CA2015297A1 - Reactivation of metal-contaminated cracking catalysts - Google Patents
Reactivation of metal-contaminated cracking catalystsInfo
- Publication number
- CA2015297A1 CA2015297A1 CA002015297A CA2015297A CA2015297A1 CA 2015297 A1 CA2015297 A1 CA 2015297A1 CA 002015297 A CA002015297 A CA 002015297A CA 2015297 A CA2015297 A CA 2015297A CA 2015297 A1 CA2015297 A1 CA 2015297A1
- Authority
- CA
- Canada
- Prior art keywords
- accordance
- cracking
- spent
- catalyst composition
- cracking catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/521—Metal contaminant passivation
Abstract
ABSTRACT
A process for reactivating a spent, metal-contaminated zeolite-containing cracking catalyst composition comprises the substantially simultaneous contacting with a fluorine compound (preferably NH4F) and a metals passivating agent (preferably a compound of Sb or Ca). The thus reactivated cracking catalyst composition is employed in a catalytic cracking process.
A process for reactivating a spent, metal-contaminated zeolite-containing cracking catalyst composition comprises the substantially simultaneous contacting with a fluorine compound (preferably NH4F) and a metals passivating agent (preferably a compound of Sb or Ca). The thus reactivated cracking catalyst composition is employed in a catalytic cracking process.
Description
~ i 32652CA
R~ACTIVATION OF METAL-CONTAMINATED CRACKING CATALYSTS
Ba k~_ound of the Invention This lnvention relates to a method of reactivatlng spent, metal-contaminated zeolite-containing catalytic cracking catalys-ts. In another aspect, this invention relates to a reactivated cracklng catalyst. In still another aspect, this invention relates to a catalytic cracking process employing a reactivated spent, metal-contflminated cracking catalyst.
Mcthods of rejuvenating deactivated zeolite-containing cracking c~talysts by treatment with fluorine compounds are known and have been dlsclosed in the patent literature, e.g., in U.S. Patents 4,8]4,066, 4,559,131 and 4,500,422. Also, the use of so-called passivatlng agents for allevlatlng the detrimental effects of me-tal contaminants on cracklng catalysts has been described ln the patent literature, e.g., ill U.S.
Patents 3,711,422, 4,337,144 and 4,549,958. Ilowever, ther~ is an evcr present need to develop n~w, more effectivc nnd/or eff-LcLerlt catnlyst reactlvation and metals pass:Lvatlon process~s.
,Summary of the_Inventlon It is flll obJect of th:Ls Inventlon to provLde a multl-step process for treflting a spent, metn'i-contamLnnte(l zeolLte-contalrlirlg crackLng catalyst composltLon, under snch condltlon~ as to enhnrlce Its catalytic crackLng actlvity and to reduce its capability of generatlng hydrogen durlng cata]ytlc cracking. It -is another c)b,3ect of thLs Lnvsntlon to provlde a reactivated spent catalyst composltLon. It ls stlll another obJect of this lnvention to provide a catalytic cracklng ...
, process employing a reactivated spent cracking catalyst composition.
Other objects and advantages will become apparent from the detailed description of the invention and the appended claims.
In accordance with this invention, a process for reac-tivating a spent cracking catalyst composition comprises the step of:
contacting a spent zeolite-containing catalytic cracking catalyst composition, which contains at leas-t one metal contaminant and at least a portion of which has previously been used in a catalytic cracking process (and has thereby lost some of its initial catalytic cracking activity, i.e., its cracking activity before its use in the catalytic cracking process), substantially simultaneously with (a) at least one fluorine compound selected from the group consisting of NH~F, NH4HF2 and HF and (b) a metals passivating agent selected from the group consisting of compolmds of an alkaline earth metal (Be, Mg, Ca, Sr, Ba), antimony, and mixtures of these compounds, under such contacting conditions as to reduce the detrimental effect of said at least one metal contaminant contained in the spent cracking catalyst composition during catalytic cracking, as measured by hydrogen generation in a test for catalytically cracking a heavy hydrocarbon-containing oil, carried out substantially in accordance with the procedure of Example II of U.S. Patent 4,794,095, the disclosure of which is herein incorporated by refsrence.
In a preferred embodiment, the fluorine compound is ammonium fluoride, more preferably di~solved in water. Tn another preferred embodiment, the passivating agent in step (d) :Ls selected from among compounds of Sb and Ca.
Also in accordance with this inventLon, a reactLvated spent catalyst havlng been prepared by the nbove-described reactivation process (comprising substflntially simultaneous contacting with at lcast one fluorine compound and at Least one pnssivating agent) Ls provLded.
Further i.tl accordanco with th:Ls invention, a catalytLc cracklng process is provided comprislng the step of contacting a hydrocarbon contnining feed stream with a zeollte-contalntng cracking catalyst composition, under such cracking condltions as to obtain at least one normally liquid (i.e., liquid at 25 and 1 atm.) hydrocarbon containing product stream having a lower initial boiling point and hi~her API
~ 32652CA
gravity than sald hydrocarbon-containing feed stream, where:in at least a po~tion of said zeollte-containing cracking catalyst composition is a reactivated spent catalys-t composi-tion having been substantially simultaneously contacted with a suitable fluorine compound and at least one passivating agent, as described above.
~etailed_Description of the ~nvention The term "cataly-tic cracking process", as used herein, implies that essen-tially no hydrocrackin& occuxs and that the catalytic cracking process is carried out with a hydrocarbon-containing oil, substantially in the absence of added hydrogen gas. The term "spent", as used herein, implies that at least a portion of the 7Jeolite-containing catalyst composition employed in step (a) has been uaed in a process for catalytically cracking hydrocarbon-containi.ng oils, in particular those containing metal (Ni, V, Cu) impurities, and has then been regenerated by stripping of adhered oil from the catalyst (such as by steam-stripping) and subsequent heating in an oxidizlng gas atmosphere (such as air) so as to burn off coke deposits on the catalyst composition. The term "reactivating", as used herein, implies that the extent of hydrogen generation (durLng catalytic cracking) caused by metal deposits on a spent cracking catalyst is reduced. Additional benefits (such as higher feed conversion, higher gasoline yield) may also be a-ttained by the reactivatlng treatment of the spent catalyst.
Any spent 7~eo].ite-conta:in:Lng catal.yst composit:Lon, which contains at least one metal contam:Lnant and at least a port:Lon of which has previously been used ln a cata].yt:lc cracklng process, can be used as starting materlal in the reactlvatl.on process of thi.s Lnventlon. The spent cntalyst compos:Lt:i.on can contaln any porti.on of SllCh regCnerflte( catalyst compos:i.tion, rangi.llg Erom lOO% to abo~t 1() we:Lgllt-% (:L.c., cont:aining 0% to flbout ~O weight-% fresh, urlllsed z~ol:Lte-corlta:lrllng cracking cntalyst compos:Ltlon). The term "spent catalyst composit:Lon", as used here:Ln, encompasses eq~lil.ibrium crackLng catalysts, wh:Lch are commonly employed in commercial cracking operatlolls and generally comprise a physical blend of regenerated used catalyst composition and fresh (unused) cracking catalyst composition. An equilibrium catalyst generally comprises a mix-ture of catalyst pflrt:Lcles o various ages, -: ~
.
' ~ 32652CA
i.e., a portion of the equilibrium catalyst particles has passed through a varying number of cracking and regeneration cycles, while a small portion of th~ eq~ilibrium catalyst particles is fresh (unused) cracking catalyst composition.
The zeoli-te component of the spent zeolite-containing cracking composition of this invention can be any natural or synthetic crystalline aluminosilicate zeolite which exhibits cracking activity. Non-limiting examples of such zeolites are fau~asite, chabazite, mordenite, offretite, erionite, Zeolon, zeolite X, zeolite Y, zeolite L, zeolite ZSM-4, zeolite ZSM-5, zeo].ite ZSM-ll, zeolite ZSM-12, zeolite ZSM-23, zeolite ZSM-35, zeolite ZSM-38, zeolite ZSM-48, and the like, and mixtures thereof.
Additional examples of suitable zeolites are listed in U.S. Patent 4,158,621, the dlsclosure of which is herein incorporated by reference.
The term "zeolite", as used herein, includes zeolites which have been pretreated, such as those from which a portion of Al has been removed from the crystalline framework, and zeolites which have been ion-exchanged with rare earth metal or ammonium or by o-ther conventional ion-exchange methods. The term "zeolite", as used herein, also includes essentially aluminum-free si].ica polymorphs, such as silicalite, chromia silicates, ferrosilicates, borosilicates, and the like, as disclosed in U.S. Patent 4,556,749, the disclosure oE which ls herein incorporated by reference.
