, th-a adsorbent bed has reached a temperature (tYpically about "150 C.) at whici-i the bed is no longer 11 able to rerr1ove hydr-ocarbons from the exhaust stream. That is, hydrocarbons 12 are actually desorbed from ti~Ãe adsorbent bed irwsteadof being adsorbed.
This, 13 regenerates the adsorbent bed so that it rari adsorb hydrocarbons dtjr-ong a 14 subsequent colc.9 start.
16 1-he prior art reveais several references dealing witil the, Use of adsorbent 17 beds to minimize hydrocarbon emissions during -a cold start engine operation.
18 One such reference is U.S. Pat. No. 3.699t683 iri which an adsorbent bed i~
19 placed after botq~:~, a reduo;ng catalyst and an oxidizirig catalyst. The patenfee$
disclose that wiyen the exhaList gas 5treami is below 20V C. the gas stream is 21 flowed through the reducing catalyst then Lttir-ougi=~ the oxidizing r-ata(yst and 22 finally through the adsorbent bed, thereby adsorbing hydrocarbons ori the 23 adGorber=t bed. When the temperature goes above 200' C. the gas stream 24 which is discharged f"roni the oxidation catalyst is divided intr:~ a major and 24 mirior portion, the rnajor portion being discharged directly inta the atmosphere 26 and the minor portion passing through the adsorbent ~~d:: whereby unburned 27 hydrocarbon is desorbecf and then flowing the resulting minor portion of this 28 exhaust stream coritaÃning the desorbed unburned hydrocafbons into tht::
29 engirre where they are burr~ed.
31 Another ref&ence;s U.S. Pat: No, 2,942,932 which teaclfiew a process for 32 oxidizing carbon monoxide and hydrocarbons which are contained in exhaust 33 gas streams. 1-he process disclosed in this patent consists of flowing an 1 exhaust strearÃ-i which is below 800' #= , into an adsarptior.. zone which adsorbs 2 the carbon monoxide ar~d hydrocarbons and then passing the resuitant 3 stream from this adsorption zone into an oxidation zc?ile. VVhen the 4 temperatÃii-e of the exhaLest gas stream reaches about 80W F. the exhaust stream is no longer passed through the adsorption zone bLIt ks passed directly 6 to the oxidation zone with the acÃditÃo!i of excess ~.~ir.
8 U. S. Patent No. 5,078,979, issued JanÃaary 7, 1992 to DLrnne1 which is 9 incorporated hE:rd=:in by reference in iiw entmÃely, discloses treatÃnc, aÃ:
exhaust ~as. stream from an engine to prevent cold start ernfssions using a molecular 11 sieve adsorbent bed. Examples rsfthe molecular sieve include faujasites, '12 c!inoptiiolites, mcrderÃites, chatrazite; silicalite, ~eoii~e Y, :altrastable zeolite Y, 13 and ZSM-5.
Canadian Patent No. 1,20500 disclc.>~~~ a method of reducing exhatist 16 emissions from an alcohol fueled automotive vehicie: This method consist's.
of 17 directing the cool engine staÃtup exhaust gas through a bed of zeoiite particles 18 and then over aii oxidation catalyst and then the gas is discharged to the 19 atmosphere. As the exhaust gas streamwarms up it is continuously passed 2i;.~ over the adsorption bed and then over the oxidation bed.
22 As stated this invention generally reflates to a process tcjr treating an engine 23 exhatÃst stream and in particular to a process for rrinir-,izing emissions di-irir~g 24 the cold start operation of an engine. The engine consists of any internal or external combustior, eÃigine which generates an exhaust gas stream 26 co;-itaining noxious components or pollutants inc,iuding ur~bi-3rÃaed of ihermaiÃy 27 degraded i-iydrocarbons or similar oraanic.s. Other Ã~OAC)LIS components 28 usualiy preseÃit in the exhaust gas include nitrogen oxides and carbon 29 monoxide, '1'he engine may be fueled byi a hydrocarbonaceous tue'. As used in this specification and in the appended claims, the term "hydrocaYbor~~~~ous 31 fuo-Ã' includes hydrocarbons, alcohols and mixtures t4-terp-of. Examples of 32 hydrocarbons which can be used to fuel the engine are the mixlures of 33 hydrocarbons which make Lip gasoline or diesei tuel. The aicohols which may ~~
..~õ,_ 1 be used to fuel engines include ethano: and methanol. Mixtures of alcohols 2 and rnixt;.Ãrey of a;coI-Ãois and hydrocari;3ons can aÃso be used. The.
engine 3 may be a jeseng;rre, gas tLÃrbire, irternal combustion engine, such as an 4 aLÃtoryiobiie, truck or bus enqine, a diesez engine o;, the ;Ãke. 'The process of this invention is pafliculariy suited for hydrocarbon, aicc-hol, or hydrocarbon-6 alcohol mixture, internal combusticin engine r1,ourited in an automot?'Ãie, For 7 convenience the desc;riptiori will use hy+drocarborx as the fuel to exemplify the 8 Ãniven#ion. The Lrse of hydrocarbon ir, the subsequent description isnot tobe 9 construed as limiting the in,rention., to hydrocarbon fLre!'ed engines.
11 When the engine is started up, it produr;es a relatively high concentration of 12 hydrocarbons in the engine exhaust gas stream as well as other poi[utants.
13 Pollutants will he used herein to collectively refer to any unburned fuf-'l 14 components and combustion bypr~ducts four3d irà the exhaust str-earii.
i==of example, when the fuel is ~hydrocarbon fuel, hydrocarbons, nitrogen ox;des, 16 carbon monoxide and other corgibustÃon byproducts will be fioLÃrtd in the engine 17 exhaLÃst gas stream. The temperature of this eiigirie exhaust stream is 18 relatively cool, generally below 500' C. and typically ir) the range of 200" to 19 400" C. This engine exhaust stream has the above characteristics during the initial period of engine operation, typically for the first 30 to 120 sec~~d,-;-, after 2-1 s+artcÃp of a coid erigÃrÃa. The engine exhaust stream will typÃeally contain, by 22 voitÃme, about 500 to 1000 ppm hydrocarbons.
24 The engine exhaust gas stream which is to be treated is flowed over a molecular sieve bed comprising i-nolecular sieve 5SZ-56 a first exhaust 26 strearr). Molecular sieve ~SZ-56 is described below. The first exhaust stream 27 5vvhact3 is discharged frorii: tt7a rrr6ecuiar sieve bed is riow flowed over a 28 catalyst to convert the pollutants contained Ãri the `:: st exh,au5i stream to 29 innocuous components and provide a treated exhaust str~~m which is discharged into the atrrosphere. It is understood that prior to discharge into 31 the atmosphere, the treated exhaust stream may be flowed through a muffler 32 or other sound reduction apparatus well known in the ari.
2 The catalyst which G used to convert the PoIfutarrts to innocuous componerrt~
3 is usual'y referred to in the, ar;as a thr'ee-component coÃitrol catalyst because 4 it can sirnuItar~eousiy oxidize any residual hydrocarbons present in the first exhaust strearn to carbon dbxide and water, oxidize any residual carbon 6 monoxide to carbon dioxide and redLice any Ães'r~~~a$, nitric oxide to rÃitrc~~er, 7 and oxygen, iri some cases the catalyst may notbe required to conve-rl nitric 8 oxide to nitrogen and oxygen, e.g., when an alcohol is used as the #Lref. In this 9 case the catalyst is called an oxidation ca#aiyst. Because of the re1atEveiy :ow temperatÃ.ire of the engine faxhaust stream and the first C-.xhaust stream, this 11 cataf;sst.. does not funr-tion at a very high efficiency, therf-'by necessitating the 12 mo?eculaà sieve bed.
14 When the mo;ecuiar sieve bed rc-~~~~~ a sufficient temperature, typically aboLit 15-0-200" C., the pollutants which are adsorbed in the bed begin to 16 desorb aÃid are carried by the first exhaust stre-am over the uataiyst. At th:is 17 point the catalyst has reached its operating temperature and is therefore 18 capable of fLeiiy eonvertirig the pollutants to innracÃaous components.
The adsorbent bed used in the iristarrf invention can be conveniently 21 employed in particulate form or the adsCrbeint can be deposited orrto a soiid 22 monolithic carrier. VVhÃ:n pardÃeuiate form is desired, the adsorbent can be 23 formed into shapes such as pills, pellets, granules, rings, spi"ieres, etc:
In the 24 em~.~poyment ot a monaiithic form, it is usually niost cc~nvenieÃit to er-nploy the adsorbent as a thin film or coating deposited ori an irieÃ-fi cari"ier material whici') 26 provides the strtictLiral support for the adsorbent. The Ãnert carrier material 27 can be any refractory ma-tefia( such as ceramic or metallic mate riais. It Ã-s 28 desirable that the carrier ÃTiateriaf be unreactive with the adsorbent and Ã:Ãot be 29 degraded by the gas to which it is expvsed= Examples of suitable ceramic rrÃateriaas include sillimanite, petalite, cordierite, mull:te, zircon, zircori mullite, ~j spondurnene, aIurniria-iitariate, etc. Additionally, metallÃc materÃalswE-aioh are 32 within the scope of this invention include metais and alloys as disclosed ir~
I U.S. Pat. .. No. 3,920,583 which are oxidatior) resistant anfA are otherwÃse 2 capable of w:thstanding high temperatt.:res.
.~;
~
4 The carrier material can best be utiiized in any rigid urÃitar;s corafiguratios~
which provides a pluralily of pores or ciiannel~ extending in the dÃrection, of f.~ gas flow. It :s preferred that the conf'gu,ation be a honeycomb c.onfiguration.
7 The honeycomb structure can be t.ised advarit~~eotisiy in eÃthL:r unitary forn'l, 8 or as an arrangeÃreÃit of multiple modules. The honeycomb structure is 9 usually or;ented such that gas flow Ãs generally wn the same d:rection as the cei1s or channeis of thp. honeycomb structure, For a more detailed discussion 11 of monolifhic WtÃCtÃ.Ãres, refer to U.S. Pai: Nos. 3,785,996 and 39:167,453.
13 The molecular sieveis deposited onto the carrier by any convenient ~a- y well 14 knowr, in the art. A preferred method invoi~~~~ preparing a slurry using the rno1ecuIar sieve and coating the rÃionolit.hÃc. honeycomb c.arm=1r with the slurry.
16 The slurry can be prepared by means known ir, the art such as combining ~~ie 17 appropriate amouna of the mo1ecu1arsiewe arid a binder with water. This 18 mixture is then blended by using means such as sonificatioÃi: milding, etc.
T'hi~
19 slurry is uses~ to coat a monolithic hc+sieyf.>r,mb by dipping the honeycomb into the siurÃv, removing the excess slurry by draining or blowing out the channels, 21 and heating to about 100J C. If the ttesired loading of molecular sieve is not 22 ac1iÃeved; the above process may be repeated as many times as requtred to 2 "'15 achieve the desired loading.
lnstead of depositing the molecular g-ieve onto a monolithic honeycomb 26 stÃ'uctijrc-, one car, take thc-.,; molecular sieve a9id #orrri 3t into a mor2o3ith:c 27 honeycomb structure by means known in the art.
29 The adsorbeÃ~t may optionally contain one or more catalytic metals clÃspersed th;:reon. The rTietals which ca:~ be dispersed on the adsorbent are the noble 31 metals wtZÃcl-i consist of platinum, palladium, rhodium, r.,thenium. and v2 rnixt:ures thereof. The (lesiÃ'ed knble metal may be ~eposÃt~~ onfo the 33 adsorbent: which actsas a support, in any suitable manner welr known in the r50 1 art. Orle example ca# a method of dispersing the r~oNe metak. onto the 2 adsorbent support involves impregnating the adsorbent sr,z poÃt with an " aqueous solution of a decomposable compound of the desired rioble rrieta( or 4 metals, drying the adsorbent which has the noble metal compound disperseci ari it and then caiciriing in aiÃ, at a temperature of about~~0' to about 5~.~0' C.
6 for a time of about 1 to about 4 hoor-s. By decoi-nposakale compor.rnd is meant 7 a compound wliÃeh upon heating in air gives the metal or metaY oxide.
8 Examples of the dewomprasaNe compounds which can be used are, set for-th 9 in US, Pata No. 4 , 791099 whÃch is incr;'rporat~~ by reference. Preferred decomposable compounds are chloroplatinic ac$d, rhodium trichloride, 11 rhlo:-opalladic acid, i~Ãexachioroiri~~~tc- (IV) acid and hexachlororuthenate. It is 12 prefp-rab1e that the noble metal be present in ari amount ranging from about 13 0.01 to about 4 weight percent of the adsorbent srappoÃl. Specifically, in the 14 case of pÃatintam and palfadiGiÃn the range is 0. 1 to 4 wxeigi-it percent, whi~~ in thc- case of rhodium and rutt~enium the range is frong about 0.01 to 2 weight 16 percent, 18 These catalytic i-rietaEs are capable ot oxidizing the hydrocarbon and carbon 19 monoxide and reducing the, nitric oxide components to innocuous praducts.
Accordingly, the adsorbent bed can act both as an adsorbent and as a 21 cataiyst:
23 The catalyst which is used iÃ-, this invention is selected frorri any three 24 component contrc,i or oxidat:on catalyst well kÃ:own iÃi the ark. Examp4es of catalysts are those described in U.S, Pat. Nos, 4;528,279; 4,791,091;
26 4:760,044; 4.868:148: and 4;868,149, wi~ieh are all incorporated by reference.
27 Preferred cata;ysts well known in the art aÃ:e those that contain platinum and 28 rhodium and optionally paIladitam, while oxidatior) ca#aIyst;, usually do not 29 contain rhodiLsÃgi. Oxddatiari catalysts usually contain platinum aÃid/or pal1ad:urn metal. These catalysts may also coiitain promoteTs and stabiiizer~
31 such as barium, cerir..;m, lanthanum, nickel, and irorr. Ta~~ noble metals 32 promoters and stabilizers are usually deposited on a support such as alumina, 33 siEsua, titar7ia, zi= conia, alumiÃ~o Oicates, and mixtures thereaf with alumina ..~.~-1 beÃng preferred. The catalyst can be conveniently employed in paÃticulate 2 form or the watalytic composite can be deposited on a 5olid monolÃthiz rarrier 3 with a monoiit~ic carrier being preferred. The parliculate form and monolithic 4 form of the cataEyst arp- prepared as described for the adsorbent above.
6 The molecular sieve used in the adsorbent bed, SSi:.vi 5, comprises a 7 crystalline Eiiof~cular sieve having STI topology and having a mole ratio of at 8 least 15 of( 1) an oxide of a first tetravalent element to (2) an oxide of a 9 trivalent element, pentavalent element, second tetravalent e?esTielit wh;ch is 1,0 different from said first tetrav@len# element or mixtuee, therecatr 12 'The present invention oomprÃses a process for catalytic conversion of a 13 feedstock comprising one or more oxygenates compÃis#ng aicohois and ethers 14 to a hydrocarbon product containing light olefins, s.e., C2, G,5 and/or C4 oiefans.
The feedstock is ;oritactr:d with the molecular sieve of the pre:~e-nt inven~tion 16 at effective process conditions to produce light oÃef;iis.
18 The term ` oxyger te" as used here's.n designates compounds sucti as 19 alcohols, ethers and rr.ixtures there of. Examples of oxygenates include, but are riot limited to, methanol and dime-t'17yrl ether.
22 The prc~ess of the present invention may be candtictied ir:~ the pr'eset7 cw of 23 one or more diluents which may be present in tYie oxyge-iate feed in an 24 amount between about 1 and aboÃi: 99 molar perc~rA, based on the total number of moles of all feed and dilueÃit comp~~~ents. Dil4ierits include, but arÃ~>
26 not limited to, heliuni, argon, nitrogen, carbr~~i monoxide, carbon dioxide, 27 hydrogen, water, paraffins, hydrocarbons (such as methane and the like), 28 aromatic compoL:nds, or mÃxtLsres thereof. U. S. Patents No, 4,861,938 arid 29 4,677,242, which are ;ncorporated by reference hereiri rr) their entirety, emphasize the use of a diluent to maintain catalyst selectivitytowai'd the 3, 1 production of light alefins, particularly ethylene.