Generally the zeolite component of the spent cracking catalyst composition is dispersed in a suitable so].id refractory inorgflnic matrix material, such as alumina, silica, silica-alumina (presently preferred), aluminum phosphate, magnesium oxide, mixtures of two or more of the above-listed materials, and the like. The preparation of such zeolite/matrix cracking catalyst composit:Lons is well known flnd is not crit:Lcal feature of this :Lnvention. GenQral].y, the surface flrea (meflsured by nitrogen fldsorption, substflnt:Lfll].y 1.n ~ccordance wi.th the BET method of Brunfluer, Emmett flnd Teller) of the spent zeolite/matrix cracking catalyst compos:Ltion used in step (A) iS ln the range of from flbout 100 to about 800 m2/g. Gener~lly, the we:Lght rfltlo of zeolite to matrix material in the spent crflck:Lng catalyst composltlon i.s :Ln the range of from about 1:20 to about 1:1.
~ 32652 The spent 7eolite-containing cracking catalyst composltion employed in the process of the inven~ion contains metal compounds as contaminants (generally as oxides), such as co~pounds (particularly oxides) of Ni, ~, Fe, and Cu, and the like. Contaminants of each metal can be present in amounts ranging from traces (about 0.01 wei~ht-%) to about 2.0 weight-% of contaminant of each metal, expressed as metal oxide. These impurities in the spent cracking catalyst compositions have generally been absorbed from the oil feed in a previous cracking process.
However, the origin of these metal impurities is not believed to be a critical feature of this invention.
Fluorine compounds which can be employed in the reactlvation process of this invention are NH4F (preferred), NH4HF2, HF, and mixtures of two or more of these compounds. The fluorine compound can be a gas or a liquid or a solid. Preferably, the fluorine compound is an inorganic fluoride, more preferably NH4F, most preferably dissolved in water.
The term "metals passivating", as used herein, implies that the detrlmental effect of generating H2 durlng catalytic cracking caused by metal deposits on a cracking catalyst composition has been mitigated.
Any suitable metals passivating agent selected from the group consisting of compounds of Be, Mg, Ca, Sr, Ba, Sb, and mlxtures thereoE can be used in the reactivation process of this invention. Non-llmiting examples of such compounds are described in U.S. Patents 3,711,422, 4,025,458, 4,321,t28, 4,337,144, 4,473,463, and 4,728,62~, the disclosures of which are incorporated herein by reference. Preferred passivating agents include: antimony trls(O,O-dlhydrocarbyl) phosphorodithtofltes, antimony oxides (Sb203, Sb205), ~ntimony carboxylates, antimony mercapt:Ldes, compounds of calcium, such as Ca nitrnte, Ca carboxylates, and the llke.
The substantlally simuLtarleous contacting of the spent, metal-contaminated zeolite-containing cracking catalyst wLth the fluorlne compound(s) and the metal pass1vatin$ agent(s) can be carried out Ln any suitable manner. In one mode of operation, the spent cracking catalyst is contacted (elther by impregnation or by spraying or the like) with a solution which contains both the fluorine compound(s) and the metals , ~ 32652CA
passivating agent(s). This mode is feasible if the fluorine compound and the metals passivating agent do not react with one another and do no-t form a precipitate.
In another mode of operation, a first solution containing at least one fluorine compound and a second solu-tion containing at leas-t one metal passivating agent are prepared. Then the spent catalyst composition is contacted with the first solution and immediately thereafter with the second solution ~either by impregnation or by spraying). Or the spent catalyst is contacted with the second solution and immediately thereafter with the first solution (either by impregnation or by spraying). Or the spent catalyst is simultaneously sprayed with the first solution and the second solution.
The contacting process can be carried out either as a batch process or as a continuous process. Any suitable time of contact of the spent cracking catalyst composition with the first and the second solutions can be employed, generally about 0.l to about l0 hours. Any suitable temperature can be employed ln the contacting process, generally about 10 to about 100C. It is generally preferable to carry out some agitation (e.g., stirring or tumbling or falling of the spent catalyst partlcles) during the contacting step.
Any suitable solvent for the fluorine compound(s) and for the metals passivating agent(s) can be employed, such as water, alcohols (such as methanol, ethanol, etc.) ester8 (such as ethyl acetate), ketones (such as acetone), liquid hydrocarbons (such as hexane, heptane, cyclohexane, ben~ene, toluene and the like). The choice of the solvent(s) will be determlned by the chemlcal nature of fluorlne compound(s) and oi the metals passivatlng agent(s), and can easily be made by those having ordinary sklll :Ln the art. Any suitable concentratLon of tbe f1uorlne compound(s) ln a solutlon can be employed, preferably abo1Jt O.Ot to about 2 moltl (more preferably about 0.l-l mol/l). Any sultable concentratlon of the metnls passLv~tlng agent(s) ln a llquld medlum, preferably a solutlon, can be employed, preferably about 0.01-0.5 mol/l (morc preferably Mbout 0.l to 0.3 mol/l). It ls withln the scope of thls lnventlon to use a colloldal dLspersion of the passlvatlng agent in a llquld medium (e.g., ln water).
Any suitable weight ratio of the contacting solution(s) to the spent zeolite-containing cracking catalyst can be employed in the reactivation process of this invention. Generally, these weight ratios are selected such that the ratio of the number of millimoles of the fluorine compound(s) to the number of grams of the spent cracking catalyst composition is in the range of from about 0.01:1 to about 10:1 (preferably about 0.2:1 to about 1:1), and the ratio of the number of grams of metals passivating agent(s) -to the number of grams of spent catalyst composition is in the range of from about 0.001:1 to about 0.5:1 (preferably about 0.002:1 to about 0.2:1). Preferably, the concentration of the metals passivating agent in solution and the ratio of solution to spent catalyst are chosen such that about 0.01 to about 5, more preferably about 0.01-2, weight-% of metals pAssivating element (i.e., Sb, Ca, etc. and mixtures thereof) is incorporated into the spent cracking ca-talyst.
Preferably, the spent cracking catalyst is heated after the contacting with the fluorine compound(s) and the metals passivating agent(s). Any suitab]e heating conditions can be employed which are effective to substantially dry the spent catalyst which has been treated with the fluorine compound(s) and metals passivating agent(s).
Preferably, the treated spent catalyst is first heated at a relatively low temperature (more preferably at about 80-200C) for a time long enough (more preferably at about 0.5-10 hours) to substantially dry the treated spent catalyst. Preferably, the obtained substantially dried catalyst materLal is tben heated ~t a higher temperature (more preFerably at about 300-500C for about 0.5-10 hours), primarily for the purpose of decomposing the metals passivating agent(s) to oxides of tho metal passivating element(s) r such as oxides of Sb, Ca and the like. The above heating steps can be carried out in arl oxldizing gas, such as Air~ or :ln an inert gas atmosphere (e.g., in a streAm of N2 or ~r or lle).
The roactivated catalyst composltion which is obtained in the reactivatlon process of thls invent:Lon can be used in any catalytic cracking process, i.e., a process for catalytLc~lly cracking hydrocarbon-containing oil feedstocks, in any sultnble cracking reactor (e.g., in a FCC reactor or in a Thermofor moving bed reactor), essentially in the absence of added hydrogen gas. The reactivated catalyst composition can be used alone or in admixture with fresh (unused) zeolite-contalning catalys-t composition in catalytic cracking processes.
The hydrocarbon-con-taining feed stream for the catalytic cracking process of this invention can be any suitable feedstock.
Generally the feed has an initial boiling point (ASTM D 1160) in excess of about 400F, preferably a boiling range of from about 400 to about 1200F, more preferably a range of from about 500 to about 1100F, measured at atmospheric pressure conditions. The API gravity (measured at 60F) generally ls in the range of from about 5 to about 40, preferably from about 10 to about 35. Frequently these feedstocks contain Ramsbottom carbon residue (ASTM D524; generally about 0.1-20 weight-%), sulfur (generally about 0.1-5 weight-% S), nitrogen (generally about 0.05-2 weight-% N), nickel (generally about 0.05-30 ppm Ni, i.e., parts by weight of Ni per million parts of feed), vanadium (generally about 0.1-50 ppm V) and copper (generally about 0.01-30 ppm Cu).