4.y 1 The oxygenate conversion is preferably conducted in the vapor phase such 2 that the oxygenate Peedstoa k is contacted in a vapor phase Ãn a reactÃon zorie 3 with the molecular sieve of this iri'vention at effective process conditions to 4 produce hydrocarbons, i.e., an effective teÃyi~.~erature, pressure, weight hourly space velocity (WHS\~) and, optionafly; an effective amoaÃi# of dilÃ.Ãenf. The 6 process is conducted for a period of time sufficient to produce the desired light 7 oIefiins. In general, the residence time employed to prodLice the desired 8 product can vary from seconds to a number of hours. It wili bp- rea~~ily 9 appreciated that the residence #EÃ-s-~p- w3lI be determined to a significant extent by the reaction temperature , the molecular sieve catalyst, the WHSV, ttie 11 phase (liquid or vapor) and process design characteristics. The oxygenate 12 feedstock fÃaw rate affects oIefira production. 1ncreasirig the feedstock flow 13 rate increases WHSV and enhances the formation of olefir productson relative 14 to paraffin prodr#ction. However, the eriianced olefin production reiatr~~
to paraffin production is offset by a dimimsl~ed ::oÃiversion of oxygenate to 16 hydrcacarbons.
18 'Fhe oxygenate cotiversÃon process i:s effectively carried out over a wide rarige 19 of pressures, inciuding aufioger3oLis pressures. At pressures between about 0.01 atmospheres (0.1 kPa) and about 1000 atmospheres (101.3 k-Pa), the 2 ?', fort-nat#cn of l4ht olefins will be affected althot#gh the aptimurn amount of 22 product will not necessarily be formed at all pte~~ures. The preferred 23 pressLire is behp,reen about 0.01 atmospheres (0,1 kPa) ~t-id abctif 1 00 24 atmospheres (10.13 k.Pa). More preferably, the pressure vviÃi range froril about I to about 10 atmospheres (10 1 .3 kPa to 1.013 Mpa). 'T'he pressur~~
26 referred to herein are exclLisiue of the, diÃÃ.ient, if any, that is present and refer 27 to the parlmai pressure of the feedstock as it relates to oxygemate.
cornpotrrÃds:
29 The temperature which r-pay be ew-np1oyed in: the oxygenate conversion process may vary over a wide range depending, at least in part, on the, 31, ÃTio1er:uiar sieve cataiyst, In general, the process can be conductp-d at ari 32 effect:ve temperature beton/een abcLsfi 200"C and about 700 u : A the lower 33 ~no' of the temper' ablire range, and t:liÃ~s generally at a lower i-:,it;
of reaction, w3-I the formation of the desired light olefins may become low, At the upper er2d uf 2 the rarige , the process may not form an opflmu=~n amoLint of light olefins and 3 catalyst deactivation may be rapid.
r, The molecular sieve catalyst preferably is incorporated into solid par-kicies in b wfijcli the catalyst is present Ãn an amount effective to promote the desired 7 conversion of ~xygeraates to light oleflns. In arie aspect, the solid particles 8 cornpr3s~ aicataEytÃcally effective amount of the catalyst and at least one 9 matrix material selected from the group consisting of binder mtiierÃaIs, õilleÃ, materials and mixtures thereof to provide adesiÃÃ:d property or properties, 11 e.g., desired catalyst dilutÃon, mechanical strength and the Iikc-, to the solid 12 partlcles. Such anatrix materials are, ofteerÃ,fo sorrie extent, porous in nature 13 and may or may not be effective to proiiiofe the desired reaction. Filler and 14 bÃnder materials 3ncluÃfe: for exarrÃp1c-, syntlie-tlc and nafurally occurring ~ 5 substances such as Ã~?~~tal oxides, clays, sil#cas; aluminas, s~l~r~~a ~1Ã: Ã~~#r~~~;
16 siliea-magnesÃas: s31ica-zirconÃas, si13ca--fhorias and the kÃice, If matrix 17 rriateria&s are included lri the catalyst composition, the molecular sieve 18 prp-fer-abI;i comprises about '4 to 99%, more preferably aboLit 5 to 90%, and 19 still more preferably aboÃ.Ãt 10 to 80% by weight of the total composition.
21 EXAMP1_-ES
23 The following examples demonstrate bLit do not limit fhe present :r3vention.
Example 1 26 Synthesis of A!-ConfainiÃ3g S5Z-7/5 28 1.5 mM of fetra rnethy ler~e- 1:4-b is-(N -m efhylpyrrol idirigu m) drca$lar, SDA
29 (3 rTÃAi OH;a was mixed m a Teflon cup (for a Parr 2-1 rr 1 reactor) with 1.26 grams of tetrzae$hy;orthosiiicate and the c p was placed irà a hood to 31 evaporate (as ethario; is formed from hydroly---i,,c;; over several days.
Wiien all 32 of the visible liquid was gc:ne, the Teflon cup was ruftivebglhed and water was 33 added to bring the HõOl&02 mole ratio to about four. Then, 12 mg of Reheiss 34 F2000 (50% A1:~C ~) was added and dissolved 6nto the reac;tion ÃnfaÃture.
This represents a starting synthesis muleratio, of Si021 A120::. of 100. Lastly, 0,135 ~54.
1 gram of 50% HF was added usinq a plastic pipette. The gel was rÃiÃxed wÃtta a 2 plastic spatuÃa and then the resaiting reaction rr:ix#are was heated iri acÃosed 3 vessel rotating at 43 RPM at 150'C for 16 days. Acrystalline product torny~~
4 which was recovered and found by X-ray dttfractirsn analysis to be molecWar sieve ~SZ-75.
7 Example 2 8 Synthesis otA~ontainingSSZ-75 The procedure described Ãri Example 1 was, repeated, except that the source 1 1 of alr.tniÃnum was l_.Z--210 zeolite (a form Ot deakin?ir=,ated FAU) and tile S021 12 A120; Mofe ratio was 70. The reaction formed SSZ-76 ir~ 10 days.
14 Exar~~~~~ 3 Svnthesis of AI-Cor?tainmnaSS~~,~_y 17 The procedLtre describe(I in Example I was repeated, except that the source 18 of aÃumind~~n was Catapa~ B (a form of pseLsdvbaehmite alumina), The 19 reaction formed SSZ-75 in 10 days.
21 Examp es 4-7 22 SynthesÃsof Al(,SilÃca SSZ-75 24 Aprocer~ure simiÃar to that of Exarrrple 1 vvas repeated using the reaction mÃxtur4 (expressed as mole ratios) aÃ3d conditions shown in the table beIow:.
26 The reactions were run until a crystaÃI;ne product was observed by SEM and 27 theki #h~ product was recovered. TÃie products are also shown ir, the table.
_,M5..
~
;--- -____- _= __- ---- _--- _-_-_-- -__--- _----_ __ ____________________ ~~~ ~r'~~.
Ex. SDr'~! S#~t N# 1.$ 15i01 H ~ a' ~#~~ ~fOl SiO2 "~..1~.P
----- __ ____________ ------------------------------ {
! - - -------------4 0.50 0.0 0.50 5.0 150/43 :... ,.______.__... :........... -=------ ---- --~ OA0 01 0.40 5.0 150r`4'o SSZ-75 ..__ _ 0: 30 0,2 0.30 5.0 150143 ~~-PA' ........... ------- ______ -------------,________ 7 0.20 o.3 O.20 i 5.0 150/43 A#ror zsm-4 P, .............. ------------------- - ....__- ---:.--------3 Example 8 4 Calcination of 13SZ-75 ---------------------------------------------------------6 The prodL3ct from Exatnple 1 was z..alcined 3r: the foIlowing manner: A thin bed 7 of material was heated m a flowir1g bed of ;air in a-nuffle turnace from rooEll 8 temperature to 120'C at a rate of I C per minute and held at 120 C for two 9 hours. The temperature is then ramped up to 540`C at the same rate and field at this ternpera.tu#re for three hours, after which 2t was increased to 594"t"
11 and held there for another three hours.
13 Example 9 14 Q_onaers:on ofMethanol 16 The calcined matenal of Example 8 (0.10) gram) was pelleted and, meshed 17 (with r~cycÃirg) to 20-40 mesh and packeci into a 3/8 i~icti stainless steel 18 reactor. After sufficierst purge with nitrogen Uarrier gas (20 cclrniri), t~~~
19 catalyst wa,,,, heated to 750'1" {399"C). A feed of 22.5% methanol in water.
~0 was ntrodu;ed into the reactor uia ;,y{s'~~~~~ ~~imp a{ a rate of 1.49 ~c/hr. A
21 sarnpie of the efFluerit stfearr~ was diverted to an ori-Iiiie gas chromatograph at .22 ten tiiinute point of feed introductÃon, SSZ .~ ~showed the following behavior~
24 MethatioI conversion = 1000/o No dimethylether detected 26 C2 ~(,4 iS about 70% of the prod;aci ..tir;..
I showed a mixture of olafins and sasLirates 2 Aromafrcs were made with ethA.arzene the most abundant single produa,~.
3 TrirF-sethylbenzene asamers were observed as the heaviest products At 100 miriL$Ekes ar7 straarn the SSZ-75 was foulang, but still produced the same 6 products (aathaugh very few aroriiatÃt,s were obsarved).
~; , _.
17 material, a-q well as minor shifts in the diff ractmon. pattern.
19 CrVstaÃiÃt~~ SS;~~~~ ~ can be used as-synthesized, but prei'erak,ly will be thermally tr~.ated (caÃciÃzed): Usually, it is desirable to remove t'ie aÃkaiimetaÃ
21 cation (if aily) by ion excharige ar~~ replace it.with hydragen; ammonium, nr 22 any desired r-nefiai ion. CaÃcÃnect SSZ-i 5 has an r`-~exarse adsorption capacity 23 of ak~oLit 0.15 cts/q.
;{3w 1 SSZ-75 can be formed into a wÃdÃ~> varaetyt of physical sP~~pels. Generally 2 speah9nq ; the i-nolecuÃar sieve cari be in the form of a powder, a granule;
or a 3 moaded product; ~uch as extrudate t;aving a partide si~~ sufficient to pass 4 through a 2-mesh Ã-l"yleri screen and be retaÃned on a 440:_rnesr} (Tyler) scr~en, fr, ccases where the catalyst is moided, sLÃch as by extrusion with an 6 organic binder, the SSZ-75 caii be extruded. before drying, or, dried or 7 partially dried and then extruded.
9 SSZ- 75 can be ~~n-ipc:sited with other materials resistant tc) ;he, temperattires and other conditions employed in organic conversÃori processes. SiAch matrix 11 materiaÃs include active and inactive materials and syritheaic or natu~'ally 12 occurri~~g zealite-, as well a,s inorganic materials such as Claya, siiÃca and 13 mefial' oxides. Examples of sucFi materials and the manner in which they can 14 be tised are disclosed i~i US, Patent No. 4,910,006, isstaed May 20: 1:990 to Zones c;t al., and US. Patent No. 5,316,753, . issued May 31, 1994 to 16 Nakagawa, both of which are incorporated by rerrrreaice hereir, in their 17 entirety.
19 H, ~~rocarbon Conversion Pr~~e-5 21 SSZ--r ~.~ molecular sieves are usefLil in hydrocarbon coriuersÃc,n reactions.
22 Hydrocarbon conversion reactions are ehern4cal and catalytic~ prace5ses an 23 which carbon containing c.campvurids are changed to different carbon 24 containing compounds. Examples of rsydrocarbon conversion reactions in which ~SZ-:r ~'~ is expected to be usefui inc:utÃe hydrocracking, dewaxirig, 26 catalytic crackiÃ~~ and olefiti and aromatics fwrmation reactions. The Catalyst~
27 are also ~~~ected't~ be useful in other petroleum, refining and hydrocarbon 28 roiiversics3-i reactions such as isarrerizir~g n-paraffiÃis and r~~phthenes, 29 polyÃrier;zing arid oligomerizing olefinic or acetylenic compounds such as ;~abLi1yIene and bute:ie-1, poÃynierÃzatgon of 1-olefins (e,q.; ethylene), 31 retiorrnÃng, isomerizing poÃyal'Kyl substituted aromatics (e.g.; m-xylene), and 32 disproportionatÃng aromatics (e,g., toluene) to provide mixtu:es of benzene, 33 xylenes and higher rnethyÃbenzerie5 and rWxidat~~n reaetÃons. Also included .:,lw I are rearr~.ar;gpment reactions to make various naphthalene ~.~erivatives, and 2 forming higher moiecul:ar weigt,f hydrocarbons trtvm lower -n-i~~~cula#
we#ght 3 hydrocarbons (e,:g., methane upgrading).
~`i The SSZ-75 catalysts Ã-fiay have high selectivity, and under hydrouar~on, 6 conversion conditÃoris can provide a high percentage of desired products 7 relative to total producxs.
9 For high catalytic activity, the ~SZ-75 Ãnoteor.rlar sieve should be predominantly in its hydrogen ion form, ~.~eneraf1y, the molecular sieve is 11 converted to its hydrogen form by arnrr onium exchange followed by 12 calcination. If the molecular sxeve, is synthesized with a high enough rati~,.} of 13 SDA cation to sodium ion, calcÃnatio#i a9one may be sufficient. It is preferred 14 that, after oatcinatioÃ7, at.1east 80% of the cation sites are occupied by hydrogen Ãosis and/or rare earth ions. As used hcrein, "predoriianatitly in the 16 hydrogen torm: means tFiat, after t:,alciÃiatian, at least 80% of the, cation s;tes 17 are occupied by hydrogen ions andtor rare earlh moris.
19 ~~~-75 molecular sieves c ar~ be Lr~ed in processing hydrc.rarboraaceaus feedstocks. Hydrocarbonaceous feedstocks contain carbori compounds and 21 cari be frorn r-nany different sources, such as virgin petroletirii fractions, 22 recycle pegroleurii fractions, shale oil, liquefied coal, tar sand oil, synthetic 23 paraffins from NAO, recycled plastic feedstocks. Other feeds include 24 synthetic feeds, such as those derived from a FÃscher 'l ropacfi process, ;ncludÃrrg ar, oRygenate-cont:aining Fis~~~er Trop'sch process boili-rg below 26 about 371'G L700 F), IÃ~ ~eneeal, the feed ~an;be any carbon containing 27 feedstock susceptible to zeolitic,:ata(y#ic reactions. Depending on the type of 28 processing the hydrocarbonaceous feed is to undergo, the 1'eed can co>-#tain 29 metal or be free of metals, it can also have high or low nitrogen or sa:,ltur impurities. It can be appreciated, howe-vrer, that in general processing wili be 31 more efficient (and the catalyst more active) the lower the metal, nitrogen, and 32 sÃaifur content of tl-ie fe-edstock, :>~
1 The conversion of ~ydrocarbon@cecaus feeds can take place Jzi ariy carivenient 2 mode, for example, in fluis~iizeÃ~ bed, rÃ-tcv:ng bed, or fixed bed reactors 3 depending crà the types of pfocc-ss des;Ã-ed. The fornnulafion of the catalyst 4 particles Mf vary ~ependirxg an the conversicÃi process and method of operation.
7 Other reactions which can be performed using the c~~~~~yst of this iravenfion 8 corltaÃnÃng a r-fiefai, e.g., a GÃ"ou~,.~ tfifà Ãiietal such platÃnLÃm, includp-9 hydroge nation-dehydroge nation reactions, denÃtr.oge nation and desufftirÃzaiior~
reactions.