Non-limiting examples of suitable feedstocks are light gas oils, heavy gas oils, vacuum gas oils, cracker recycle oils (cycle oils), residua (such as distillation bottoms fractions), hydrotreated resid-ua (e.g., hydrotreated in the presence of Ni, Co, Mo-promoted alumina catalysts), liquid coal pyrolyzates, liquid products from extraction or pyrolysis of tar sand, shale oils, heavy fractions of shale oils, and the like. The presently most preferred feedstocks are heavy gas oils and hydrotreated residua.
Any suitable reac-tor can be used for the catalytic cracking process of this invention. Generally, a fluidized-bed catalytLc cracking (FCC) reactor (preferably containing one or more rlsers) or a moving-bed catalytic cracking reactor (e.g., a Thermofor catalytic cracker) ls employed, preferably a FCC rlser crackLng unlt. Examples of such FCC
cracking unlts are descrLbed in U.S. Patents 4,377,470 and 4,424,116.
Generally, a catalyst regeneration unlt tfor removal of coke deposlts) Ls combined with the FCC crackLng unit, as Ls ShOWII in the above-cLted patents.
Speclflc operatlng condltlons of the cracking operatlon depend greatly on the type of feed, the type and dimenslons of the cracklng reactor and the oll feed rate. Examples of operating condltions are ~ Pl~ 32652CA
described in the above-cited patents and in many other publications. In an FCC operation, genera]ly the weight ratio of catalyst composition to oil feed (i.e., hydrocarbon-containing feed) ranges from about 2:1 to about 10:1, the contact -time between oil feed and catalyst is in the range of from about 0.2 to about 2.0 seconds, and the cracking temperature is in the range of from about 800 to about 1200CF.
Generally, steam is added with the oil feed to the FCC reactor so as to aid in the dispersion of the oil as droplets. Generally, the weight ratio of steam to oil feed is in the range of from about 0.05:1 to about 0.5:~.
The separation of spent (i.e., used) cracking catalyst from gaseous and liquid cracked products and the saparation of cracking products into various gaseous and liquid product fractions can be carried out by any conventional separation means. The most desirable product fraction is gasoline (ASTM boiling range: about 180-400F).
Non-limiting examples of such separation schemes are shown in "Petroleum Refining" by James H. Gary and Glenn E. Handwerk, Marcel Dekker, Inc., 1975.
Generally, cracking catalysts are regenerated, preferably by steam stripping for removal of adhered oll and subsequent heating under oxidlzing conditions so as to burn off carbon deposits. At least a portion of the regenerated cracking catalyst composition can then be treated by the reactivation process of this invention and thereafter be recycled to the catalytic cracking reactor, generally in admixture wlth fresh tunused) cracking catalyst.
The following examples are present to further illustrate this invention and are not to be considerod as unduly limiting the scope of this invention.
E AMPLE I
This example illustrates the reactivation of a metal-contamlnated zeollte-containing equllibrium catalyst, i.e., a catalytlc crackirlg cfltfllyst a portlon of which had previously been employed in a catalytic cracking process and had then been rcgenerflted.
Cfltfllyst A (Control) was a GX0-40 equil:Lbrium cfltalyst, which hfld been supplied as fresh catfllyst by Dnvison Chemicfll Dlvision of ~ 3265ZCA
W. R. Grace and Company, Baltimore, MD, and had previously been employed in a commercial FCC cracking process in a refinery of Phillips Petroleum Company and thereafter had been regenerated by heating in air. The fresh catalyst contained about 25 weight-% ~eolite and about 75 weight-%
silica-alumina matrix. Catalyst A contained abou-t 0.24 weight-% Ni, about 0.34 weight-% V, about 0.61 welght-% Fe, about 0.01 weight-% Cu, 0.05-0.15 weight-% Sb, and about 0.36 weight-% Na. Catalyst A had a surface area of 113 m2/g, a total pore volume of 0.23 cc/~, an apparent bulk densi-ty of 0.89 g/cc, and a 7.eollte unit cell size of 24.39 ~.
Catalyst B (Control) was prepared by pouring a solution of 0.36 grams Vanlube 672 (provided by R. T. Vanderbilt Company; Norwalk, CT;
containing Sb tris(0,0-dipropyl) phosphordithioate at a concentration of 10.7 weight-% Sb) in 50 cc toluene over 33.5 grams of Catalyst A. The mixture of the antimony solution and Catalyst A was stirred and heated to dryness. The dried material was placed into a quartz reactor and heated in a stream of nitrogen at a temperature which was gradually raised from 400F (initial) to 1200F (final) within one hour. The catalyst material was then calcined for 1 hour in air at 1250F.
Catalyst C (Control) was prepared by impregnating 100 grams of Catalyst A with a solution of 3.8 grams of NH4F in 100 cc water and dried in air for 2 hours at 120C.
Catalyst D (Invention) was prepared by pouring first a solution of 1.9 grams of NH4F in 24 cc water and immediately thereafter a mixture of 0.288 grams of Phil-AD CA 6000 (an aqueous dispersion of Sb20s, containing about 20 weight-% Sb; prov:lded by Ca-talyst Resources, Inc.;
Pasadena, TX) and 24 cc water over Catalyst A. The entire mixture of Catalyst A, NH4E solution and antimony dispersion was s-tirred and heated to dryness in a:Lr at 120C.
Catalysts A through D were then evaluated in a MCBU
(micro-confi.ned bed unit) cracking test reactor, substAntially in accordance with the procedure of Example II of U.S. Patetlt 4,794,095.
Cracking test condi.tions comprised a temperaturc of about 950F, a catalyst to oil weight ratio of 6:1, and the use of a hydrotreated residuuln as oil feed having API gravity at 60C of 18.7, sulfur content of 0.53 weight-%, basic nitrogen conterlt of 0.09 wei.ght-%, Conradson carbon content of 6.7 weight-%1 nickel content of 10.6 ppm (parts per ~3 ~ 32652CA
million by weight~ and vanadium content of 12.7 ppm~ Tcst results are summarized in Table I.
':
.~
G ~ a~ a~o C~
,~
~hd h~ ~ I
~ 8 -u r rc C) I
~i:
I
I
o ~ ,~ ol ol O O O~ l o o oOI a~l o o ol ol O
to ~ ~
H ~ ~d ~ A
o I .3 ,~ l h I ~ ~ ~ ~1 ~1 ~ ~ C~ l ol ~1 ~ ~ ~1~$1 0 R a h o h e ~ _ _ _ ( '4~ c ~ ~ c cd ~a O h ~ Z h ~ ~d Z ~ + a) ~ ~ a P P ~ P U~ P
~ ~ ¢ ~: ~ ~ ~ F~
o4 X
~G
I .s::: m: _: ~_: ~_ _ I ,~
I
~ 32652CA
Test results in Table I show that the amount of hydrogen generated by the metfll-contamlnated equilibrium cracking catalyst was lowest when it had been ~reated simultaneously with an antimony compound and ammonium fluoride. Furthermore, the reduction in ~l2 generation caused by trea-tment with Sb and NH4F (Catalyst D), unexpectedly, was higher than the cumulative reduction in ll2 generation caused by treatment with Sb alone (Catalyst B) and with NH4F alone (Catalyst C).
Example II
This example provides additional test results on the reactivation of a metal-contaminated equilibrium cracking catalyst.
Catalyst F (Control) was a copper contaminated equilibrium cracking catalyst, similar to Catalyst A but containing more Cu than Catalyst A. Catalyst F contained 320 ppm Cu.
Catalyst G (Control) was similar to Catalyst C (Example I) but contained more Cu. The NH4F-treated Catalyst F contained 5000 ppm F.
Catalyst H (Control) was similar to Catalyst B but contained more Cu. The Sb205-treated Catalyst F (treated with Phil-Ad CA 6000;
see Example I) contained 740 ppm Sb.
Catalyst I (Invention) WRS similar to Catalyst D (see Example I) but contained more Cu. It contained 5000 ppm F and 740 ppm Sb.
Catal~st J (Control) was SbF3-treated Catalyst F (rather than NH4F/Sb20s-treated Catalyst F). Catalyst J contained 740 ppm Sb (as SbF 3 ) .
Catalyst K (Control) was a calcium-treated Catalyst F, and was prepared by stirrlng Catalyst F with an aqueous solution of Ca(N03)2-4ll20, fol~.owed by hea-ting to dryness. Cata]yst K contained 238 ppm Ca.
~ y~__ (Invention) was prepared by stirring Catnlyst F with an aqueous solution of NH"F and :Lmmediately thereafter with an aqueous solution of Ca(N03)2~4H2O, fo].lowed by heating to dryness. Catalyst L
contained 238 ppm Ca and 5000 ppm F.