12 'Fhe following faNe indi:.qfos typical reaction c~ndÃfiorts whic,i-Ã Ãilay be 13 employed when using catalysts comprising SSZ-75 in the f~ydrocarbon 14 coriversÃon reactions of this iriver9tion. Preferred coÃiditions are indicated in parentheses.
~?N
Temp. `C Presstire SV
t-iydroerackÃng 175.-485 0.5-350 bar ---------=--------------- ""-~ ....- -- ---------D~;a~a;~ia~ g 200-475 15-3000 psÃ+~, 01-`~Q
(2 50<~4,90) 0.103-20.7 Mpa (0.2-10) ga ge (200-3000, 11.38..
20- 7 Mpa gauge) ------- -------- ------------ r----------- ------"" -"--"-"_"
_-" __--___ -__________ ~
fr~r~~a~'jon (480-55M
- - -- - - ------------ -Cat: Ã racÃsinq A
atni. ) -- --_____ _ -,7--------------- - --_______---t7Ãic~or~~erizat;or~ 2:~2-649A ~a: 1 -50 atta~ (1,2 -,5 10-232" OM-2.
(27.-204)4' --------- { -____~.
~ar~~ins to 100-700 0-1000 psig arornatics - ----- ------ --- -------- --------- -- -------- ------ ____-_- -Corideiisation ot 2b.~-1000 psÃg, 0.5-50 -aÃcoÃ-iois = 0.00345-6.89 Mpa gauge --------- ------------------------ - ~" ------------" --_ ____ __ Ãsomerizatior~ 93-538 50-1000 psig, 1-10 #'204-3153 0.345--&89 Mpa (1-4) gauge ------------------------------------------ ----_-XyÃ~ne.
isoÃiaerizatior~ ...26O-593 ~'i~~ ~t~i~ (0.6-50), ,..
a8-3tf1.r 1-200 atm.4 ~ 15 - -5 '`~
~----------- _ -------------- "------------ - --------.-----""----_____"_~~ -. ----- ...... ~
2 ~evera4 hundred ;~~~~~~spÃietes 3 ` Gas phase rea~.~tion 4 ' Fiydrtsc:arboa-i partial ~~~~sune " Liquid phase reaction ~ 6 wÃ-isv 7 Other reaction cordi õ~~ons and parameters are proyridUd beÃow.
'14 ~
2 ~ ~~ocrackinq 4 Usmg a catalyst which comprises SSZ-75, preferably predom,nant:ly+ in the hydrogen form, and a hyciroger t>on pror-noter, heavy petroleum residual 6 teedstoi;ks, cyciÃcstoc;~~ and other hydrocrackate charge 'stocks can be 7 hydrocracked using the process conditions and catalyst components 8 dlscbsed in the atore P-nent3oned U.S. Patent No. 4,910,006 and U.S. Paterit 9 Nca. 5,316,753, 11 The hydrocracking catalysts corÃtain, an effectwe amount of at ieast one 12 hydrogenation cc#rnponent of the type ;:ommon3y employed in hydrocracking 13 catatysts. The hydrogenation component is generally selected from the, grcrÃ,Ãp 14 of hydrogenation catalysts consisting of one of more metals of Group VIB ar-~~
Group ;,t'iil. inci~idirig the saits, complexes arid solutions containing such. 'T`he 16 hydrogertakmori catalyst is preferai,;ly selected from the group of metals, salts 17 and cOmpiexes t~ef-eof of tt3e group consisting of at least one of platinum, 18 palladium, rhodiÃ.im, iridium, ruthenium and mixtures thereof or the group 19 s_.orisisting of at least one of nickeir molybdenum, cobalt, tLingsten, titanium, chromium and rnlxlures thereof, RetereÃ-ice to the catalytically active metal or 21 B-netals is BnterÃded to. encompass such metal or metals in the elemental state 22 or in some form such as an oxide, sLÃIfide, halide, carboxylate and the like.
23 The hydrogenatiosi catalyst is present iri ari effective amount to provide the 24 h}rdrogenationfuÃ`Ãction otti^ie hydrocracking catalyst, and prefarabiy in the rarige of from 0.05 to 25% by weight.
27 Dewaxing 29 For dewaxing processes, the catalyst comprises arnolecular sieve having STi tpology and hav;rig a Ãn6e ratio of at Ãeast 15 of (1) an oxide of a first 31 tetravalent element to (2) an oxide of a tF'#valarit element, pentavalee-.t element, 32 secoE'id tetravalent element which is different from said tirst te.trava[enT
33 eIement or mixture thereof. Thus, the molecular sieve may be SSZ-75 or-''~-1 TNU-10, preterainly predomÃnantly in the hydrogen torm, The catalyst can o.~
2 used to dewax hydrocaribar>aceous feeds by selectively removing straight 3 chain paraffÃm-s; Typically, the viscosity Ãradex of the dewaced product is 4 improved (eompared to the waxy t~~~) when the waxy feed is contacted with S SZ-75 or T'NU-10 urider isornerization i~ewaxÃrkg concÃiti~.~ns.
7 The catalytic dewaxing conditions are c~ependeait ir, large measure on the 8 feed used and upon the desired pour point. Hydrogen is preferably present in 9 the reaction zone during thp- catalytic ~ewaxing: process. The hydrogen to feed ratio is typir,a11y k~~~~~~~ about 500 and about 30,000 ~~F/bbi (standaru 11 cubic feet per barrel) (0.089 to 5.34 SCM/liter ;standard cLibic mete rsr`i:te r)), -12 preferab1~ about 1000 to abo~at 20,000 SC:;FF`bb! (0.178 to 3.56 SCM/iiter)~
13 Generally, hydrogen wii[ be separated from the product and recycled to the 14 reaction zoa-ae, Typical reedstor;ks include light gas oil, heavy gas oi~~
and reduced crudes boiling above aboui~501'i" L'177,C;.
17 ~"a typical dewaxing process is the catalytic dewaxing of a hydrocarbon oil 18 feedstock boilir~~ above about 350UF (17; ,"C) and containirig straighL
chain 19 and sl ;!htly branched chain hydrocarbons by contacting the hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pr~~sure of 21 about 15-3000 psi (0.103-20.7 Mpa) with a catalyst comprising SSZ-75 and at 22 least orie Group VIià metal, 24 The SSZ--75 or TNU-10 hydrodewaxing catalyst may optionally contain a hydrageriatÃon component of the type commonIy employed wn dewaxing 26 catalysts. See the, aforementioned U.S. Patent No. 4,910,006 and U.S.
27 i`'aketit No. 5,3416;753 f~.?r exaÃ~ip1es of ti'=~~~ehydrogenation Ct3rr,ponents.
29 The hydrogenation component is preseiit in an effect;ve arnu:ant to provide an.-effective hydrodewaxing and hydroisonierization catalyst preferably in the 31 range of from about 0.05 to 5% by weight. The catalyst Ã-nL~y be run in such a 32 mode to increase isomerization c~ewaxing at the expense of cracking 33 reactions.
2 The teaci may be hydroCra.cked, foll~~vp-d by dewaxing. This type of two stage 3 process and typical hydr~cracking condations are described #n U.S. Patent 4 No, 4,921,594, issuec9 :May 1, 1990 to Miller, wt7icti is incorporated herein by reference in its enkir-eiy.
7 S5Z-75 or 't-i=3U--10 may also be utÃfized as a cor-iib:riataor? of catalysts. That 8 is, the cataiyst comprises acombinatior-~ comprising rrioiectjlar sieve SSZ
f5 9 or TNir1-10 and atleast orie Group Viil rneta,~, and a second catalyst comprising an aiummosiiicate zeolite vvrtich. is more shape selective than 11 mcslecLilar sieve SSZ- l5 or TNLt 10. The combination may be comprised of 12 1ayers. The LÃse of layered catalysts is disclosed in U.S. Patent 13 Na. 5, 149,421, issued Septer~ber 22, 1992 to Miller, which is incorporated by 14 reference herein in its entirety. The layering may also include abect of SSZ-75 or TNU=10 layered withi a r:or-Ã-zeolÃtic component deslgF-.ed for eÃt(ier 16 hydrocrac;kir~g or liyrtrofiriishing.
18 S5Z-75 or 1'NU-10 may also be used to dewax raffriates, irtcludisig t3rlght 19 stock, Lsnder conditions sE~~~~ as. those cilsef.ase(i in U. S. Patent No. 4,181,598, Ã~stied January 1, 1980 to Gillespie et ai., which is 21 incorporated by reference herein in its entirety.
23 It is otter-r desirab!e to use mild hydrogariat#on (sometimes referred to as 24 hydrofinÃsh:iig) to produce more stable dewaxed products. The hydrotinishirg step can be performed either before or after the dewaxing step, and 26 preferably attes-. H, drotinÃshing is typicairy cond~~~~ed at tempera.tures ranging 27 from about 19VC to about 340 C atipreSsur-Ã:s from about 400 psiva to about 28 3000 psig (2.76 to 20.7 Mpa gatige) at space veItac3ties tLHSV; be'tbq~~~~
29 abcsrJt 0.1 anti 20 and a hydrogen recycle r ate of about 400 to 1500 SCiFlbl~+i (0.071 to 0.27 SCM/liter). The hydrogenation cafalvst employed must be 31 aative eraough riot only to hydrogenate the olefins, dioEetins and color bodÃ~~
32 which may be present, but afso to reduce the ararnati;; content, gLrltabIe.
33 hydrogeriat;or catalyst are discl~~e(J ;n U. S. Patent No. 4,92.111a594, isSiUed .,.~
1 May 1, 1090 to Miller, ,whic:h is #ncarpoÃated by reference herein in its entÃrety:
2 Thehydrofin;shing step is beneficial in prapanng an acceptably stable product 3 (e:g;, a lL,bric.atirag oil) sir~~~ ~ewaxed: products prepared froÃii hydrocracked 4 stocks tend to ~p- uristabfe to air and !Ãght aiid terid to form sludges spontaneously and quickly.
7 Lube oil may be prepared using SSZ-7 5 or TNU-1 0. For exampEe, a C20_> lube 8 oil may be rr,ac#~ by isornerizing a~~0, oIefÃn feed over a 4ata(yst compr`ssing 9 SSL-,75 or TNU-10 in the hydrogen form and at least one Group Vill metal.
Alternatively, the lubricating oil may be made by hydrocracking in a 11 hydrocracking zone a hydrocarbonaceous feedstock to obtain an efffuentt.
1'y.' comprising a hydrocracked o#i, and catalytically dewaxing the effluent at a 13 temperature of at feast about 4WF (204 C) and at apressÃare of from abotÃt 14 15 psig to about 3000 psig (0.1031-201 Mpa gauge) in the presen:ce of added hydrogen gas with a cataiyst comprising SSZ-75 or TNU- 1OF in the hydrogeri 16 form and at least one Group Vill metal.
18 Aromatics Formation SSZ-75 cran be used to convert light straightrLan naphthas and similar 21 mixtures to highly aromatic Ãnixtutes, Thus, normal ar7d slightly branched 22 chained hydrOcarbans, preferably t ving ababiiÃig range above about 4Ã3 t;
23 and less than about 200"C, can be converted to prodEaCt~ having ~substantsaf 24 higher octane aromatics content by contacting the hydrocarbon feed with a catalyst comprising SSZ-75. It is also possible to conveat heavier feeds into 26 B'T-X or riaphthaler-e dei-ivatives of vaiÃ.:e using a catalyst comprisiÃ~g SSZ-75.
28 T~~~ ~onversion catalyst preferabiy contains aGrs~~~p VIII mp-tal compound to 2 9 have sufficient activity for commercial use. By Group VIII iiieta&
~~~~lpauÃkd as used he--eiÃi is meaÃit the metal itself or a cctmpoLir;d thereof. The Group Vlll 31 noble metals and their compounds, piatisium, palladau:m, and irictiurTi, or 32 combinations thereof caÃi be cised. Rhenium or tin or a mixture thereof may 33 also be used ;n corijuÃictiori with, the Group ViIl iiiet~t compouFnd and _._'~
I prt-farab(y a noble metai compound. The most preferredr.r~Ãetal is piaiÃnurn.
2 The amoLint of Grcatsp Vlil metal preseÃit in the conversion catalyst should t~~
3 within the normal range of use in reforÃ-ni-tsg catalysts, from about 0.05 to 4 . 2.0 weight percent, preferably 0.2 to 0.8 weight perceÃ7t.
6 It is crrt~cal to thie selective production of aromatic$ in tiseful qtiantities that the 7 conversion catalyst be sLibstantiail~ free of aaidity, for exarrÃple, by 8 ne tra(izing the molecular sieve with a basic metal, e.g., a(kals metal, 9 compound_ Methods for rendering the catalyst free of acidity are knownÃr:
the art. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Paterit 11 No. 5,316,753 for a description of sr.:ch mettiods.
13 The preferred alkali metals are sodium, potassium, rubidiurn and casium;
The 14 moÃecular sieve itself can be substar<fialiy free of acidityj only at ver)r higt) si!Ãca:alurziÃna mole ratios.
17 Catalytic _ QracliÃ~~c 19 Hydrocarbon cracking stocks can be catalytically cra cked in the absence of hydrogen using SSZ-75r preferably predominantly in the hydrogen form.
22 When SSZ-75 is used as a catalytic cracking catalyst iÃi tiie absence of 23 hydres<;eÃt, the catalyst may be employed in conjunction wÃtti traditional 24 craek,inQ~ cataiysts, e;g., any aIurninosiiica~.te heretofore empIoyed as a component in cracking catalysts. "i ypically, i:t~~se ai-e lar:~~ pore, crystailine 20- awtamÃr#asificates. Exampies of these tra,ditioriai cr~cking catalysts are 27 disclosed in the, atorer?ierytior.ed U.S. Patent No, 4,910,006 and U.S.
Patent 28 No 5.316,753. W~en a traditionaC cracking cataiyst (TC) corrrporient Ãs 29 employed, #tie Ãelative weight ratio of the TC tc) the SSZ-75 is generally bertvVeer) about 1 : 10 and about 500:1, desirably between aboÃÃt t :'s'. C
and 31 about 200:1, pre#erabiyf betvveen about 1:2 and abo:it 50:1, and most 32 preferably is bet~*reen about I :1 and about 20: 1. 'T'he novel molecular sieve .~:t~~
1 and/cxÃ- the traditional cracki~~9 coii1ponent may be further ion exchanged with 2 rare earih: ions tonnod:fy selectivity, 4 The cracking catalysts are typicai'ly empb~~(i with an inorganic oxide matrix component. See the aforementioned U.S. Patent No. 4,910;006 and US.
5 Patent No. 5.316,753 for examples of such matrix components.
a isor~er#zatiot) ( t~~ present catalyst is highly active and highly selective for isornerrzRr3gC4 to 11 C-7 hydroGaÃ-batis, Theac>tivity means that the catalyst can operat~ at 1:2 relatively low temperature which thet'modynamically favors highly branched 1:3 pat-~.~ffins, ~._oÃ-~~equeritly, t~~e catWyst can produce a high octane profjLjct..
14 The high selectivity means that a relatively hig.hi liquid yield can be achieued when the +~,@ta!yst is rusi at ah;gi~ actane.
17 The present process comprises contacting the isomc-tÃzation catalyst, i.e., a 18 cataiy5t comprising SSZ-75 in the Ãiydr~~en form, with ~~~~~~rocar=bon feed 19 r_ander isomerlzation conditions. T1'ap, feed is preferably a 1Ãgtit straight r-tit~
fraction, boiling within the range of 30'F to 250'1:=- ~--1IC to ~~~'C) and 21 ~re-ferably from 60'F to 240"~ (16 C to 93 'C). Preierably, the hydrocarbon 22 feed for the pi'c-scess comprises a substantial ainount of C.j to C;
nor'rnaI and 23 slightly tararictied low octane h7ydr-ocar-tYc.r-is, riiare preferably CE, arid C6 24 hydrocarborss:
2~'?