Catalysts F through L were eva].uated in a MCBU cracking test reactor a-t the conditi.ons descri.bed in Example I. Test results are summarized in Table II.
14 2 ~ 7 I
I
~A
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a) o ~ ~ ~o o o o o r~ u) ~D r~ ~ ~J o o~ o r~ oo r~ r~ r~ o o c o P o r~ r~ r~ r~ r~ ~o oo oc o~ r~ r~ r~ r~ r~ oo cr r~ oo r~ r~ r~ r~ r~ ~ o co O l I ~ ~ ~ I Z ~1 td ~ ~ I Z ~ - ~ + ~ +
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Test results listed in Table II show that treatment of a copper-contamiDate(i equilibrium cracking catalyst with an antimony or a calcium compound alone had no beneficlal effect on hydrogen generation (compare runs 15-18 with runs 22-25 and wl-th runs 30-32). It is thus most surprising that the combination of NH4F with the antimony compound and the combinatlon of NH4F with the calcium compound were more effective ln reduclng hydrogen generatlon than treatment wlth NH4F alone (compare runs 19-21 wlth runs 26-28 and runs 33-35). Furthermore, the combinatlon of antimony compound and NH4F was much more effectlve in suppressing H2 generation than SbF3 (compare runs 26-28 wlth run 29).
Reasonable varlations, modlflcations and adaptations for various conditions and uses can be made within the scope of the disclosure and appended claims.
R~ACTIVATION OF METAL-CONTAMINATED CRACKING CATALYSTS
Ba k~_ound of the Invention This lnvention relates to a method of reactivatlng spent, metal-contaminated zeolite-containing catalytic cracking catalys-ts. In another aspect, this invention relates to a reactivated cracklng catalyst. In still another aspect, this invention relates to a catalytic cracking process employing a reactivated spent, metal-contflminated cracking catalyst.
Mcthods of rejuvenating deactivated zeolite-containing cracking c~talysts by treatment with fluorine compounds are known and have been dlsclosed in the patent literature, e.g., in U.S. Patents 4,8]4,066, 4,559,131 and 4,500,422. Also, the use of so-called passivatlng agents for allevlatlng the detrimental effects of me-tal contaminants on cracklng catalysts has been described ln the patent literature, e.g., ill U.S.
Patents 3,711,422, 4,337,144 and 4,549,958. Ilowever, ther~ is an evcr present need to develop n~w, more effectivc nnd/or eff-LcLerlt catnlyst reactlvation and metals pass:Lvatlon process~s.
,Summary of the_Inventlon It is flll obJect of th:Ls Inventlon to provLde a multl-step process for treflting a spent, metn'i-contamLnnte(l zeolLte-contalrlirlg crackLng catalyst composltLon, under snch condltlon~ as to enhnrlce Its catalytic crackLng actlvity and to reduce its capability of generatlng hydrogen durlng cata]ytlc cracking. It -is another c)b,3ect of thLs Lnvsntlon to provlde a reactivated spent catalyst composltLon. It ls stlll another obJect of this lnvention to provide a catalytic cracklng ...
, process employing a reactivated spent cracking catalyst composition.
Other objects and advantages will become apparent from the detailed description of the invention and the appended claims.
In accordance with this invention, a process for reac-tivating a spent cracking catalyst composition comprises the step of:
contacting a spent zeolite-containing catalytic cracking catalyst composition, which contains at leas-t one metal contaminant and at least a portion of which has previously been used in a catalytic cracking process (and has thereby lost some of its initial catalytic cracking activity, i.e., its cracking activity before its use in the catalytic cracking process), substantially simultaneously with (a) at least one fluorine compound selected from the group consisting of NH~F, NH4HF2 and HF and (b) a metals passivating agent selected from the group consisting of compolmds of an alkaline earth metal (Be, Mg, Ca, Sr, Ba), antimony, and mixtures of these compounds, under such contacting conditions as to reduce the detrimental effect of said at least one metal contaminant contained in the spent cracking catalyst composition during catalytic cracking, as measured by hydrogen generation in a test for catalytically cracking a heavy hydrocarbon-containing oil, carried out substantially in accordance with the procedure of Example II of U.S. Patent 4,794,095, the disclosure of which is herein incorporated by refsrence.
In a preferred embodiment, the fluorine compound is ammonium fluoride, more preferably di~solved in water. Tn another preferred embodiment, the passivating agent in step (d) :Ls selected from among compounds of Sb and Ca.
Also in accordance with this inventLon, a reactLvated spent catalyst havlng been prepared by the nbove-described reactivation process (comprising substflntially simultaneous contacting with at lcast one fluorine compound and at Least one pnssivating agent) Ls provLded.
Further i.tl accordanco with th:Ls invention, a catalytLc cracklng process is provided comprislng the step of contacting a hydrocarbon contnining feed stream with a zeollte-contalntng cracking catalyst composition, under such cracking condltions as to obtain at least one normally liquid (i.e., liquid at 25 and 1 atm.) hydrocarbon containing product stream having a lower initial boiling point and hi~her API
~ 32652CA
gravity than sald hydrocarbon-containing feed stream, where:in at least a po~tion of said zeollte-containing cracking catalyst composition is a reactivated spent catalys-t composi-tion having been substantially simultaneously contacted with a suitable fluorine compound and at least one passivating agent, as described above.
~etailed_Description of the ~nvention The term "cataly-tic cracking process", as used herein, implies that essen-tially no hydrocrackin& occuxs and that the catalytic cracking process is carried out with a hydrocarbon-containing oil, substantially in the absence of added hydrogen gas. The term "spent", as used herein, implies that at least a portion of the 7Jeolite-containing catalyst composition employed in step (a) has been uaed in a process for catalytically cracking hydrocarbon-containi.ng oils, in particular those containing metal (Ni, V, Cu) impurities, and has then been regenerated by stripping of adhered oil from the catalyst (such as by steam-stripping) and subsequent heating in an oxidizlng gas atmosphere (such as air) so as to burn off coke deposits on the catalyst composition. The term "reactivating", as used herein, implies that the extent of hydrogen generation (durLng catalytic cracking) caused by metal deposits on a spent cracking catalyst is reduced. Additional benefits (such as higher feed conversion, higher gasoline yield) may also be a-ttained by the reactivatlng treatment of the spent catalyst.
Any spent 7~eo].ite-conta:in:Lng catal.yst composit:Lon, which contains at least one metal contam:Lnant and at least a port:Lon of which has previously been used ln a cata].yt:lc cracklng process, can be used as starting materlal in the reactlvatl.on process of thi.s Lnventlon. The spent cntalyst compos:Lt:i.on can contaln any porti.on of SllCh regCnerflte( catalyst compos:i.tion, rangi.llg Erom lOO% to abo~t 1() we:Lgllt-% (:L.c., cont:aining 0% to flbout ~O weight-% fresh, urlllsed z~ol:Lte-corlta:lrllng cracking cntalyst compos:Ltlon). The term "spent catalyst composit:Lon", as used here:Ln, encompasses eq~lil.ibrium crackLng catalysts, wh:Lch are commonly employed in commercial cracking operatlolls and generally comprise a physical blend of regenerated used catalyst composition and fresh (unused) cracking catalyst composition. An equilibrium catalyst generally comprises a mix-ture of catalyst pflrt:Lcles o various ages, -: ~
.
' ~ 32652CA
i.e., a portion of the equilibrium catalyst particles has passed through a varying number of cracking and regeneration cycles, while a small portion of th~ eq~ilibrium catalyst particles is fresh (unused) cracking catalyst composition.
The zeoli-te component of the spent zeolite-containing cracking composition of this invention can be any natural or synthetic crystalline aluminosilicate zeolite which exhibits cracking activity. Non-limiting examples of such zeolites are fau~asite, chabazite, mordenite, offretite, erionite, Zeolon, zeolite X, zeolite Y, zeolite L, zeolite ZSM-4, zeolite ZSM-5, zeo].ite ZSM-ll, zeolite ZSM-12, zeolite ZSM-23, zeolite ZSM-35, zeolite ZSM-38, zeolite ZSM-48, and the like, and mixtures thereof.
Additional examples of suitable zeolites are listed in U.S. Patent 4,158,621, the dlsclosure of which is herein incorporated by reference.
The term "zeolite", as used herein, includes zeolites which have been pretreated, such as those from which a portion of Al has been removed from the crystalline framework, and zeolites which have been ion-exchanged with rare earth metal or ammonium or by o-ther conventional ion-exchange methods. The term "zeolite", as used herein, also includes essentially aluminum-free si].ica polymorphs, such as silicalite, chromia silicates, ferrosilicates, borosilicates, and the like, as disclosed in U.S. Patent 4,556,749, the disclosure oE which ls herein incorporated by reference.