26 It is preferable to ~~~~ out the isomerization reaction ir, tlle presence of 27 hydrogen. Preferably, hydrogen :s added to give a hydrogen to hydrocarbon 28 ratio (~2,41C) of 'r?et'weet) 0.5 and 10 112r'1-IC, more preferably between I and 29 8 H21HC. See the aforementioiied L.J.S. Patent No. 4,910,006 and U.S.
Patent No. 5,316,753 for a tr.irther dÃsc;Ãssicap, of isomerization process conditions.
32 A 'loYv sulfur feed is especially preferred in the pre'sent process. The feed 33 pi-eter-ably contains less tharb 10 ppryi, -nore preferably less than I
:xipm, af:d 1 most preferably less than 0 . 1 ppm sulfur. Iri the case of a feed which is not 2 already low in sulfur, acceptable levels car: be reached by hydrogenating the 3 feed in a presaturation zone with a hydrogenating catalyst which is r-esistar-t to 4 suIfuÃ- poisoning; See the aforementioned U.S. Patent No, 4,910,006 and U.S. Patent No. 5;3167753 for a further dÃskusuia~ of this hydrodesulfurÃzation, 6 process.
8 It is ~~eferable to!Ãm!t the nitrogen level and the water content of the feed 9 Catalysts and processes which are suitable f{Drfhese purposes arp- known to those skilled in the art.
12 After a period of operation, the catalyst can becsime deactivated by sÃ.ÃiÃur or 13 ~ok.e. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent 14 No. 5;316,753 for a #uÃ-ther discussion of methods of removing tHs su3fur arid coke, and of regeneratirig the catalyst.
17 The conversion catalyst preferably coritaÃrss a Group Vill r~ietal compound to 18 E~ave sufficient activity for comniercÃai use, By Gr~~~p Vlli metal compound as 19 used herein is meant the metal itself or a compound thereof. The Group VIII
noble metals aand their compounds, platinum, paI[adiurn, and iridium, or 21 corrrtiiaiatÃorrs thereof can be used. Rhenium and tin may also be used in 22 conjunction with the noble metal. The most prefe-rred liietal is platlnum.
The 23 amo~int of Group VIli rnetal present in the conversion catalyst shotild be withi;l 24 the normal range of use in isornerizing catalysts, from about 0.06 to 2.0 weight percent, preferabiy 0.2 to 0.8 weight percent.
27 Alkylatior~ ~~d.TransalkyLation 29 SSZ-75 c:~.~Ã~ be used in a process for the alkylation or transalkylation of ar~
arc-ma#3c hydrocarbon. The process coiiiprises contacting the aromatic 431 hydrocarbon with a C2 tO 0<6 OIetin aIlcylating agent or a polyalkyl aromatic 32 hydrocarbon transalkylating agent, ~~~rAer at least partial liquid phase 33 conditions, and in the presence of a catalyst comprising SSZ-75.
-3t-2 SSZ--75 cari also be tised for rernoving benxerae frorn gasoline by ~ikyiating 3 th:e benzene as described above and removing the alkylated prodtict from the 4 gaso1ine,, 6 For high r:atalytic activity, t#ie, SSZ-75 rno(ecuiar sieve should be 7 predominantly En its hydrogen ion forrn. It ispreter~~ed that, afte-r calcination, at 8 luast 80% of the cation sites are occupied by hydrogen ior7~ andlor rare earth 9 ions.
11 Examples of suitaWe aromatic hydrocarbon feedstocks which may be 12 alkylated or transaikyEated by the prc~~~ss, of 5he, invention ;ne:;ude, aromatic 13 compounds such as benzene, toluene and x-v(ene. The preferred aromatic 14 hyrir'ocarbor is benz.eille. There may be occasions where naphthalene or t~aphtr#aferie derivatives sticr'h as clRmethyIpaphthalene may be desirabte.
16 Mixtures of aromatic Frydrocar-bor3s may also be employed.
18 Suitab1e olefins for the alkylation of the aromatic hydr'ccarbor, are those 19 contairiinr.~ 2 to 20, preferably Z to 4, carbon atoms, %Ac h as ethylene, propylene, buter:ze-I ; trans-butene-Z and cis-bGitene-2; or rnixtures therenf.
21 There may be instances where pentenes are desirable, -rhe preferred olefins 22 are ethylene and propylene. Lor~goar chain alpha r11efins may be used ~s well.
24 When tran-saiky?ation is desired, the transalkylatirig agent is ~polyalky;
arornatic. hydrocarbon :.ontaining two or more alkyl groL,ps ttiat each may 26 have from 2 to about 4 carbon atorrs: For example, suitable polya~kyi 27 aromatic hydrocarbons include di--õ trÃ- and ietfa-alkyl aromatic hydrocarbons, 28 suchi as dieti^>y1benzene, triethyÃbenzene; dÃethy;methylber~~ene 29 (diethyltoluene), di-isopru~~lbt>;r~~~ne, di-isopropyltoluene, dibutylbenzene, and the like. Preferred po9yalkyl ararnatic hydrocarbons are the dialky;
31 benzer-tes> A par-~~cuIariy preferred pofyalky~ aromatic hydrocarbon, is 32 dkisopropylberzzene.
::.. , ~:..
1 When aIkylatiori is the process conducted, re~.~..c;tiort conditions are as follows, 2 The aromatic hydrocarf~on feed should be present Ãn sto#chiometric excess.
It `~ is preferred that molar ratio of arornatics to oIefir-s be greater than four-tc--ore 4 to prevent rapid catalyst foulirrg. The reaction temperatLrre rnay; rarige from 100'F to 600~~ (38 C to 31YC), preferably 250"f" to 450''F (1''~1 C tr~ ~
~~CC).
6 The reaction pressure should be sufficient to maÃntairi at least a partial liquid 7 phase in order to retard catalyst fouiing. 'f`Ns is typically 550 psig to 1000 psig 8 (0.345 tt-, 6.89:Mpa gauge) depending on the feedstock and reaction 9 teniperature, Contact time may range from 10 seconds to 10 hours, but r~
usuaiiy from 5 m;inutes to an hour. The weight hourly space vefc+city~ (WHSV), 11 in terÃnu of grams (pounds) of aromatxr: hydrocaÃbon and olefin per gram 12 (pound) of catalyst per hour, is generally witfiiri the range of about 0,5 to 60.
14 When transalkylation is the process conducted, the molar ratio of aromatic ~1 5 hydrocarbon wÃ1Ã generally rar:ge froÃ~~ about 1:1 to 25;1, and preferably froÃ-n 16 about 2:1 to 20:1. The reactiori temperature may rangra from about 1006 Fto 17 640`F= (380C to ~~ 50C), but it is preferably about 250s F to 450'F=" ~ 121 FC to 18 232cC}. The reaction pressure should be sufficient to maintain at least a 19 partiai liqfiid pf3ase: typicaq(y in the range of abc~~~~ 50 psig to 1000 psig (0.345 to 6.89 Mpa ~auge), preferably 300 psig to 600 psig (2,07 to 4.14 Mpa 21 ~~~ge): The weight hourly space velocity vvEll range from about 0.1 to 10.
22 U.S. Patent No. 5,082,990 issued on January 21, 1992 to f-isÃeti, et al.
23 ciesf;sibes such processes and is incorporated herein by refer'ence, Conversion of Paraffins to AroÃnatic-,, , paraffins to higher moI~cLilar 27 SSZ 7 5 can be tised to convert lig l-it gas C2 Cr 28 weiglRf hydrocarbons including aromatic compounds. Preferably, the 29 molecrj3ar sieve will contain a catalyst metal or metal oxide wherein said metal is selected from the gÃoup consisting of Groups 18, I18, VÃfl and IIIA of the :31 Periodic Table: Preferably, the metal is gallium, niobiurn, ~tidirim ot' zinc irl the 32 range of fsoÃn about 0.06 to 5,1/o by aveight.
r;3 ,,..
1 fsomerization of Olefins ~.
3 SSZ-75 r:ar, be used to isomerize oletir:s. The feed stream is a hydrocarbon 4 stream containing at Eeast orÃeGr-~, O1efio., preferably a C~ F, normal 6e#wn, more preferably normal butene. Normal buter:~ as used in this specification means 6 all forms of normal buterie, e.g., 1-butene, cis-2..butene, and trarls-2-buter,e.
7 'Typlcally, hydrocarbons other than normal butene or other '4 ~ normal olefins 8 will be presergt in the feed stream,. These other hydrocarbons may include, 9 e.g., alkaries, other olefins, aromatics, hy.droger-1, and inert gases.
11 'T'he feed stream typqcaEly may be the eftlueÃif frorn a fluid catalytic cracking 12 urrit or a methyl-t:ert-bu#yI ether uriit. A fluid cat~lytic, cracking ullit effluent 13 typically contaxris aboLAt 40-60 weight percent normal butenes. A
14 methy:-tertNbu#yl ethereingt e-ffluent ty+~.~Ãcally contains 40-100 weight percent normal buterre, The feed stream preferably contains at least about 40 weight 16 percent normal butene, more preferably at ieast about 65 weight percent 17 normal btitene. The terms isovolefar~ and rnethy+! branched iso-oÃefin may be 18 used interchangeably Ãp this specificatÃon.
The prof-ess is carried out under isomerlratiora corrditi:aris. The hydrocarbon 21 feed is contacted ~r%, a vapor phase wi'th a catalyst waniprlslÃig the ~SZ-i -5.
22 The process may be carried out generally at a temperature froÃ-Ãi about 625 '~
23 to about 950u~ (329-510UC), for butenU s, preferably from aboLFt 700uF to 24 about 900"F (37a-482`C); and about 360'F to about 650+ (1 f 7-343"C) fur pentenes and fiexenes. The pressure ranges from sr.rõatrnospherac to about 26 200 ps;g ; 1.~8 Mpa ~auge)> preferably froril abc rst 15 psig tr) about 200 psig 27 ( Ø 103 to 1.38 Mpa gauge), and more preterably troni about ~ ps-1g to about 28 150 psig (0.00689 to 1.03 1Vipa gauge).
Tiie liquid hourly space velocity during contacting is generally from about 0.
31 to about 50 hr '.; based or, the hydrocarbon teed, preferably from about 0.1 to 32 about 20 hr', more preferably frc1r;~ ~~OLst 0.2 to abou#. 10 hr"i, ntost preferably 33 from about I to abutit 5 I'-ir". A hydrogen/hydrocarbon molar ratiois v34., 1 mairitaEr-ied from about 0 to about 30 or higher> 'T'he hydrogen can be added 2 dErect@y to k},e feed stream or directly ta the isomerÃzatiar) zone. The reaction, 3 is prefera~ly substantiaHy free of water, typically tess than abaL,t two weigtzt 4 percent based on the fr~ed. The process can be carried out 3n a packed C~ed rp-actor; a fixed bed, fELiidszed bed reactor, or amovir-rg bed reactor: The bed 6 of the ; atalyst can rr:ove upward or dowr3ward. The r?-ioI~ percent conversion 7 of, e:g., rrarmal br,aierze to iso-butene is at least 10: preferably at least 25, and 8 more preferaNy at least 35.
~. I~~~~~~ornerirats~r, 1'1 12 ~SZ-75 may also be u,5etul in a process for asomarizir~g one or more xylene 13 isomers. in aCa aromatic t~ed to obtain ortt3o-, meta--, ar:d para-xylene in a 14 ratio approaching the equilÃbriLim vaiue. In particular, xylene isomerization is used in conjunction with a separate proce<ss, tt) marrufactL3re para-xylene:
For 16 example, a portior, oof the para-xylene in a mixed Ca aromatics straarii may be 17 rer:overed by erystaflization and centrifugatican. `~he, mother liquor trom the 18 crystallizer is then reacted under xylene isomerization conditions to restore 19 ortho-, meta- and pa-a-xyieries to a near equilibrium ratio. At the same time, part of the ethylber~~ene in the mother liquor is converted to xyfer~es, or to 21 products whÃch are easiiy separated by fi1tration. -rhe isomerate is blended 22 with fresh feed and ttie cgombiÃied stream is distilled to remove heavy as-id light 23 bv_praducts. The resuÃtar3t Ca aromatics stream is then sent to the crystallizer 24 to repeat the cy1cle:
26 Optiorially; isomerization in the vapor phase is conducted in the presence of 27 3.0 to 30,0 moles of hydrogen per mole of alkylberizetie (e:g.;
ethy;benxene), 28 If hydrogen is used, the catalyst should comprise about 0.1 to 2.0 VA.% of a 29 h:ydrogenatm:orr'dehvdroqp-natsorw componerii selected from ~`~ror,~~~ VilI
(of the Periodic 1abie) metal component, especially platinum or nickel. By Grou;p VIII
31 metal cor~ponerit Ãs meant the metWs and their compounds such as oxides 32 and s1.3lf4C$es.
1 Optionally, the isornerizatioÃ, feed rnay contairi IQ to 90 wt. of a diluent such 2 as folrione, trimethylbenzene: naphthenes or paÃ-affiiis.
r~
u 4 'Oligomerization 6 it iz,-, expected that SSZ 75 can also be used to oligomerÃze straight a-ld 7 bran&ed chair~ olefins having from about 2 to 21 and preferably 2-5 ~arbon 8 atams. ` The oIÃgomers which are the. prodricts of the process are mediurn to 9 heavy olefins wh~ch are useful for both fuels, i.e., gasoline or a c~asso1 me blending stock and ctiemicals:
12 The o;igomerixatiorà process c:orY7wri~~s, contacting the olefin #eedstock in the 13 gaseous or liquid phase with a catalyst comprising SSZ--75.
The n~~~ol~cuÃar sieve can have the original cations associated therewith 16 replaced by a wide variety of other cations according to tÃ~~chniqr_r~s well 17 known in the art, Typical cations would include hydrogen, ~~nmonit-im and 18 metal cations incii.iding mÃxlures of the same. Of the replacing irieta113~
19 cations, particular preference is given tc3 cations of met~l~s such as rare earth metals, manganese, calcium, as well as metals of Group li of the Periodic 21 Table, e.g., zinc, and Group VIII oÃthe Periodic Table, e.q., r3ickei, One of the 22 prirne requisites is that the molecular sieve have a fairly low aromatization 23 activity, i.e., in which the amoiant of r.~rorr'ati~s produced is not more than 24 about 20% by weight. This is accamplistied by using a molecular sieve with controlled acid activity aspizz~ va3iie' of from about 0.1 to about 120;
preferably 26 from about 0. 1 to about 100, as rÃ~~~~ured by its ability to crack r0hexane.
28 Alpha vaiue; are defiried by a standard test known in the art, as sf?obvri 29 in U.S. Patent No. 3,960:978 issued on June 1, 1976 to Givens et al. which is incorporated totally herein by reference. -f required, such molecular sieves 31 may be obtained by steam:ng, by use in a conversrori process or by any other 32 rr~~thod which may occurtc. one skilled inthis art.
'~ r~..
I Condensation of Alcohols 3 SSZ-75 can be used to condense lbwer aliphatic aico+iols haviiig 1 to 4 10 carbon atoÃns to a gasol;rÃe boiling point hydrocarbori pioduct coÃnprising mixed aliphatic and aromatic hydrocarbon. The process disclosed iri U,S.
6 Patent N'o. 3,894,107, issued July 8, 1975 to BcÃttei-et aIõ describes the 7 process conditions used in this process, 'ii1'hi~h patent is i:'1corp:}~"'ated totally 8 herein by reference:
E_, The catalyst may be in the ~~~rr-)ger3 form or may be base exchanged or 11 impregnated to contain ammonium or a metal catioci complement, prefierabEy 12 in the : ange of from about 0,05 to 5% by weight. The metal cations that may 13 be present incRude any of the metals of the Groraps I through VIl1 of the 14 Periodic Table, However, in Yhe- case of GrouF? IA metals, the ca;iori rontent ~~ould in no case be so large as to effectively iÃiactivate the catalyst, nor 16 should the exchange be such as to eliminate all acsdity, There may be cithei-17 processes invo1virig treatment of oxygenated substrates where a basic 18 catalyst is desired.
Mthaiap_Q~adÃnc~
22 Higher moiecula weight Iiydrocarbons can be formed from lower mal~cuiaÃ2.3 weight hydror.arbor~s by contacting the lower molecular weight hydrocarbon 24 with a catalyst comprising SSZ-75 and a meta4 or metaE compourid capable of converting the lower nio1ecLÃlar wesght hydrocarbon to a higher molecular 26 weight t-Ãydrocart3on, Examples of *,uch reactions Ãr-icitÃde the conversion of 27 Ã-nethane to G, , hydrocarbons such as ethylene or ~~nzeÃie ot both:
28 Exam,,1es, of useful mei~~~ ~tid metal c-oÃiipourids include ~anttaarlid~
w',d or 29 actinide metals or metal corr;pozinds:
31 The-se reactions, the metals or rrie'tal compoLind~ employed and the 32 conditions Linder which they can be run are disclosed in U.S. Paten:ts No, 33 4.734s537, issued March 29, 1988 to Devries e; al. 4,939 .31 1 Ysswed July 3"
-.:=y:7...
1 1990 to W~~~~~heck et al., 4,962,261: IsSUed October 9, 1990 to Abrevaya et 2 aI.: 5,095.1 61, issued March 10, 1992 to Abrevaya et aL; 5,105,044, issued 3 Aprii 14, 1992 to Han et al,; 5,105,046, issued Aprif 14, 1992to Washecheck;
4 5,238,698, issued August 24, 1993 to Han et a1.; 5,321,185, issued June 14, 1994 to van der Vaart; and 5.336;825, issLied August 9, 1994 to ChoLadhaÃy et 6 al., each of which is #r3cf3''pCtra:'~~d herein by reference in its entir'ety;
fy 8 Poly#'ne9Ezat3on vf 1-0leÃans The molecular sieve of the pr~sent. irivnnÃÃon may be used in a catalyst for the 11 poIymerizatiori of '#role#Ãns, e:g., the polymerization of ethylerle. -Fo #orm. the 12 olefin poIyryierizatÃon catalyst, the mo'ecular sieve as hereinbefore described 13 is reacted with a particular type of csrganomeÃai1ic cornpotind.
Organametaflif.
14 t: mpous-tds useful in forming the polymei-ixaÃion catalyst inCfude trivalent and tetravalent orgarioÃÃÃanium and organoc,lii-omÃum compounds having ilkyÃ
16 moaeÃÃes and, optionally, lialo moieties. 1>i the context of the preserit invention 17 the term "alkyi" ificiudes both straight and bran:cE~~d chain alkyl, cycloalkyl arld 18 a1karyi groups sr"rch as benzyl.
Examp:es of trivalent and tetravalerit argar-roch rOMir_ini and cj~ganotifaniGrrn 21 : ornpraunds are disclosed in U. S. Patent No. 4,376, 722, issued March 15, 22 1983 to Chester et ai,, U. S. Patent No. 4,37 7,49?, issued March 22, 1983 to 23 Chester ent aÃ.; U. S. Patent No. 4,446,243, issued May 't ; 1984 to ~`,;
hester et 24 a1., and U. S. Patent No. 4,526,942, issued Jufy 2, 1985 to Chester et al.
The disc"osure of the aforementioned patents are. incorporated herein by reference 26 in their enÃÃreby..
:...' 7 28 ExainpÃes of the organorrretalk compounds r:ised to form the polymerization 29 catalyst iric:IL~de, but are not iimited to, compourids corresponding to the general #om)u1a,;
32 MY,Xf,,:, -. .>
~>., I wherein M is a metal selected frun-, titanium and chrorriium; Y is aiky1; X
is 2 iialoger# (e,.g,, CÃ or Br); n is 1-4; aizd ni is greater th~~~~ or equal to r, and is 3 3 or 4.
Exam.ples of organotitanium and organoGFiromiurn compounds encompassed t by such a formula compounds of the Iffirmula CrY4, CrY:, CrY5X, 7 CrY2X, Cry=,X2, Cr"YXr; C rYX;, TiY4, TX3, TiY3K l"iY2X, `T'iY?X, TiYX.::, TiYXv :
8 wherein X can be CÃ or Br and Y can be methyl, ethyl, propyl, isopropyl, butyl, 9 isob;:Ãfyl, sec-butyl, teÃ-trbutyl, perifyl, #sopentyi, ne,+penty+l, hexyl, isohexyl:
neohexyl, 2-ethybutyl, octyl, 2--ethgrlhexy&, 2,2-d:ethylbuty(; 2-i~~~~~pyÃ-3~
~ 1 methyÃbutyl, etc:, cye ohexylallcyl~ such as, for example, cyclo he:xyim ethyl, 2-1 21 cyclohexylefhyl, 3-wycly hexyÃp ropyl, 4-cyc#ohexylbutyÃ,* and the t,oÃ-responding 13 a#kyl-substktuted cyclohexyl radicals as, for example, 14-14 methyleyclahexyl)mekhyl; neophyl, i;e., beta, heta-dimethyl--phenethyl, benzyl..
ethylbenzyl, and p--ise~.~ropylbenzyd. l"'referre~ exaimples of Y include C;--5 alkyl, 16 especÃaily htityl.
'~
18 The organotitaniurn and organochromium fTlaterials employed in the catalyst 19 can be prepared by techniques well known iri the ad. See, for example th<.
aforementioned Chester et aI, patents.
22 The organotitanluÃ~i or organochromium compouricfs c-asi, be with ttie 23 molecular sieve of the present irweni;on, such as by reactir-ig the 24 orgar o metalI Ãc compound and the molecular sieve, in order to form the oiefÃÃ-i polymerization catalyst. Generally, such a reaction takes place in the samp-26 reaction med~~im used to prepare the organ ometaiiic compound under 27 conditions which prornote formation of such a reaction prc~~uct. The 28 molecular sieve eari: simply be added to the reaction mixture after formation of 29 the oÃgartofnetallic compound has been completed. Molecular sieve is added 3 () in ari amount sufficient to provide fr~~ about0,'i to 10 parts by weight, 31 preferably from about 0.5 to 5 parts by weigl-jt, of organametallic compound in u2 the reaction mediuni per 100 parts by weiglit of molecular saeve.
.. !.~}_.:
2 Ternperature of the reaction mec'aum durÃng r~action ot orgenvmetaili~
3 compoL;nd with rnafecu;ar sieve is also maintained at a level which is low 4 enough to er ssure, the stability of thip, organometallic reactar#t. Thus, terflperatures in the range of froni about -150 C, to 50" C., pa-eferabiy from 6 about --8W C, to O" C. can be usefully employed. Reaction times of from 7 about 0.0 1 to '&C, hours, more preferably frorn- about 0.1 to 1 hour, can be, 8 employed in reacting the organotitanium or organor:hrorr3>um Wors?paund with 9 the molecu(ar, sieve_ 11 Upon completion of the reacticn. the catalyst mater~al so formed Ãrlay be 12 recovered and tirA~d by evaporating the reaction medii._,m solvent under a 13 nitrogen atmosphere. Alternat#vc-ly, olefÃti poIyrrserizatiori r-~actions can be 14 conducted in this sarrie solvent based reaction mediuryi useci to forrri the catalyst.
'16 .
17 The polyi-nerÃzation catalyst r:~~~ be used to catalyze polymerizat{oel of1 -IS olefins. The polymers produced r:ising thecatalysts of this inventiori are 19 normallyso4ad polymers of at least one mon,a-l-oletin coritair;irrg from 2 to 8 f-arborr, atoms per moiecuie. T~~~c- polymers are normally solid 2-1 homopolymers of ethylene or cc?poiyrTiers of ethylene wiÃra another rnono-l-.
22 olefin coriLtaining 3 to 8 carbon atoiiis per mo~~~~..sile. Exemplary copcalymer6 23 iii;..;iude ttiose of ettiylenelprapylene, ethylene/1-butenÃ:, ethylene:111-hexane, 24 and ethykes~e/i -o+;ter3e and the iike. The major portior~ of such copolymers is derived fro$r, ~thy3ene afid generally consists of about 80-99, preferably 95-26 mole percent of ethylene. These palymers are well suited for eAr,.rsion;
blow 27 mofdirig, injection molding and the ~~ke.
29 Thip, polymerization reaction can be cotiduCtec~ by confactdng monomer or monomers, e.g., eti7ylene, alor~e or with one c-t rriore other oiefÃr;s, and in the 31 substarstial absence of cafaiyst poisons such as moisture and air, with a 32 catalytic a3rtiaurrt of the supported organometwIl,c caia:ysi at a temperature 33 and at a pressure sufficient to 3riitiate the polymerization re-actiorl, If desired, _:_l==0 1 ari iraert organic soivent may be used as a diluent an{ to facilitate materÃa!s 2 handling if tt~e polymerization reaction is {:,or,dur:ted' with the re-actants in the 3 liquid phase, e.g. in a particle form (slurry) or soiu#>on process. The reaction 4 Ãyiay also be conducted with reactants in the vapor phase, e:g:, in a tluid':zed bed arrangement in the abser3cp- of a sc.lvetit but, if desired, in the presence of 6 an inert gas such as nitrogen.
;f 8 Thp- polymerization reaction is carried out at temperatures of frcarr, abotit 30`
9 C. or less, tip to about 200" C. or rnore; depeslding to a great extent on the operating pressure, the pressure of ti-se o'etjri monomers, and the particulaB'.
11 catalyst being used and its concentration. Naturally, the selected operating 12 temperature is also depeÃider?t upon the desired polymer melt index since 13 temperature is definitely a tactor iÃ) ad,iusiing the molecular weigtit of the 1,4 polymer. i~'referably, the temperature Lrsed is from about 30" C. to about 00' C. in a cor;vention',.-A slurry or "particle forming" process or from 10~.r"
C. tO
16 150' C. in, a "soIut;ori forming" process. A ternperature of from about 70' C to 17 11 D" C. can be emplayr:d for fluidized bed processes.
19 ~I-te pressure to be used in the polymerization reactions can be any pressure sufficient to initiate the poIymerizatioÃi of the moriomer(s) to high molecular 21 weight pralyÃ~er. The pre5sure, ttterefore, can range from subatmospheric 22 prp-ssures, using arà inert gas as diluent, to ~uperatmc~~~hf-rÃ~, pressLires of up 23 tc, about 30,000 psig or mare. The preferred pressure is from atmospheric (0 24 psig) up to about 1000 psig. As a ggeneral ruie, a pressure of 20 to 800 psig is most pr~fe-rred.
27 The selectiori of an inert orgariic solvent mediuÃ~n to be employed in the 28 so#Litian or slurry process embodiments of this invention is not too critical, but 29 the ;oives-it should be ineil to the supported organometallic catalyst and olefin polymer produced, and be stabÃe. at the reaction temperature used. It is not 31 necessary, t~~ow~.~ver, that t.iie inert organic solvent medium also serv'p-as a 32 solvent for the. poiymer to be tarod~iced. Among the i>;ert organic soivents 33 applicable for stich purposes rriav bc mentioned saturated aliphatic -4-1, `I hydrocarbons having from aboarPt 3 kc) 12 car-taon atoms per rno1~cuie such as 2 hexane, heptane, pentane, #sooctane, parmf,ed kerosene arid the like;
3 sat4araied cyicica'~~~haÃic hydrocarbons having from a~.~oL,t 5 to 12 carbor?
4 asorTss per rrFole,:~le such as cyclohexane, cyclopentane, dimethylcyclopentane and methyIoyclohexane and the l;ka and aromitas;
6 hydr"ocarbor'is having from about 6 to 12 carbon atoms per mralecuÃe such as 7 benzene, toluene, xylene, and the like. PartÃctilarly preferred soIveFit ri-iedia 8 are cycbhexane, peritane, hexane and heptane.
Hydrogen ~.an be.sntrodUced into the polymerization reaction zone in order to 11 decrease the molecular wetgFat of the polyrners producaci k1l.e.. give a much 12 higher Melt 1nd;:x, M1). PartEaE pressure of hydrogen when hydrogen is used 13 car~ be withi;n the rarige of 5 to 100 psig, preferably 25 to 75 psig. The mel':t 14 indices o#the, polymeÃ-s pr~ducedÃrr aceordaÃice with the instant invt.ntion can range frorri aboLit 0.1 to about 70 or even higher.
x~
1More detailed descrlption of suitable poAymerÃzatior, Ã,oÃiditÃons irieludmn~
18 exarxipl~s of particle form, solution and fluidized bed polymerization 19 arrangements are #or.:nd in Karapiraka; U.S. Pat. Rlo. 3.709,853, Issued Jan. 9, 1973 and Karol et al; U.S. Pat. I*to. 4,086,408; Issued Apr. 215, 1978. Both of 21 these patents are incorporated herein by r=e-fererice.
23 ~ +c~ iÃ~r~tr:an SSZ-75 f:aÃ) be used in a catalyst to catalyze hydrogenation of a hydr=ocarbor~
2 f 3 feed containing unsaturated hydrocarbons. The unsaturated hydrocarbons 27 c ~n, comprise. olefins, dienes, polyenes, aromatic compounds and the like.
29 Hydrogenation is accomplished by contacting the hydrocarbon feed containing wnsaturated hydrocarbons with hydrogen in the prewence of a 31 catalyst comprising SSZ- 75. The catalyst car; also coÃitaan one or more 32 ,-netals ofi Group VIB and Gror~p VIII, including salts, complexes and solutions 33 thereof, Reference to these catalytically active metals rss gntentled to -4.2-1 encompass such metals rjr meta$s in the elemental state or in sÃ?nre roÃ-ÃYl such 2 as an oxide, sulfide, tiaf#de, carboxylate and the leke: Exarnples of suvh, 3 metals include metals, salts or r:oÃ~~~~~~~58 wherein ti-ie nrtetai is selected from 4 the gr-aiip consisting of platinum, palladium, rhodium, iridium or combinations tfiereof; or the grou:p consisting of riickel, moiybder-rurn; cobalt, tungsten, 6 fitani;.r9-n, cttron7ium, vanadium, rhenium, manganese and comb#rations 7 thereof.
9 "(_he hydrogenation component of tt~~ catalyst (i.e., th -0 at:rarementi~..~ned rr#et,al) is pÃeserit #r, an amount effective to provide the- hydrogenation function of the 1.1 catalyst, preferably in. the range of from 0.05 to 25% by v~eight.
13 Hydrogenation conditions, sr_icti as tr:mperats:Ãre., iaressure, space veiowities, 14 contact time and the like are weIE known Ãri tlio-, art.
16 ~SZ-75 is usefuo as aÃi adsorbent tor gas separations (owing to its hÃqh pore 17 voiut-Tie wh,ile maintaining difftision control arid hydrophot}icity). SSZ-75 can 18 also be used ir~ a catalyst for converting oxygenates (such as metnaÃzoi) to 19 olefins, and for r-ciakirag small amines, SSZw7 5 can be used to reduce oxides of nitrogen in gas streams (such as automotive ex~~L3st) . SSZ-71: can aliso be 21 used ~~ a cold start hydrocarbon trap Ãri coz-rTbt_istiorr engine polfu.ivl3 control 22 syster-rTs. S5Z-75 is particularly useful for tÃappiÃig G; fragr-nenis.
24 T'he molecular ~~p-ve of the preser3t. invention can be used to separate ~~ss'es.
For example, it cari be used to separate carbon dioxide from natural gas.
26 T1{pieaiiy, the molecular sieve is Ãised as a cornponent in a memdrane, that is 27 used to separate the gasses. Examples of such membranes are disclosed in 28 U. S. Patent No. 6,508,86Qs ,ssa~red January 21 , 2003 to Kulkarni et a1., which 29 i!~ incorporated by re-fereÃi;e herein in its entirety.