Generally the zeolite component of the spent cracking catalyst composition is dispersed in a suitable so].id refractory inorgflnic matrix material, such as alumina, silica, silica-alumina (presently preferred), aluminum phosphate, magnesium oxide, mixtures of two or more of the above-listed materials, and the like. The preparation of such zeolite/matrix cracking catalyst composit:Lons is well known flnd is not crit:Lcal feature of this :Lnvention. GenQral].y, the surface flrea (meflsured by nitrogen fldsorption, substflnt:Lfll].y 1.n ~ccordance wi.th the BET method of Brunfluer, Emmett flnd Teller) of the spent zeolite/matrix cracking catalyst compos:Ltion used in step (A) iS ln the range of from flbout 100 to about 800 m2/g. Gener~lly, the we:Lght rfltlo of zeolite to matrix material in the spent crflck:Lng catalyst composltlon i.s :Ln the range of from about 1:20 to about 1:1.
~ 32652 The spent 7eolite-containing cracking catalyst composltion employed in the process of the inven~ion contains metal compounds as contaminants (generally as oxides), such as co~pounds (particularly oxides) of Ni, ~, Fe, and Cu, and the like. Contaminants of each metal can be present in amounts ranging from traces (about 0.01 wei~ht-%) to about 2.0 weight-% of contaminant of each metal, expressed as metal oxide. These impurities in the spent cracking catalyst compositions have generally been absorbed from the oil feed in a previous cracking process.
However, the origin of these metal impurities is not believed to be a critical feature of this invention.
Fluorine compounds which can be employed in the reactlvation process of this invention are NH4F (preferred), NH4HF2, HF, and mixtures of two or more of these compounds. The fluorine compound can be a gas or a liquid or a solid. Preferably, the fluorine compound is an inorganic fluoride, more preferably NH4F, most preferably dissolved in water.
The term "metals passivating", as used herein, implies that the detrlmental effect of generating H2 durlng catalytic cracking caused by metal deposits on a cracking catalyst composition has been mitigated.
Any suitable metals passivating agent selected from the group consisting of compounds of Be, Mg, Ca, Sr, Ba, Sb, and mlxtures thereoE can be used in the reactivation process of this invention. Non-llmiting examples of such compounds are described in U.S. Patents 3,711,422, 4,025,458, 4,321,t28, 4,337,144, 4,473,463, and 4,728,62~, the disclosures of which are incorporated herein by reference. Preferred passivating agents include: antimony trls(O,O-dlhydrocarbyl) phosphorodithtofltes, antimony oxides (Sb203, Sb205), ~ntimony carboxylates, antimony mercapt:Ldes, compounds of calcium, such as Ca nitrnte, Ca carboxylates, and the llke.
The substantlally simuLtarleous contacting of the spent, metal-contaminated zeolite-containing cracking catalyst wLth the fluorlne compound(s) and the metal pass1vatin$ agent(s) can be carried out Ln any suitable manner. In one mode of operation, the spent cracking catalyst is contacted (elther by impregnation or by spraying or the like) with a solution which contains both the fluorine compound(s) and the metals , ~ 32652CA
passivating agent(s). This mode is feasible if the fluorine compound and the metals passivating agent do not react with one another and do no-t form a precipitate.
In another mode of operation, a first solution containing at least one fluorine compound and a second solu-tion containing at leas-t one metal passivating agent are prepared. Then the spent catalyst composition is contacted with the first solution and immediately thereafter with the second solution ~either by impregnation or by spraying). Or the spent catalyst is contacted with the second solution and immediately thereafter with the first solution (either by impregnation or by spraying). Or the spent catalyst is simultaneously sprayed with the first solution and the second solution.
The contacting process can be carried out either as a batch process or as a continuous process. Any suitable time of contact of the spent cracking catalyst composition with the first and the second solutions can be employed, generally about 0.l to about l0 hours. Any suitable temperature can be employed ln the contacting process, generally about 10 to about 100C. It is generally preferable to carry out some agitation (e.g., stirring or tumbling or falling of the spent catalyst partlcles) during the contacting step.
Any suitable solvent for the fluorine compound(s) and for the metals passivating agent(s) can be employed, such as water, alcohols (such as methanol, ethanol, etc.) ester8 (such as ethyl acetate), ketones (such as acetone), liquid hydrocarbons (such as hexane, heptane, cyclohexane, ben~ene, toluene and the like). The choice of the solvent(s) will be determlned by the chemlcal nature of fluorlne compound(s) and oi the metals passivatlng agent(s), and can easily be made by those having ordinary sklll :Ln the art. Any suitable concentratLon of tbe f1uorlne compound(s) ln a solutlon can be employed, preferably abo1Jt O.Ot to about 2 moltl (more preferably about 0.l-l mol/l). Any sultable concentratlon of the metnls passLv~tlng agent(s) ln a llquld medlum, preferably a solutlon, can be employed, preferably about 0.01-0.5 mol/l (morc preferably Mbout 0.l to 0.3 mol/l). It ls withln the scope of thls lnventlon to use a colloldal dLspersion of the passlvatlng agent in a llquld medium (e.g., ln water).
Any suitable weight ratio of the contacting solution(s) to the spent zeolite-containing cracking catalyst can be employed in the reactivation process of this invention. Generally, these weight ratios are selected such that the ratio of the number of millimoles of the fluorine compound(s) to the number of grams of the spent cracking catalyst composition is in the range of from about 0.01:1 to about 10:1 (preferably about 0.2:1 to about 1:1), and the ratio of the number of grams of metals passivating agent(s) -to the number of grams of spent catalyst composition is in the range of from about 0.001:1 to about 0.5:1 (preferably about 0.002:1 to about 0.2:1). Preferably, the concentration of the metals passivating agent in solution and the ratio of solution to spent catalyst are chosen such that about 0.01 to about 5, more preferably about 0.01-2, weight-% of metals pAssivating element (i.e., Sb, Ca, etc. and mixtures thereof) is incorporated into the spent cracking ca-talyst.
Preferably, the spent cracking catalyst is heated after the contacting with the fluorine compound(s) and the metals passivating agent(s). Any suitab]e heating conditions can be employed which are effective to substantially dry the spent catalyst which has been treated with the fluorine compound(s) and metals passivating agent(s).
Preferably, the treated spent catalyst is first heated at a relatively low temperature (more preferably at about 80-200C) for a time long enough (more preferably at about 0.5-10 hours) to substantially dry the treated spent catalyst. Preferably, the obtained substantially dried catalyst materLal is tben heated ~t a higher temperature (more preFerably at about 300-500C for about 0.5-10 hours), primarily for the purpose of decomposing the metals passivating agent(s) to oxides of tho metal passivating element(s) r such as oxides of Sb, Ca and the like. The above heating steps can be carried out in arl oxldizing gas, such as Air~ or :ln an inert gas atmosphere (e.g., in a streAm of N2 or ~r or lle).
The roactivated catalyst composltion which is obtained in the reactivatlon process of thls invent:Lon can be used in any catalytic cracking process, i.e., a process for catalytLc~lly cracking hydrocarbon-containing oil feedstocks, in any sultnble cracking reactor (e.g., in a FCC reactor or in a Thermofor moving bed reactor), essentially in the absence of added hydrogen gas. The reactivated catalyst composition can be used alone or in admixture with fresh (unused) zeolite-contalning catalys-t composition in catalytic cracking processes.
The hydrocarbon-con-taining feed stream for the catalytic cracking process of this invention can be any suitable feedstock.
Generally the feed has an initial boiling point (ASTM D 1160) in excess of about 400F, preferably a boiling range of from about 400 to about 1200F, more preferably a range of from about 500 to about 1100F, measured at atmospheric pressure conditions. The API gravity (measured at 60F) generally ls in the range of from about 5 to about 40, preferably from about 10 to about 35. Frequently these feedstocks contain Ramsbottom carbon residue (ASTM D524; generally about 0.1-20 weight-%), sulfur (generally about 0.1-5 weight-% S), nitrogen (generally about 0.05-2 weight-% N), nickel (generally about 0.05-30 ppm Ni, i.e., parts by weight of Ni per million parts of feed), vanadium (generally about 0.1-50 ppm V) and copper (generally about 0.01-30 ppm Cu).