31 The molecular sieve of the present inventaor, c.ar3 be used in aca¾aiyst to 32 prepare methylamine or dÃmethyEarliirre. DÃmethytamisRe is generally prepared 33 in EÃtdtÃstrial quantities bw ~ontinuo "; r~act:on of methanol (andior "I dirr;ethÃyIeifieÃ-j and ammonia in the preserÃce of a siÃica~-aluE-nina c.atalyst. The 2 reactants are typic~.ai9y combined in the vapor phase, at temperatures in the 3 range of 300"C; to 500'0, and at elevated pressures. Such a process is 4 disc:'Ioaed in U. S. Patent No. 4737,592, issued April 12, 1988 to Abrams et aL> wh_ch?s incorporated by reference in its entirety.
7 The catalyst is i-Ãsed ir: its acid form. Acid forms of moEecularsieves can be 8 prepared by a variety of tecfir;iq(jes. Preferably, the molecular sieve used to 9 prepare dimethylamine will be in tt~ehydrogen forÃY),, or have an alkali or a,kafinw earth metal, such as Na, K, W or Cs, ic:n-exchanged into it.
.z.t 12 The process of the present invention involves reactnc~ m eth~=I o>,:
133 dimethylether or a mixture thereof and ammonia in amotAnts siaff icient to 14 provide a c~arbon/nitrc~~en. "CIN} ratio from about 0.2 to about -1.5j preferably about 0,5 to aboÃ.it 1.2. The r~actior~ ~s conducted at a temperatt#i-e from 16 about 2a0t'~.:~ to about 450 G, preferably about 300 C to about ~`~00"C..
17 Reaction pressL:res can vary from about T-7000 kPa ( 1 -1000 psi), preferably 18 about 70-3000 kPa (10-~500 psi). A methanol and1oà d=ÃnethyletheÃspace time 19 of about 0.01-80 :~ours, preferably 0,10-1.5 hours, is typically used. ThÃs space time is calculated as the mass of cataÃyst divided by the mass flow rate 21 of rne}hano!rFdsrnethylether introduced into the reactor.
23 SSZ-75 may be t_Ãsed f{ar the cataiyk~c. reduction of the oxides of nitrogen in a 24 gas stream. Typically, the gas strearp, also contains oxygen, often a stoichiometric exz: ess t1-3ereaf; Also, the molecular ~~eve may contain a metal 26 ar, metal ioà s of on it which are cva~aWe of catalyzing the reduction of 27 the raitÃ-agen: oxides. Examples of such rneta14 or metal ions include cobalt, 28 coppeÃ-, platinum, iron, chrommm, mangai~aese, raickol, zinc, ;an}har;~urn, 29 palladium, rhodiuiri and mixtures thereof.
31 Orie example of such a process for the catalytic reduction of oxides of 32 nifrc,geÃ) in the ~reseÃice of a zeo1-tc ,s dascfosud !M US. Patent No.
4,297,328;
33 issued October 27, 1981 to Pitsctze-- et al., which is incorporated by reference -44.-1 tiereirl. There, the catalytic process is iiie coriabustioÃi of c;arbo-i m~.~rloxsd~
2 2 ' aÃtd hydrocaÃboris and the catalyt{c redÃ.FctÃon of the oxides of riitroger, 3 contained in a gas stream, such as the exhaust gas from an interr;al 4 combLÃstion engine. The zeoiite used is metal ion-exchanged, doped e.~r5 loaded sufficiently so as to provide an effective amoukit of catalytic copper 6 metal or copper ions withiÃi or on the zeolite. IÃi addition, the process is 7 condLicted in an excess of oxidant, e.g., oxygeri 9 Gaseous waste products resulting from the combustion of hydrocarbonaceous fuels, such as gasoline and fuel oils, comprise carbor, mar*axide;
11 ~ydrracark;=s and nitrogen oxides a5 cTroducts of tõornbust:c~n cir incomplete 12 combustion, and pose ~.~ serious health problem with respect to poElÃat:onof the 13 atmosphere, While exhaust gases from other carbcanac~eotis fuel-burning 14 soL,rces, such as stationary engines, iradustrial furnaces, etu:, contribute substantially to air pollotiori, the exhaust gases from aLrtcma}ive e~,ngines are a 16 principal source of pollutiorÃ. Bo-caLise of these bealtr7 problem concerns, ttie 17 Environmental Protection Agency (EPA) ~~~s promulgated strict controls on 18 the amouÃits of carbor, monoxide, hydrocarbons and Ãiitrogen oxides which 19 aritomobiic:s can emit. The implementation of these controls has resulted in the Lese of catalytic converters to reduce the amount of pollutants ernifted from 21 automobiles.
23 In order to achieve the simultaneous conversion of ~arbori n-Ãonoxide, 24 hydrocarbon and nitr~geti oxide pOilufasits, st has becoÃi3e the practice to employ catalysts in conjLxÃir;tic.ri with a=r-ro-tuel ratio control nnearÃs.
which 26 functions in response to a feedback signal from an oxygen sensor in the 27 engine exhaust system. Although these three component control cataly~~~~
28 work quite well after they have reached operating temperature of about 300V
29 C., at lower temperatures they are. not able to convert substantial amoLirit~ of the pollutants. What this rrÃeans- is that when an engine and in partccu#ar ar~
31 automobile engine is started up, the three compoÃ;eit control catalyst is not 32 able to convert the hydrr3c;arbon5 aÃid other pollutants to 3nnocuoLis 33 , ompoÃar,cfs.
_45._ 2 Adsorbent beds have beer~ used to adsorb the hydrocarbons during the wold':
3 start portion of the engine. Although the process typicaily w;I~ be used with 4 hydrocarbon fLÃe1s, th:e instant invention cari aw:~o be taseci to treat exhaust streams from alcohol fueled erÃgirres. The adsorbent bed is, iypically placed 6 immediately before the catalyst. Thus, the exhaust stream is first flowed 7 through the adsorberit bed and then through the Cataiyst. The adsorbent bed 8 preferentially adsorbs hydrocarbons over water under the conditions ~.~,resent 9 in the exhaust st:ream. After a certain arriount of tirne, th-a adsorbent bed has reached a temperature (tYpically about "150 C.) at whici-i the bed is no longer 11 able to rerr1ove hydr-ocarbons from the exhaust stream. That is, hydrocarbons 12 are actually desorbed from ti~Ãe adsorbent bed irwsteadof being adsorbed.
This, 13 regenerates the adsorbent bed so that it rari adsorb hydrocarbons dtjr-ong a 14 subsequent colc.9 start.
16 1-he prior art reveais several references dealing witil the, Use of adsorbent 17 beds to minimize hydrocarbon emissions during -a cold start engine operation.
18 One such reference is U.S. Pat. No. 3.699t683 iri which an adsorbent bed i~
19 placed after botq~:~, a reduo;ng catalyst and an oxidizirig catalyst. The patenfee$
disclose that wiyen the exhaList gas 5treami is below 20V C. the gas stream is 21 flowed through the reducing catalyst then Lttir-ougi=~ the oxidizing r-ata(yst and 22 finally through the adsorbent bed, thereby adsorbing hydrocarbons ori the 23 adGorber=t bed. When the temperature goes above 200' C. the gas stream 24 which is discharged f"roni the oxidation catalyst is divided intr:~ a major and 24 mirior portion, the rnajor portion being discharged directly inta the atmosphere 26 and the minor portion passing through the adsorbent ~~d:: whereby unburned 27 hydrocarbon is desorbecf and then flowing the resulting minor portion of this 28 exhaust stream coritaÃning the desorbed unburned hydrocafbons into tht::
29 engirre where they are burr~ed.
31 Another ref&ence;s U.S. Pat: No, 2,942,932 which teaclfiew a process for 32 oxidizing carbon monoxide and hydrocarbons which are contained in exhaust 33 gas streams. 1-he process disclosed in this patent consists of flowing an 1 exhaust strearÃ-i which is below 800' #= , into an adsarptior.. zone which adsorbs 2 the carbon monoxide ar~d hydrocarbons and then passing the resuitant 3 stream from this adsorption zone into an oxidation zc?ile. VVhen the 4 temperatÃii-e of the exhaLest gas stream reaches about 80W F. the exhaust stream is no longer passed through the adsorption zone bLIt ks passed directly 6 to the oxidation zone with the acÃditÃo!i of excess ~.~ir.
8 U. S. Patent No. 5,078,979, issued JanÃaary 7, 1992 to DLrnne1 which is 9 incorporated hE:rd=:in by reference in iiw entmÃely, discloses treatÃnc, aÃ:
exhaust ~as. stream from an engine to prevent cold start ernfssions using a molecular 11 sieve adsorbent bed. Examples rsfthe molecular sieve include faujasites, '12 c!inoptiiolites, mcrderÃites, chatrazite; silicalite, ~eoii~e Y, :altrastable zeolite Y, 13 and ZSM-5.
Canadian Patent No. 1,20500 disclc.>~~~ a method of reducing exhatist 16 emissions from an alcohol fueled automotive vehicie: This method consist's.
of 17 directing the cool engine staÃtup exhaust gas through a bed of zeoiite particles 18 and then over aii oxidation catalyst and then the gas is discharged to the 19 atmosphere. As the exhaust gas streamwarms up it is continuously passed 2i;.~ over the adsorption bed and then over the oxidation bed.
22 As stated this invention generally reflates to a process tcjr treating an engine 23 exhatÃst stream and in particular to a process for rrinir-,izing emissions di-irir~g 24 the cold start operation of an engine. The engine consists of any internal or external combustior, eÃigine which generates an exhaust gas stream 26 co;-itaining noxious components or pollutants inc,iuding ur~bi-3rÃaed of ihermaiÃy 27 degraded i-iydrocarbons or similar oraanic.s. Other Ã~OAC)LIS components 28 usualiy preseÃit in the exhaust gas include nitrogen oxides and carbon 29 monoxide, '1'he engine may be fueled byi a hydrocarbonaceous tue'. As used in this specification and in the appended claims, the term "hydrocaYbor~~~~ous 31 fuo-Ã' includes hydrocarbons, alcohols and mixtures t4-terp-of. Examples of 32 hydrocarbons which can be used to fuel the engine are the mixlures of 33 hydrocarbons which make Lip gasoline or diesei tuel. The aicohols which may ~~
..~õ,_ 1 be used to fuel engines include ethano: and methanol. Mixtures of alcohols 2 and rnixt;.Ãrey of a;coI-Ãois and hydrocari;3ons can aÃso be used. The.
engine 3 may be a jeseng;rre, gas tLÃrbire, irternal combustion engine, such as an 4 aLÃtoryiobiie, truck or bus enqine, a diesez engine o;, the ;Ãke. 'The process of this invention is pafliculariy suited for hydrocarbon, aicc-hol, or hydrocarbon-6 alcohol mixture, internal combusticin engine r1,ourited in an automot?'Ãie, For 7 convenience the desc;riptiori will use hy+drocarborx as the fuel to exemplify the 8 Ãniven#ion. The Lrse of hydrocarbon ir, the subsequent description isnot tobe 9 construed as limiting the in,rention., to hydrocarbon fLre!'ed engines.
11 When the engine is started up, it produr;es a relatively high concentration of 12 hydrocarbons in the engine exhaust gas stream as well as other poi[utants.
13 Pollutants will he used herein to collectively refer to any unburned fuf-'l 14 components and combustion bypr~ducts four3d irà the exhaust str-earii.
i==of example, when the fuel is ~hydrocarbon fuel, hydrocarbons, nitrogen ox;des, 16 carbon monoxide and other corgibustÃon byproducts will be fioLÃrtd in the engine 17 exhaLÃst gas stream. The temperature of this eiigirie exhaust stream is 18 relatively cool, generally below 500' C. and typically ir) the range of 200" to 19 400" C. This engine exhaust stream has the above characteristics during the initial period of engine operation, typically for the first 30 to 120 sec~~d,-;-, after 2-1 s+artcÃp of a coid erigÃrÃa. The engine exhaust stream will typÃeally contain, by 22 voitÃme, about 500 to 1000 ppm hydrocarbons.
24 The engine exhaust gas stream which is to be treated is flowed over a molecular sieve bed comprising i-nolecular sieve 5SZ-56 a first exhaust 26 strearr). Molecular sieve ~SZ-56 is described below. The first exhaust stream 27 5vvhact3 is discharged frorii: tt7a rrr6ecuiar sieve bed is riow flowed over a 28 catalyst to convert the pollutants contained Ãri the `:: st exh,au5i stream to 29 innocuous components and provide a treated exhaust str~~m which is discharged into the atrrosphere. It is understood that prior to discharge into 31 the atmosphere, the treated exhaust stream may be flowed through a muffler 32 or other sound reduction apparatus well known in the ari.
2 The catalyst which G used to convert the PoIfutarrts to innocuous componerrt~
3 is usual'y referred to in the, ar;as a thr'ee-component coÃitrol catalyst because 4 it can sirnuItar~eousiy oxidize any residual hydrocarbons present in the first exhaust strearn to carbon dbxide and water, oxidize any residual carbon 6 monoxide to carbon dioxide and redLice any Ães'r~~~a$, nitric oxide to rÃitrc~~er, 7 and oxygen, iri some cases the catalyst may notbe required to conve-rl nitric 8 oxide to nitrogen and oxygen, e.g., when an alcohol is used as the #Lref. In this 9 case the catalyst is called an oxidation ca#aiyst. Because of the re1atEveiy :ow temperatÃ.ire of the engine faxhaust stream and the first C-.xhaust stream, this 11 cataf;sst.. does not funr-tion at a very high efficiency, therf-'by necessitating the 12 mo?eculaà sieve bed.
14 When the mo;ecuiar sieve bed rc-~~~~~ a sufficient temperature, typically aboLit 15-0-200" C., the pollutants which are adsorbed in the bed begin to 16 desorb aÃid are carried by the first exhaust stre-am over the uataiyst. At th:is 17 point the catalyst has reached its operating temperature and is therefore 18 capable of fLeiiy eonvertirig the pollutants to innracÃaous components.
The adsorbent bed used in the iristarrf invention can be conveniently 21 employed in particulate form or the adsCrbeint can be deposited orrto a soiid 22 monolithic carrier. VVhÃ:n pardÃeuiate form is desired, the adsorbent can be 23 formed into shapes such as pills, pellets, granules, rings, spi"ieres, etc:
In the 24 em~.~poyment ot a monaiithic form, it is usually niost cc~nvenieÃit to er-nploy the adsorbent as a thin film or coating deposited ori an irieÃ-fi cari"ier material whici') 26 provides the strtictLiral support for the adsorbent. The Ãnert carrier material 27 can be any refractory ma-tefia( such as ceramic or metallic mate riais. It Ã-s 28 desirable that the carrier ÃTiateriaf be unreactive with the adsorbent and Ã:Ãot be 29 degraded by the gas to which it is expvsed= Examples of suitable ceramic rrÃateriaas include sillimanite, petalite, cordierite, mull:te, zircon, zircori mullite, ~j spondurnene, aIurniria-iitariate, etc. Additionally, metallÃc materÃalswE-aioh are 32 within the scope of this invention include metais and alloys as disclosed ir~
I U.S. Pat. .. No. 3,920,583 which are oxidatior) resistant anfA are otherwÃse 2 capable of w:thstanding high temperatt.:res.
.~;
~
4 The carrier material can best be utiiized in any rigid urÃitar;s corafiguratios~
which provides a pluralily of pores or ciiannel~ extending in the dÃrection, of f.~ gas flow. It :s preferred that the conf'gu,ation be a honeycomb c.onfiguration.
7 The honeycomb structure can be t.ised advarit~~eotisiy in eÃthL:r unitary forn'l, 8 or as an arrangeÃreÃit of multiple modules. The honeycomb structure is 9 usually or;ented such that gas flow Ãs generally wn the same d:rection as the cei1s or channeis of thp. honeycomb structure, For a more detailed discussion 11 of monolifhic WtÃCtÃ.Ãres, refer to U.S. Pai: Nos. 3,785,996 and 39:167,453.
13 The molecular sieveis deposited onto the carrier by any convenient ~a- y well 14 knowr, in the art. A preferred method invoi~~~~ preparing a slurry using the rno1ecuIar sieve and coating the rÃionolit.hÃc. honeycomb c.arm=1r with the slurry.
16 The slurry can be prepared by means known ir, the art such as combining ~~ie 17 appropriate amouna of the mo1ecu1arsiewe arid a binder with water. This 18 mixture is then blended by using means such as sonificatioÃi: milding, etc.
T'hi~
19 slurry is uses~ to coat a monolithic hc+sieyf.>r,mb by dipping the honeycomb into the siurÃv, removing the excess slurry by draining or blowing out the channels, 21 and heating to about 100J C. If the ttesired loading of molecular sieve is not 22 ac1iÃeved; the above process may be repeated as many times as requtred to 2 "'15 achieve the desired loading.
lnstead of depositing the molecular g-ieve onto a monolithic honeycomb 26 stÃ'uctijrc-, one car, take thc-.,; molecular sieve a9id #orrri 3t into a mor2o3ith:c 27 honeycomb structure by means known in the art.
29 The adsorbeÃ~t may optionally contain one or more catalytic metals clÃspersed th;:reon. The rTietals which ca:~ be dispersed on the adsorbent are the noble 31 metals wtZÃcl-i consist of platinum, palladium, rhodium, r.,thenium. and v2 rnixt:ures thereof. The (lesiÃ'ed knble metal may be ~eposÃt~~ onfo the 33 adsorbent: which actsas a support, in any suitable manner welr known in the r50 1 art. Orle example ca# a method of dispersing the r~oNe metak. onto the 2 adsorbent support involves impregnating the adsorbent sr,z poÃt with an " aqueous solution of a decomposable compound of the desired rioble rrieta( or 4 metals, drying the adsorbent which has the noble metal compound disperseci ari it and then caiciriing in aiÃ, at a temperature of about~~0' to about 5~.~0' C.
6 for a time of about 1 to about 4 hoor-s. By decoi-nposakale compor.rnd is meant 7 a compound wliÃeh upon heating in air gives the metal or metaY oxide.
8 Examples of the dewomprasaNe compounds which can be used are, set for-th 9 in US, Pata No. 4 , 791099 whÃch is incr;'rporat~~ by reference. Preferred decomposable compounds are chloroplatinic ac$d, rhodium trichloride, 11 rhlo:-opalladic acid, i~Ãexachioroiri~~~tc- (IV) acid and hexachlororuthenate. It is 12 prefp-rab1e that the noble metal be present in ari amount ranging from about 13 0.01 to about 4 weight percent of the adsorbent srappoÃl. Specifically, in the 14 case of pÃatintam and palfadiGiÃn the range is 0. 1 to 4 wxeigi-it percent, whi~~ in thc- case of rhodium and rutt~enium the range is frong about 0.01 to 2 weight 16 percent, 18 These catalytic i-rietaEs are capable ot oxidizing the hydrocarbon and carbon 19 monoxide and reducing the, nitric oxide components to innocuous praducts.
Accordingly, the adsorbent bed can act both as an adsorbent and as a 21 cataiyst:
23 The catalyst which is used iÃ-, this invention is selected frorri any three 24 component contrc,i or oxidat:on catalyst well kÃ:own iÃi the ark. Examp4es of catalysts are those described in U.S, Pat. Nos, 4;528,279; 4,791,091;
26 4:760,044; 4.868:148: and 4;868,149, wi~ieh are all incorporated by reference.
27 Preferred cata;ysts well known in the art aÃ:e those that contain platinum and 28 rhodium and optionally paIladitam, while oxidatior) ca#aIyst;, usually do not 29 contain rhodiLsÃgi. Oxddatiari catalysts usually contain platinum aÃid/or pal1ad:urn metal. These catalysts may also coiitain promoteTs and stabiiizer~
31 such as barium, cerir..;m, lanthanum, nickel, and irorr. Ta~~ noble metals 32 promoters and stabilizers are usually deposited on a support such as alumina, 33 siEsua, titar7ia, zi= conia, alumiÃ~o Oicates, and mixtures thereaf with alumina ..~.~-1 beÃng preferred. The catalyst can be conveniently employed in paÃticulate 2 form or the watalytic composite can be deposited on a 5olid monolÃthiz rarrier 3 with a monoiit~ic carrier being preferred. The parliculate form and monolithic 4 form of the cataEyst arp- prepared as described for the adsorbent above.
6 The molecular sieve used in the adsorbent bed, SSi:.vi 5, comprises a 7 crystalline Eiiof~cular sieve having STI topology and having a mole ratio of at 8 least 15 of( 1) an oxide of a first tetravalent element to (2) an oxide of a 9 trivalent element, pentavalent element, second tetravalent e?esTielit wh;ch is 1,0 different from said first tetrav@len# element or mixtuee, therecatr 12 'The present invention oomprÃses a process for catalytic conversion of a 13 feedstock comprising one or more oxygenates compÃis#ng aicohois and ethers 14 to a hydrocarbon product containing light olefins, s.e., C2, G,5 and/or C4 oiefans.
The feedstock is ;oritactr:d with the molecular sieve of the pre:~e-nt inven~tion 16 at effective process conditions to produce light oÃef;iis.
18 The term ` oxyger te" as used here's.n designates compounds sucti as 19 alcohols, ethers and rr.ixtures there of. Examples of oxygenates include, but are riot limited to, methanol and dime-t'17yrl ether.
22 The prc~ess of the present invention may be candtictied ir:~ the pr'eset7 cw of 23 one or more diluents which may be present in tYie oxyge-iate feed in an 24 amount between about 1 and aboÃi: 99 molar perc~rA, based on the total number of moles of all feed and dilueÃit comp~~~ents. Dil4ierits include, but arÃ~>
26 not limited to, heliuni, argon, nitrogen, carbr~~i monoxide, carbon dioxide, 27 hydrogen, water, paraffins, hydrocarbons (such as methane and the like), 28 aromatic compoL:nds, or mÃxtLsres thereof. U. S. Patents No, 4,861,938 arid 29 4,677,242, which are ;ncorporated by reference hereiri rr) their entirety, emphasize the use of a diluent to maintain catalyst selectivitytowai'd the 3, 1 production of light alefins, particularly ethylene.
4.y 1 The oxygenate conversion is preferably conducted in the vapor phase such 2 that the oxygenate Peedstoa k is contacted in a vapor phase Ãn a reactÃon zorie 3 with the molecular sieve of this iri'vention at effective process conditions to 4 produce hydrocarbons, i.e., an effective teÃyi~.~erature, pressure, weight hourly space velocity (WHS\~) and, optionafly; an effective amoaÃi# of dilÃ.Ãenf. The 6 process is conducted for a period of time sufficient to produce the desired light 7 oIefiins. In general, the residence time employed to prodLice the desired 8 product can vary from seconds to a number of hours. It wili bp- rea~~ily 9 appreciated that the residence #EÃ-s-~p- w3lI be determined to a significant extent by the reaction temperature , the molecular sieve catalyst, the WHSV, ttie 11 phase (liquid or vapor) and process design characteristics. The oxygenate 12 feedstock fÃaw rate affects oIefira production. 1ncreasirig the feedstock flow 13 rate increases WHSV and enhances the formation of olefir productson relative 14 to paraffin prodr#ction. However, the eriianced olefin production reiatr~~
to paraffin production is offset by a dimimsl~ed ::oÃiversion of oxygenate to 16 hydrcacarbons.
18 'Fhe oxygenate cotiversÃon process i:s effectively carried out over a wide rarige 19 of pressures, inciuding aufioger3oLis pressures. At pressures between about 0.01 atmospheres (0.1 kPa) and about 1000 atmospheres (101.3 k-Pa), the 2 ?', fort-nat#cn of l4ht olefins will be affected althot#gh the aptimurn amount of 22 product will not necessarily be formed at all pte~~ures. The preferred 23 pressLire is behp,reen about 0.01 atmospheres (0,1 kPa) ~t-id abctif 1 00 24 atmospheres (10.13 k.Pa). More preferably, the pressure vviÃi range froril about I to about 10 atmospheres (10 1 .3 kPa to 1.013 Mpa). 'T'he pressur~~
26 referred to herein are exclLisiue of the, diÃÃ.ient, if any, that is present and refer 27 to the parlmai pressure of the feedstock as it relates to oxygemate.
cornpotrrÃds:
29 The temperature which r-pay be ew-np1oyed in: the oxygenate conversion process may vary over a wide range depending, at least in part, on the, 31, ÃTio1er:uiar sieve cataiyst, In general, the process can be conductp-d at ari 32 effect:ve temperature beton/een abcLsfi 200"C and about 700 u : A the lower 33 ~no' of the temper' ablire range, and t:liÃ~s generally at a lower i-:,it;
of reaction, w3-I the formation of the desired light olefins may become low, At the upper er2d uf 2 the rarige , the process may not form an opflmu=~n amoLint of light olefins and 3 catalyst deactivation may be rapid.
r, The molecular sieve catalyst preferably is incorporated into solid par-kicies in b wfijcli the catalyst is present Ãn an amount effective to promote the desired 7 conversion of ~xygeraates to light oleflns. In arie aspect, the solid particles 8 cornpr3s~ aicataEytÃcally effective amount of the catalyst and at least one 9 matrix material selected from the group consisting of binder mtiierÃaIs, õilleÃ, materials and mixtures thereof to provide adesiÃÃ:d property or properties, 11 e.g., desired catalyst dilutÃon, mechanical strength and the Iikc-, to the solid 12 partlcles. Such anatrix materials are, ofteerÃ,fo sorrie extent, porous in nature 13 and may or may not be effective to proiiiofe the desired reaction. Filler and 14 bÃnder materials 3ncluÃfe: for exarrÃp1c-, syntlie-tlc and nafurally occurring ~ 5 substances such as Ã~?~~tal oxides, clays, sil#cas; aluminas, s~l~r~~a ~1Ã: Ã~~#r~~~;
16 siliea-magnesÃas: s31ica-zirconÃas, si13ca--fhorias and the kÃice, If matrix 17 rriateria&s are included lri the catalyst composition, the molecular sieve 18 prp-fer-abI;i comprises about '4 to 99%, more preferably aboLit 5 to 90%, and 19 still more preferably aboÃ.Ãt 10 to 80% by weight of the total composition.
21 EXAMP1_-ES
23 The following examples demonstrate bLit do not limit fhe present :r3vention.
Example 1 26 Synthesis of A!-ConfainiÃ3g S5Z-7/5 28 1.5 mM of fetra rnethy ler~e- 1:4-b is-(N -m efhylpyrrol idirigu m) drca$lar, SDA
29 (3 rTÃAi OH;a was mixed m a Teflon cup (for a Parr 2-1 rr 1 reactor) with 1.26 grams of tetrzae$hy;orthosiiicate and the c p was placed irà a hood to 31 evaporate (as ethario; is formed from hydroly---i,,c;; over several days.
Wiien all 32 of the visible liquid was gc:ne, the Teflon cup was ruftivebglhed and water was 33 added to bring the HõOl&02 mole ratio to about four. Then, 12 mg of Reheiss 34 F2000 (50% A1:~C ~) was added and dissolved 6nto the reac;tion ÃnfaÃture.
This represents a starting synthesis muleratio, of Si021 A120::. of 100. Lastly, 0,135 ~54.
1 gram of 50% HF was added usinq a plastic pipette. The gel was rÃiÃxed wÃtta a 2 plastic spatuÃa and then the resaiting reaction rr:ix#are was heated iri acÃosed 3 vessel rotating at 43 RPM at 150'C for 16 days. Acrystalline product torny~~
4 which was recovered and found by X-ray dttfractirsn analysis to be molecWar sieve ~SZ-75.
7 Example 2 8 Synthesis otA~ontainingSSZ-75 The procedure described Ãri Example 1 was, repeated, except that the source 1 1 of alr.tniÃnum was l_.Z--210 zeolite (a form Ot deakin?ir=,ated FAU) and tile S021 12 A120; Mofe ratio was 70. The reaction formed SSZ-76 ir~ 10 days.
14 Exar~~~~~ 3 Svnthesis of AI-Cor?tainmnaSS~~,~_y 17 The procedLtre describe(I in Example I was repeated, except that the source 18 of aÃumind~~n was Catapa~ B (a form of pseLsdvbaehmite alumina), The 19 reaction formed SSZ-75 in 10 days.
21 Examp es 4-7 22 SynthesÃsof Al(,SilÃca SSZ-75 24 Aprocer~ure simiÃar to that of Exarrrple 1 vvas repeated using the reaction mÃxtur4 (expressed as mole ratios) aÃ3d conditions shown in the table beIow:.
26 The reactions were run until a crystaÃI;ne product was observed by SEM and 27 theki #h~ product was recovered. TÃie products are also shown ir, the table.
_,M5..
~
;--- -____- _= __- ---- _--- _-_-_-- -__--- _----_ __ ____________________ ~~~ ~r'~~.
Ex. SDr'~! S#~t N# 1.$ 15i01 H ~ a' ~#~~ ~fOl SiO2 "~..1~.P
----- __ ____________ ------------------------------ {
! - - -------------4 0.50 0.0 0.50 5.0 150/43 :... ,.______.__... :........... -=------ ---- --~ OA0 01 0.40 5.0 150r`4'o SSZ-75 ..__ _ 0: 30 0,2 0.30 5.0 150143 ~~-PA' ........... ------- ______ -------------,________ 7 0.20 o.3 O.20 i 5.0 150/43 A#ror zsm-4 P, .............. ------------------- - ....__- ---:.--------3 Example 8 4 Calcination of 13SZ-75 ---------------------------------------------------------6 The prodL3ct from Exatnple 1 was z..alcined 3r: the foIlowing manner: A thin bed 7 of material was heated m a flowir1g bed of ;air in a-nuffle turnace from rooEll 8 temperature to 120'C at a rate of I C per minute and held at 120 C for two 9 hours. The temperature is then ramped up to 540`C at the same rate and field at this ternpera.tu#re for three hours, after which 2t was increased to 594"t"
11 and held there for another three hours.
13 Example 9 14 Q_onaers:on ofMethanol 16 The calcined matenal of Example 8 (0.10) gram) was pelleted and, meshed 17 (with r~cycÃirg) to 20-40 mesh and packeci into a 3/8 i~icti stainless steel 18 reactor. After sufficierst purge with nitrogen Uarrier gas (20 cclrniri), t~~~
19 catalyst wa,,,, heated to 750'1" {399"C). A feed of 22.5% methanol in water.
~0 was ntrodu;ed into the reactor uia ;,y{s'~~~~~ ~~imp a{ a rate of 1.49 ~c/hr. A
21 sarnpie of the efFluerit stfearr~ was diverted to an ori-Iiiie gas chromatograph at .22 ten tiiinute point of feed introductÃon, SSZ .~ ~showed the following behavior~
24 MethatioI conversion = 1000/o No dimethylether detected 26 C2 ~(,4 iS about 70% of the prod;aci ..tir;..
I showed a mixture of olafins and sasLirates 2 Aromafrcs were made with ethA.arzene the most abundant single produa,~.
3 TrirF-sethylbenzene asamers were observed as the heaviest products At 100 miriL$Ekes ar7 straarn the SSZ-75 was foulang, but still produced the same 6 products (aathaugh very few aroriiatÃt,s were obsarved).
~; , _.