Non-limiting examples of suitable feedstocks are light gas oils, heavy gas oils, vacuum gas oils, cracker recycle oils (cycle oils), residua (such as distillation bottoms fractions), hydrotreated resid-ua (e.g., hydrotreated in the presence of Ni, Co, Mo-promoted alumina catalysts), liquid coal pyrolyzates, liquid products from extraction or pyrolysis of tar sand, shale oils, heavy fractions of shale oils, and the like. The presently most preferred feedstocks are heavy gas oils and hydrotreated residua.
Any suitable reac-tor can be used for the catalytic cracking process of this invention. Generally, a fluidized-bed catalytLc cracking (FCC) reactor (preferably containing one or more rlsers) or a moving-bed catalytic cracking reactor (e.g., a Thermofor catalytic cracker) ls employed, preferably a FCC rlser crackLng unlt. Examples of such FCC
cracking unlts are descrLbed in U.S. Patents 4,377,470 and 4,424,116.
Generally, a catalyst regeneration unlt tfor removal of coke deposlts) Ls combined with the FCC crackLng unit, as Ls ShOWII in the above-cLted patents.
Speclflc operatlng condltlons of the cracking operatlon depend greatly on the type of feed, the type and dimenslons of the cracklng reactor and the oll feed rate. Examples of operating condltions are ~ Pl~ 32652CA
described in the above-cited patents and in many other publications. In an FCC operation, genera]ly the weight ratio of catalyst composition to oil feed (i.e., hydrocarbon-containing feed) ranges from about 2:1 to about 10:1, the contact -time between oil feed and catalyst is in the range of from about 0.2 to about 2.0 seconds, and the cracking temperature is in the range of from about 800 to about 1200CF.
Generally, steam is added with the oil feed to the FCC reactor so as to aid in the dispersion of the oil as droplets. Generally, the weight ratio of steam to oil feed is in the range of from about 0.05:1 to about 0.5:~.
The separation of spent (i.e., used) cracking catalyst from gaseous and liquid cracked products and the saparation of cracking products into various gaseous and liquid product fractions can be carried out by any conventional separation means. The most desirable product fraction is gasoline (ASTM boiling range: about 180-400F).
Non-limiting examples of such separation schemes are shown in "Petroleum Refining" by James H. Gary and Glenn E. Handwerk, Marcel Dekker, Inc., 1975.
Generally, cracking catalysts are regenerated, preferably by steam stripping for removal of adhered oll and subsequent heating under oxidlzing conditions so as to burn off carbon deposits. At least a portion of the regenerated cracking catalyst composition can then be treated by the reactivation process of this invention and thereafter be recycled to the catalytic cracking reactor, generally in admixture wlth fresh tunused) cracking catalyst.
The following examples are present to further illustrate this invention and are not to be considerod as unduly limiting the scope of this invention.
E AMPLE I
This example illustrates the reactivation of a metal-contamlnated zeollte-containing equllibrium catalyst, i.e., a catalytlc crackirlg cfltfllyst a portlon of which had previously been employed in a catalytic cracking process and had then been rcgenerflted.
Cfltfllyst A (Control) was a GX0-40 equil:Lbrium cfltalyst, which hfld been supplied as fresh catfllyst by Dnvison Chemicfll Dlvision of ~ 3265ZCA
W. R. Grace and Company, Baltimore, MD, and had previously been employed in a commercial FCC cracking process in a refinery of Phillips Petroleum Company and thereafter had been regenerated by heating in air. The fresh catalyst contained about 25 weight-% ~eolite and about 75 weight-%
silica-alumina matrix. Catalyst A contained abou-t 0.24 weight-% Ni, about 0.34 weight-% V, about 0.61 welght-% Fe, about 0.01 weight-% Cu, 0.05-0.15 weight-% Sb, and about 0.36 weight-% Na. Catalyst A had a surface area of 113 m2/g, a total pore volume of 0.23 cc/~, an apparent bulk densi-ty of 0.89 g/cc, and a 7.eollte unit cell size of 24.39 ~.
Catalyst B (Control) was prepared by pouring a solution of 0.36 grams Vanlube 672 (provided by R. T. Vanderbilt Company; Norwalk, CT;
containing Sb tris(0,0-dipropyl) phosphordithioate at a concentration of 10.7 weight-% Sb) in 50 cc toluene over 33.5 grams of Catalyst A. The mixture of the antimony solution and Catalyst A was stirred and heated to dryness. The dried material was placed into a quartz reactor and heated in a stream of nitrogen at a temperature which was gradually raised from 400F (initial) to 1200F (final) within one hour. The catalyst material was then calcined for 1 hour in air at 1250F.
Catalyst C (Control) was prepared by impregnating 100 grams of Catalyst A with a solution of 3.8 grams of NH4F in 100 cc water and dried in air for 2 hours at 120C.
Catalyst D (Invention) was prepared by pouring first a solution of 1.9 grams of NH4F in 24 cc water and immediately thereafter a mixture of 0.288 grams of Phil-AD CA 6000 (an aqueous dispersion of Sb20s, containing about 20 weight-% Sb; prov:lded by Ca-talyst Resources, Inc.;
Pasadena, TX) and 24 cc water over Catalyst A. The entire mixture of Catalyst A, NH4E solution and antimony dispersion was s-tirred and heated to dryness in a:Lr at 120C.
Catalysts A through D were then evaluated in a MCBU
(micro-confi.ned bed unit) cracking test reactor, substAntially in accordance with the procedure of Example II of U.S. Patetlt 4,794,095.
Cracking test condi.tions comprised a temperaturc of about 950F, a catalyst to oil weight ratio of 6:1, and the use of a hydrotreated residuuln as oil feed having API gravity at 60C of 18.7, sulfur content of 0.53 weight-%, basic nitrogen conterlt of 0.09 wei.ght-%, Conradson carbon content of 6.7 weight-%1 nickel content of 10.6 ppm (parts per ~3 ~ 32652CA
million by weight~ and vanadium content of 12.7 ppm~ Tcst results are summarized in Table I.
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Test results in Table I show that the amount of hydrogen generated by the metfll-contamlnated equilibrium cracking catalyst was lowest when it had been ~reated simultaneously with an antimony compound and ammonium fluoride. Furthermore, the reduction in ~l2 generation caused by trea-tment with Sb and NH4F (Catalyst D), unexpectedly, was higher than the cumulative reduction in ll2 generation caused by treatment with Sb alone (Catalyst B) and with NH4F alone (Catalyst C).
Example II
This example provides additional test results on the reactivation of a metal-contaminated equilibrium cracking catalyst.
Catalyst F (Control) was a copper contaminated equilibrium cracking catalyst, similar to Catalyst A but containing more Cu than Catalyst A. Catalyst F contained 320 ppm Cu.
Catalyst G (Control) was similar to Catalyst C (Example I) but contained more Cu. The NH4F-treated Catalyst F contained 5000 ppm F.
Catalyst H (Control) was similar to Catalyst B but contained more Cu. The Sb205-treated Catalyst F (treated with Phil-Ad CA 6000;
see Example I) contained 740 ppm Sb.
Catalyst I (Invention) WRS similar to Catalyst D (see Example I) but contained more Cu. It contained 5000 ppm F and 740 ppm Sb.
Catal~st J (Control) was SbF3-treated Catalyst F (rather than NH4F/Sb20s-treated Catalyst F). Catalyst J contained 740 ppm Sb (as SbF 3 ) .
Catalyst K (Control) was a calcium-treated Catalyst F, and was prepared by stirrlng Catalyst F with an aqueous solution of Ca(N03)2-4ll20, fol~.owed by hea-ting to dryness. Cata]yst K contained 238 ppm Ca.
~ y~__ (Invention) was prepared by stirring Catnlyst F with an aqueous solution of NH"F and :Lmmediately thereafter with an aqueous solution of Ca(N03)2~4H2O, fo].lowed by heating to dryness. Catalyst L
contained 238 ppm Ca and 5000 ppm F.
Catalysts F through L were eva].uated in a MCBU cracking test reactor a-t the conditi.ons descri.bed in Example I. Test results are summarized in Table II.
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Test results listed in Table II show that treatment of a copper-contamiDate(i equilibrium cracking catalyst with an antimony or a calcium compound alone had no beneficlal effect on hydrogen generation (compare runs 15-18 with runs 22-25 and wl-th runs 30-32). It is thus most surprising that the combination of NH4F with the antimony compound and the combinatlon of NH4F with the calcium compound were more effective ln reduclng hydrogen generatlon than treatment wlth NH4F alone (compare runs 19-21 wlth runs 26-28 and runs 33-35). Furthermore, the combinatlon of antimony compound and NH4F was much more effectlve in suppressing H2 generation than SbF3 (compare runs 26-28 wlth run 29).