Claims (96)
1. A crystalline molecular sieve molecular sieve having STI topology and having a a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
2. The molecular sieve of claim 1, wherein the molecular, sieve has a mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
3. The molecular sieve of claim 1 having, after calcination, the X-ray diffraction lines of Table II.
4. The molecular sieve of claim 2 having, after calcination, the X-ray diffraction lines of Table II.
5. A crystalline molecular sieve having a composition comprising, as synthesized and in the anhydrous state, in terms of mole ratios, the following:
SiO2 / X c O d at least 15 M2 / n SiO2 0 - 0.03 Q / SiO2 0.02 -0.08 F / SiO2 0.01 - 0.04 wherein X is aluminum, gallium, iron, boron, titanium indium and mixtures thereof, c is 1 or 2; d is 2 when c is 1, or d is 3 or 5 when c is 2, M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M; Q is a tetra methylene -1,4-bis-(N-methylpyrrolidinium) dication and F is fluoride.
SiO2 / X c O d at least 15 M2 / n SiO2 0 - 0.03 Q / SiO2 0.02 -0.08 F / SiO2 0.01 - 0.04 wherein X is aluminum, gallium, iron, boron, titanium indium and mixtures thereof, c is 1 or 2; d is 2 when c is 1, or d is 3 or 5 when c is 2, M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M; Q is a tetra methylene -1,4-bis-(N-methylpyrrolidinium) dication and F is fluoride.
6. A method of preparing a crystalline material, said method comprising contacting under crystallization conditions (1) a source of silicon oxide, (2) a source of aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixture thereof, (3) fluoride ions and (4) a structure directing agent comprising a tetramethylene-1,4-bis-(N-methylpyrrolidinium dication.
7. The method of claim 6 wherein the crystalline material is prepared from a reaction mixture comprising silicon oxide and, in terms of mole ratios, the following:
SiO2 / XaOb at least 15 OH- / SiO2 0.20 -0.80 Q / SiO2 0.20-0.80 M2/n / SiO2 0-0.04 H2O / SiO2 2-10 HF / SiO2 0.20 - 0.80 wherein X is aluminum, gallium, iron, boron, titanium, indium and mixtures thereof, a is 1 or 2, b is 2 when a is 1, b is 3 when a is 2, M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M and Q is a tetramethylene-1,4-bis-(N-methylpyrrolidinium; dication.
SiO2 / XaOb at least 15 OH- / SiO2 0.20 -0.80 Q / SiO2 0.20-0.80 M2/n / SiO2 0-0.04 H2O / SiO2 2-10 HF / SiO2 0.20 - 0.80 wherein X is aluminum, gallium, iron, boron, titanium, indium and mixtures thereof, a is 1 or 2, b is 2 when a is 1, b is 3 when a is 2, M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M and Q is a tetramethylene-1,4-bis-(N-methylpyrrolidinium; dication.
8. A process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
9. The process of Claim 9 wherein the molecular sieve has a mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
10. The process of Claim 9 wherein the molecular sieve is predominantly in the hydrogen form.
11. The process of Claim 9 wherein the molecular sieve is substantially free of acidity.
12 The process of Claim 9 wherein the process is a hydrocracking process comprising contacting the catalyst with a hydrocarbon feedstock under hydrocracking conditions.
13. The process of Claim 9 wherein the process is a process for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatics content comprising contacting a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range above about 40°C and less than about 200°C
under aromatic conversion conditions with the catalyst.
under aromatic conversion conditions with the catalyst.
14. The process of Claim 13 wherein the molecular sieve is substantially free of acid.
15. The process of Claim 13 wherein the molecular sieve contains a Group VIII metal component.
16. The process of Claim 9 wherein the process is a catalytic cracking process comprising contacting a hydrocarbon feedstock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with the catalyst.
17. The process of Claim 16 wherein the catalyst additionally comprises a large pore crystalline cracking component.
18. The process of Claim 9 wherein the process is an isomerization process for isomerizing C4 to C7 hydrocarbons, comprising contacting a feed having normal and slightly branched C4 to C7 hydrocarbons under isomerizing conditions with the catalyst.
19. The process of Claim 18 wherein the molecular sieve has been impregnated with at least one Group VIII metal.
20. The process of Claim 18 wherein the catalyst has been calcined in a steam/air mixture at an elevated temperature after impregnating of the Group VIII metal.
21. The process of Claim 19 wherein the Group VIII metal is platinum.
22. The process of Claim 9 wherein the process is a process for alkylating an aromatic hydrocarbon which comprises contacting under alkylation conditions at least a molar excess of an aromatic hydrocarbon with a C2 to C20 olefin Linder at least partial liquid phase conditions and in the presence of the catalyst.
23 The process of Claim 22 wherein the olefin is a C2 to C4 olefin.
24. The process of Claim 23 wherein the aromatic hydrocarbon and olefin are present in a molar ratio of about 4:1 to about 20.1, respectively.
25. The process of Claim 23 wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthtalene, naphthalene derivatives, dimethylnaphthalene or mixtures thereof.
26. The process of Claim 9 wherein the process is a process for transalkylating an aromatic hydrocarbon which comprises contacting under transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of the catalyst.
27. The process of Claim 26 wherein the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon are present in a molar ratio of from about 1:1 to about 25:1, respectively.
28. The process of Claim 26 wherein, the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof.
2 The process of Claim 26 wherein the polyalkyl aromatic, hydrocarbon is a dialkylbenzene.
30. The process of Claim 9 wherein the process is a process to convert paraffins to aromatics which comprises contacting paraffins under conditions which cause paraffins to convert to aromatics with, a catalyst comprising the molecular sieve and gallium, zinc, or a compound of gallium or zinc.
31. The process of claim 9 wherein the process is a process for isomerizing olefins comprising contacting said olefin under conditions which cause isomerization of the olefin with the catalyst.
32. The process of Claim 9 wherein the process is a process for isomerizing are isomerization feed comprising an aromatic C8 stream of xylene isomers or mixtures of xylene isomers and ethylbenzene, wherein a more nearly equilibrium ratio of ortho-, meta and para-xylenes is obtained, said process comprising contacting said feed under isomerization conditions with the catalyst
33. The process of Claim 9,wherein the process is a process for oligomerizing olefins comprising contacting an olefin feed under oligomerization conditions with the catalyst.
34. A process for converting oxygenated hydrocarbons comprising contacting said oxygenated hydrocarbon under conditions to produce liquid products with a catalyst comprising a molecular sieve having a mole ratio of at least 15 of an oxide of a first tetravalent element to an oxide of a second tetravalent element which is different from said first tetravalent element, trivalent element, pentavalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table II.
35. The process of Claim 34 wherein the oxygenated hydrocarbon is a lower alcohol.
36. The process of Claim 35 wherein the lower alcohol is methanol.
37. The process of Claim 9 wherein the process is a process for the production of higher molecular weight hydrocarbons from lower molecular weight hydrocarbons comprising the steps of:
(a) introducing into a reaction zone a lower molecular weight hydrocarbon-containing gas and contacting said gas in said zone under C2+ hydrocarbon synthesis conditions with the catalyst and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon; and (b) withdrawing from said reaction zone a higher molecular weight hydrocarbon-containing stream
(a) introducing into a reaction zone a lower molecular weight hydrocarbon-containing gas and contacting said gas in said zone under C2+ hydrocarbon synthesis conditions with the catalyst and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon; and (b) withdrawing from said reaction zone a higher molecular weight hydrocarbon-containing stream
38. The process of Claim, 37 wherein the metal or metal compound comprises a lanthanide or actinide metal or metal compound,
39. The process of Claim 37 wherein the lower molecular weight hydrocarbon is methane.
40. A catalyst composition for promoting polymerization of 1-olefins said composition comprising (A) a crystalline molecular sieve having a mole, ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide, of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table II; and (B) an organotitanium, or organochromium compound.
41. The process of Claim 9 wherein the process is, a process for polymerizing 1-olefins, which process comprises, contacting 1-olefin monomer with a catalytically effective amount of a catalyst composition comprising (A) a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminium oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof; and (B) an, organotitanium or organochromium compound.
under polymerization conditions which include a temperature and pressure suitable for initiating and promoting the polymerization reaction
under polymerization conditions which include a temperature and pressure suitable for initiating and promoting the polymerization reaction
42. The process of Claim 41 wherein the 1-olefin monomer is ethylene.
43 The process of Claim 9 wherein the process, is a process for hydrogenating a hydrocarbon feed containing unsaturated hydrocarbons, the process comprising contacting the feed with, hydrogen under conditions which cause hydrogenation with the catalyst.
44. The process of Claim 43 wherein the catalyst contains metals, salts or complexes wherein the, metal is selected from the group consisting of platinum, palladium, rhodium, iridium or combinations thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, rhenium, manganese and combinations thereof.
45. A dewaxing process comprising contacting a hydrocarbon, feedstock under dewaxing conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) oxide of a first tetravalent element to (2) an, oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
46. A process for improving the viscosity index of a dewaxed product of waxy hydrocarbon feeds comprising contacting a waxy hydrocarbon feed under isomerization dewaxing conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
47. A process for producing a C20+ tube oil from a C20+ olefin feed comprising isomerizing said olefin feed under isomerization conditions, over a catalyst comprising a crystalline molecular sieve having STI topology a mole ratio of at least about 14 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
48. The process of Claim 47 wherein the catalyst further comprises at least one Group VIII metal.
49. A process for catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350°F (177°C) and containing straight chain and slightly branched chain hydrocarbons comprising contacting said hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) under dewaxing conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element of mixture thereof.
50. The process of Claim 49 wherein the catalyst further comprises at least one Group VIII metal.
51. The process of Claim 49 wherein said catalyst comprises a combination comprising a first catalyst comprising the molecular sieve and at least one Group VIII metal, and a second catalyst comprising an aluminosilicate zeolite which is more shape selective than the molecular sieve of said first catalyst.
52. A process for preparing a lubricating oil which comprises:
hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil; and catalytically dewaxing said effluent comprising hydrocracked oil at a temperature of at least about 400°F (204°C) and at a pressure of from about 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge) in the presence of added hydrogen gas with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil; and catalytically dewaxing said effluent comprising hydrocracked oil at a temperature of at least about 400°F (204°C) and at a pressure of from about 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge) in the presence of added hydrogen gas with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
53. The process of Claim 52 wherein the catalyst further comprises at least one Group VIII metal.
54. A process for isomerization dewaxing a raffinate comprising contacting said raffinate in the presence of added hydrogen under isomerization dewaxing conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
55. The process of Claim 54 wherein the catalyst further comprises at least one Group VIII metal.
56. The process of Claim 54 wherein the raffinate is bright stock.
57. The process of Claim 46, 47, 48, 49, 50, 51, 52, 53, 54, 55 or 56 wherein the molecular sieve has a mole ratio of at least about 14 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium, oxide, indium oxide and mixtures thereof.
58. The process of Claim 12, 16, 18, 22, 26, 45, 46, 47, 49, 52 or 54 wherein the molecular sieve is predominantly in the hydrogen form.
59. In a process for separating gasses using a membrane containing a molecular sieve, the improvement comprising using as the molecular sieve a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 or (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
60. The process of Claim 59 wherein the molecular sieve has a mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminumoxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
61 The process of Claim 59 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
62. The process of Claim 60 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
63. A process for producing methylamine or dimethylamine comprising reacting methanol, dimethyl ether or a mixture thereof and ammonia in the gaseous phase in the presence of a catalyst comprising a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
64. The process of Claim 63 wherein the molecular sieve has a mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
65. The process of Claim 63 wherein the molecular sieve has, after calcination, the X-ray diffraction, lines of Table II.
66. The process of Claim 64 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II
67. The process of Claim 64 wherein the methanol, dimethylether or mixture thereof and ammonia are present in amounts sufficient to provide a carbon/nitrogen ratio from about 0.2 to about 1.5.
68. The process of Claim 64 conducted at a temperature of from about 250°C to about 450°C.
69. A process for the reduction of oxides of nitrogen contained in a gas stream wherein said process comprises contacting the gas stream with a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
70. The process of Claim 69 wherein the molecular sieve has a mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
71. The process of Claim 69 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
72. The process of Claim 70 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
73. The process of Claim 70 conducted in the presence of oxygen.
74. The process of Claim 70 wherein said molecular sieve contains a metal or metal ions capable of catalyzing the reduction of the oxides of nitrogen.
75. The process of Claim 74 wherein the metal is cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof.
76. The process of Claim 69 wherein the gas stream is the exhaust stream of an internal combustion engine.
77. The process of Claim 75 wherein the gas stream is the exhaust stream of an internal combustion engine.
78. A process for treating a cold-start engine exhaust gas stream containing hydrocarbons and other pollutants consisting of flowing said engine exhaust gas stream over a molecular sieve bed which preferentially adsorbs the hydrocarbons over water to provide a first exhaust stream, and flowing the first exhaust gas stream over a catalyst to convert any residual hydrocarbons and other pollutants contained in the first exhaust gas stream to innocuous products and provide a treated exhaust stream and discharging the treated exhaust stream into the atmosphere, the molecular sieve bed comprising a crystalline molecular sieve having STI
topology and having a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
topology and having a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
79. The process of Claim 78 wherein the molecular sieve has a mole ratio of at least 16 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
80. The process of Claim 78 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
81. The process of Claim 79 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
82. The process of Claim 79 wherein the engine is an internal combustion engine.
83. The process of Claim 82 wherein the internal combustion engine is an automobile engine.
84. The process of Claim 79 wherein the engine is fueled by a hydrocarbonaceous fuel.
85. The process of Claim 79 wherein the molecular sieve has deposited on it a metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof.
86. The process of Claim 85 wherein the metal is platinum.
87. The process of Claim 85 wherein the metal is palladium.
88. The process of Claim 85 wherein the metal is a mixture of platinum and palladium.
89. A process for the production of light olefins from a feedstock comprising an oxygenate or mixture of oxygenates, the process comprising reacting the feedstock at effective conditions over a catalyst comprising a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a tetravalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.
90. The process of claim 89 wherein the molecular sieve has a mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
91. The process of Claim 89 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
92. The process of Claim 90 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II.
93. The process of Claim 90 wherein the light olefins are ethylene, propylene, butylene or mixtures thereof.
94. The process of Claim 93 wherein the light olefin is ethylene.
95. The process of Claim 90 wherein the oxygenate is methanol, dimethyl ether or a mixture thereof.
96. The process of Claim 95 wherein the oxygenate is methanol.
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| PCT/US2007/070210 WO2007146622A2 (en) | 2006-06-08 | 2007-06-01 | Molecular sieve ssz-75 composition of matter and synthesis thereof |
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| US9938217B2 (en) | 2016-07-01 | 2018-04-10 | Res Usa, Llc | Fluidized bed membrane reactor |
| US9981896B2 (en) | 2016-07-01 | 2018-05-29 | Res Usa, Llc | Conversion of methane to dimethyl ether |
| US10189763B2 (en) | 2016-07-01 | 2019-01-29 | Res Usa, Llc | Reduction of greenhouse gas emission |
Also Published As
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| AU2007258049B2 (en) | 2012-05-17 |
| EP2038220A2 (en) | 2009-03-25 |
| US7651603B2 (en) | 2010-01-26 |
| KR101385396B1 (en) | 2014-04-14 |
| WO2007146622A3 (en) | 2008-02-14 |
| WO2007146622A2 (en) | 2007-12-21 |
| US20070284284A1 (en) | 2007-12-13 |
| CA2653928C (en) | 2014-09-09 |
| JP5295953B2 (en) | 2013-09-18 |
| JP2009539747A (en) | 2009-11-19 |
| AU2007258049A1 (en) | 2007-12-21 |
| KR20090021376A (en) | 2009-03-03 |
| US8177961B2 (en) | 2012-05-15 |
| US20100121122A1 (en) | 2010-05-13 |
| WO2007146622A8 (en) | 2008-04-03 |
| EP2038220A4 (en) | 2010-08-11 |
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