Reasonable varlations, modlflcations and adaptations for various conditions and uses can be made within the scope of the disclosure and appended claims.
Claims (40)
1. A process for reactivating a spent cracking catalyst composition comprising the step of contacting a spent zeolite-containing catalytic cracking catalyst composition which contains at least one metal contaminant substantially simultaneously with (a) at least one fluorine compound selected from the group consisting of NH4F, NH4HF2 and HF and (b) a metals passivating agent selected from the group consisting of compounds of beryllium, magnesium, calcium, strontium, barium, antimony, and mixtures of said compounds, under such contacting conditions as to reduce the detrimental effect of said at least one metal contaminant contained in said spent zeolite-containing cracking catalyst during catalytic cracking.
2. A process in accordance with claim 1, wherein said at least one metal contaminant in said spent cracking catalyst composition is selected from the group consisting of compounds of nickel, vanadium, iron and copper.
3. A process in accordance with claim 2, wherein the level of said at least one metal contaminant in said spent cracking catalyst composition is in the range of from about 0.01 to about 2.0 weight-% of each contaminant metal, expressed as metal oxide.
4. A process in accordance with claim 1, wherein said at least one fluorine compound is NH3F.
5. A process in accordance with claim 4, wherein NH4F is dissolved in water so as to form an aqueous solution.
6. A process in accordance with claim 5, wherein the concentration of NH4F in said aqueous solution is about 0.01-2 mol/l.
7. A process in accordance with claim 1, wherein said metals passivating agent is at least one compound of antimony.
8. A process in accordance with claim 1, wherein said metals passivating agent is at least one compound of calcium.
9. A process in accordance with claim 1, wherein said at least one passivating agent is selected from the group consisting of compounds of calcium and antimony, and is dissolved, or, alternatively, colloidally dispersed in a liquid medium and is present in said liquid medium at a concentration of about 0.01-0.5 mol/l.
10. A process in accordance with claim 1, wherein the ratio of the number of millimoles of said fluorine compound to the number of grams of said spent cracking catalyst is in the range of from about 0.01:1 to about 10:1.
11. A process in accordance with claim 10 wherein said fluorine compound is NH4F.
12. A process in accordance with claim 1, wherein the weight ratio of said passivating agent to said spent cracking catalyst composition is in the range of from about 0.001:1 to about 0.5:1.
13. A process in accordance with claim 12, wherein said passivating agent is selected from the group consisting of compounds of calcium and antimony.
14. A process in accordance with claim 13, wherein said fluorine compound is NH4F, and said passivating agent is selected from the group consisting of Sb2O3, Sb2O5, Sb tris(0,0-dihydrocarbyl) phorphordithioates and Ca(NO3)2.
15. a process in accordance with claim 1 additionally comprising the step of substantially drying said spent cracking catalyst composition after said contacting step.
16. A process in accordance with claim 15 comprising the additional step of heating the spent catalyst composition, which has undergone said contacting and drying steps, at about 300-500°C for about 0.5-10 hours.
17. A cracking process comprising the step of contacting a hydrocarbon-containing feed stream with a zeolite-containing cracking catalyst composition, under such cracking conditions as to obtain at least one normally liquid hydrocarbon-containing product stream having a lower initial boiling point and higher API gravity than said hydrocarbon-containing feed stream;
wherein at least a portion of said cracking catalyst composition is a reactivated spent catalyst composition having undergone a reactivation process comprising the step of contacting a spent zeolite-containing catalytic cracking catalyst composition which contains at least one metal contaminant substantially simultaneously with (a) at least one fluorine compound selected from the group consisting of NH4F, NH4HF2 and HF and (b) a
wherein at least a portion of said cracking catalyst composition is a reactivated spent catalyst composition having undergone a reactivation process comprising the step of contacting a spent zeolite-containing catalytic cracking catalyst composition which contains at least one metal contaminant substantially simultaneously with (a) at least one fluorine compound selected from the group consisting of NH4F, NH4HF2 and HF and (b) a
18 metals passivating agent selected from the group consisting of compounds of beryllium, magnesium, calcium, strontium, barium, antimony, and mixtures of said compounds, under such contacting conditions as to reduce the detrimental effect of said at least one metal contaminant contained in said spent zeolite-containing cracking catalyst during catalytic cracking.
18. A process in accordance with claim 17, wherein said at least one metal contaminant in said spent cracking catalyst composition is selected from the group consisting of compounds of nickel, vanadium, iron and copper.
18. A process in accordance with claim 17, wherein said at least one metal contaminant in said spent cracking catalyst composition is selected from the group consisting of compounds of nickel, vanadium, iron and copper.
19. A process in accordance with claim 18, wherein the level of said at least one metal contaminant in said spent cracking catalyst composition is in the range of from about 0.01 to about 2.0 weight-% of each contaminant metal, expressed as metal oxide.
20. A process in accordance with claim 17, wherein said at least one fluorine compound is NH4F.
21. A process in accordance with claim 17, wherein NH4F is dissolved in water so as to form an aqueous solution.
22. A process in accordance with claim 21, wherein the concentration of NH4F in said aqueous solution is about 0.01-2 mol/l.
23. A process in accordance with claim 17, wherein said metals passivating agent is at least one compound of antimony.
24. A process in accordance with claim 17, wherein said metals passivating agent is at least one compound of calcium.
25. A process in accordance with claim 17, wherein swilled at least one passivating agent is selected from the group consisting of compounds of calcium and antimony, and is dissolved, or, alternatively colloidally dispersed in a liquid medium and is present in said liquid medium at a concentration of about 0.01-0.5 mol/l.
26. A process in accordance with claim 17, wherein the ratio of the number of millimoles of said fluorine compound to the number of grams of said spent cracking catalyst is in the range of from about 0.01:1 to about 10:1.
27. A process in accordance with claim 26, wherein said fluorine compound is NH4F.
28. A process in accordance with claim 17, wherein the weight ratio of said passivating agent to said spent cracking catalyst composition is in the range of from about 0.001:1 to about 0.5:1.
29. A process in accordance with claim 28, wherein said passivating agent is selected from the group consisting of compounds of calcium and antimony.
30. A process in accordance with claim 29, wherein said fluorine compound is NH4F, and said passivating agent is selected from the group consisting of Sb2O3, Sb2O5, Sb tris(0,0-dihydrocarbyl) phorphordithioates and Ca(NO3)2.
31. A process in accordance with claim 17 additionally comprising the step of substantially drying said spent cracking catalyst composition after said contacting step.
32. A process in accordance with claim 31 comprising the additional step of heating the spent catalyst composition which has undergone said contacting and drying steps, at about 300-500°C for about 0.5-10 hours.
33. A cracking process in accordance with claim 17, wherein said hydrocarbon-containing feed stream has an initial boiling point, determined in accordance with ASTM method D 1160, of at least 400°F, measured at atmospheric pressure conditions, and an API gravity in the range of from about 5 to about 40.
34. A cracking process in accordance with claim 33, wherein said hydrocarbon-containing feed stream has a boiling range of from about 500°F to about 1110°F and an API gravity in the range of from about 10 to about 35.
35. A cracking process in accordance with claim 17, wherein said hydrocarbon-containing feed stream contains about 0.1-20 weight-%
Ramsbottom carbon residue, about 0.1-5 weight-% sulfur, about 0.05-2.0 weight-% nitrogen, about 0.05-30 ppm nickel, about 0.1-50 ppm vanadium and about 0.01-30 ppm copper.
Ramsbottom carbon residue, about 0.1-5 weight-% sulfur, about 0.05-2.0 weight-% nitrogen, about 0.05-30 ppm nickel, about 0.1-50 ppm vanadium and about 0.01-30 ppm copper.
36. A cracking process in accordance with claim 17, wherein said hydrocarbon-containing feed stream is selected from the group consisting of heavy gas oils and hydrotreated residue.
37. A cracking process in accordance with claim 17, wherein said cracking conditions comprise a temperature in the range of from about 800 to about 1200°F, and a weight ratio of said catalyst composition to said hydrocarbon-containing feed in the range of from about 2:1 to about 10:1.
38. A cracking process in accordance with claim 17, wherein steam is present at a weight ratio of steam to said hydrocarbon-containing feed stream in the range of from about 0.05:1 to about 0.5:1.
39. A cracking process in accordance with claim 17 comprising the additional steps of separating used cracking catalyst composition from gaseous and liquid cracked products, steam-stripping the thus separated used cracking catalyst composition, and heating the steam-stripped cracking catalyst composition under oxidizing conditions so as to burn off coke deposited thereon.
40. A reactivated spent zeolite-containing catalytic cracking catalyst composition produced by the process of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/370,670 US4935121A (en) | 1989-06-22 | 1989-06-22 | Reactivation of metal-contaminated cracking catalysts |
| US07/370,670 | 1989-06-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2015297A1 true CA2015297A1 (en) | 1990-12-22 |
Family
ID=23460660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002015297A Abandoned CA2015297A1 (en) | 1989-06-22 | 1990-04-24 | Reactivation of metal-contaminated cracking catalysts |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4935121A (en) |
| EP (1) | EP0408927A1 (en) |
| JP (1) | JPH0332743A (en) |
| CA (1) | CA2015297A1 (en) |
| NO (1) | NO902769L (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954244A (en) * | 1989-06-22 | 1990-09-04 | Phillips Petroleum Company | Treatment of spent cracking catalysts |
| US5096568A (en) * | 1990-04-04 | 1992-03-17 | Phillips Petroleum Company | Metals passivation |
| US5037786A (en) * | 1990-04-04 | 1991-08-06 | Phillips Petroleum Company | Metals passivation-zeolite containing cracking catalysts |
| US5021377A (en) * | 1990-06-05 | 1991-06-04 | Phillips Petroleum Company | Demetallization and passivation of spent cracking catalysts |
| US5151391A (en) * | 1991-02-15 | 1992-09-29 | Phillips Petroleum Company | Reactivation of spent, metal-containing cracking catalysts |
| US5141904A (en) * | 1991-02-15 | 1992-08-25 | Phillips Petroleum Company | Reactivation of spent cracking catalysts |
| US5192724A (en) * | 1992-03-17 | 1993-03-09 | Phillips Petroleum Company | Reactivation of spent cracking catalysts |
| US5188995A (en) * | 1992-03-24 | 1993-02-23 | Phillips Petroleum Company | Reactivation and passivation of spent cracking catalysts |
| US5935890A (en) * | 1996-08-01 | 1999-08-10 | Glcc Technologies, Inc. | Stable dispersions of metal passivation agents and methods for making them |
| US5972208A (en) * | 1997-07-11 | 1999-10-26 | The M. W. Kellogg Company | FCC metals passivation additives applied to catalyst |
| RU2603964C2 (en) * | 2011-11-21 | 2016-12-10 | Басф Корпорейшн | Improved metal passivator/trap for fcc processes |
| MY173596A (en) | 2013-01-22 | 2020-02-06 | Anellotech Inc | Gas jet injector reactor for catalytic fast pyrolysis |
| JP2016517344A (en) | 2013-03-12 | 2016-06-16 | アネロテック・インコーポレイテッドＡｎｅｌｌｏｔｅｃｈ，Ｉｎｃ． | Regeneration of catalytic rapid pyrolysis catalyst |
| CN108479847B (en) * | 2018-03-20 | 2020-09-01 | 中国科学院大连化学物理研究所 | Preparation method of molecular sieve catalyst for reaction of acrolein, propionaldehyde and ammonia gas |
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|---|---|---|---|---|
| US2331473A (en) * | 1940-06-10 | 1943-10-12 | Velsicol Corp | Catalytic material |
| US2618613A (en) * | 1948-10-27 | 1952-11-18 | Standard Oil Dev Co | Treatment of hydrocarbon conversion catalysts |
| US2651599A (en) * | 1949-09-08 | 1953-09-08 | Standard Oil Dev Co | Treating conversion catalysts |
| US2643971A (en) * | 1950-06-14 | 1953-06-30 | Standard Oil Co | Combination hf treating catalytic cracking process |
| US2681305A (en) * | 1951-02-28 | 1954-06-15 | Standard Oil Dev Co | Revivification of a silicious cracking catalyst by treating with fluosilicic acid |
| US2673187A (en) * | 1951-06-07 | 1954-03-23 | Standard Oil Co | Beryllia regeneration of ironpoisoned cracking catalysts |
| US3364151A (en) * | 1966-01-26 | 1968-01-16 | Sinclair Research Inc | Catalyst containing silica-alumina and finely divided caf2, mgf2, srf2, alf3 or inf3 |
| US3711422A (en) * | 1970-09-08 | 1973-01-16 | Phillips Petroleum Co | Cracking catalyst restoration with antimony compounds |
| US3933983A (en) * | 1971-06-07 | 1976-01-20 | W. R. Grace & Co. | Method of increasing the thermal stability of crystalline zeolites |
| US4025458A (en) * | 1975-02-18 | 1977-05-24 | Phillips Petroleum Company | Passivating metals on cracking catalysts |
| US4111845A (en) * | 1977-02-11 | 1978-09-05 | Mckay Dwight L | Cracking catalyst modified by antimony thiophosphate |
| US4158621A (en) * | 1978-07-21 | 1979-06-19 | Gulf Research & Development Company | Process for increasing gasoline yield and quality during catalytic cracking of high metals content charge stocks using an alumina-aluminum phosphate-silica-zeolite catalyst |
| US4289608A (en) * | 1978-12-07 | 1981-09-15 | Union Oil Company Of California | Process for catalytically cracking metals-containing hydrocarbon feedstocks |
| US4473463A (en) * | 1980-01-15 | 1984-09-25 | Phillips Petroleum Company | Use of cracking catalysts passivated by barium |
| US4321128A (en) * | 1980-05-19 | 1982-03-23 | Atlantic Richfield Company | Phosphorus passivation process |
| US4337144A (en) * | 1980-05-19 | 1982-06-29 | Atlantic Richfield Company | Aluminum passivation process |
| US4728629A (en) * | 1980-08-05 | 1988-03-01 | Phillips Petroleum Company | Cracking catalyst restoration with aluminum compounds |
| US4377470A (en) * | 1981-04-20 | 1983-03-22 | Ashland Oil, Inc. | Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion |
| US4551231A (en) * | 1981-10-13 | 1985-11-05 | Ashland Oil, Inc. | Ammonia contacting to passivate metals deposited on a cracking catalyst during reduced crude processing |
| US4427788A (en) * | 1982-03-08 | 1984-01-24 | Mobil Oil Corporation | Activation of zeolites |
| US4424116A (en) * | 1982-03-25 | 1984-01-03 | Ashland Oil, Inc. | Converting and stripping heavy hydrocarbons in two stages of riser conversion with regenerated catalyst |
| US4549958A (en) * | 1982-03-30 | 1985-10-29 | Ashland Oil, Inc. | Immobilization of vanadia deposited on sorbent materials during treatment of carbo-metallic oils |
| US4559131A (en) * | 1983-02-04 | 1985-12-17 | Mobil Oil Corporation | Reactivation of steam-deactivated catalysts |
| US4596704A (en) * | 1983-11-22 | 1986-06-24 | Mobil Oil Corporation | Activation of zeolites |
| US4556749A (en) * | 1984-04-16 | 1985-12-03 | Atlantic Richfield Company | Catalytic conversion of olefins to higher hydrocarbons |
| US4800185A (en) * | 1986-08-11 | 1989-01-24 | Chemcat Corporation | Regeneraation of metal contaminated hydrocarbon conversion catalytsts |
| EP0295019A1 (en) * | 1987-06-08 | 1988-12-14 | Mobil Oil Corporation | Treatment of aluminosilicate zeolites |
| NZ224702A (en) * | 1987-06-11 | 1989-08-29 | Mobil Oil Corp | Activation of aluminium-deficient zeolite catalyst |
| US4794095A (en) * | 1987-07-02 | 1988-12-27 | Phillips Petroleum Company | Catalytic cracking catalyst |
| US4814066A (en) * | 1988-05-19 | 1989-03-21 | Phillips Petroleum Company | Reactivation of spent catalytic cracking catalyst |
-
1989
- 1989-06-22 US US07/370,670 patent/US4935121A/en not_active Expired - Fee Related
-
1990
- 1990-04-24 CA CA002015297A patent/CA2015297A1/en not_active Abandoned
- 1990-06-15 JP JP2157411A patent/JPH0332743A/en active Pending
- 1990-06-21 NO NO90902769A patent/NO902769L/en unknown
- 1990-06-22 EP EP90111892A patent/EP0408927A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| US4935121A (en) | 1990-06-19 |
| NO902769D0 (en) | 1990-06-21 |
| EP0408927A1 (en) | 1991-01-23 |
| NO902769L (en) | 1990-12-27 |
| JPH0332743A (en) | 1991-02-13 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19931025 |