CA2248039A1 - Alkylation process using hydrogen fluoride-containing alkylation catalysts - Google Patents
Alkylation process using hydrogen fluoride-containing alkylation catalysts Download PDFInfo
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- CA2248039A1 CA2248039A1 CA002248039A CA2248039A CA2248039A1 CA 2248039 A1 CA2248039 A1 CA 2248039A1 CA 002248039 A CA002248039 A CA 002248039A CA 2248039 A CA2248039 A CA 2248039A CA 2248039 A1 CA2248039 A1 CA 2248039A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
- C07C2527/1206—Hydrogen fluoride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/025—Sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
Abstract
A feedstock is alkylated in presence of a hydrogen fluoride containing catalyst, which also comprises a carrier. Possible carriers are: a synthetic water soluble polymer like sodium acrylate or a salt like ammonium trifluoroacetate, ammonium sulfate or ammonium methanesulfonate.
Description
W O 97/32834 PCTnUS97/03269 ~ ALKYLATION PROCESS USING HYD~OGEN E~LUORIDE-CONTAIN~G
ALKYLATION CATALYSTS
Field of the Invention This invention relates to eatalysts for aikylation l~ . tionc and their p~c~alion. More pa~ uLul~ the invention reiates to an aikylation process using a l.~d,u~n fluo,ide con~ alkylation cataiyst, whieh catalyst may be safely and 10 easiiy h~n~ .~sl,o-led, and stored.
Bacl~o~.ld ofthe Llve.~tion AL~cylation .en~il;o~c are aeid cataiyzed re~ct;onC in which an alkyl group is inco.~ol~ed into an organic r~e _'e~ The aikylated organic ~ ~le ~ c, or 15 aikylates, ~c~ u~ from the l~ tion may be used as oetane number cnk ~ g co,.lponcnls for gPC~ C or in det~ ellt forrn~ tioT-~
A widdy used cataiyst in aikylation re~tionC is hydrogen fluoride.
IIydlo4e~l fl--ori~ is adv~ntzg~o~c in that its cl~ 1 stability makes it suitable 20 for use over a wide range of cQ~ Ho~vever, h~/dlu2~l fiuoride is disad~ A~eu~, in that it is a volatile s ~l.,j~... ~ United States Patent No.
5,073,674 ~iic~lo~s a method for dccl~ g hydrogen fluoride volatility by using co.. ~p1~e5 of z-.. ,~i~ or amine polyh~.llugen fluoride. This method is u.,d~s~ tue to the toxicity of the Cc.~ 5 Thus, a need exists for a 25 lly~l~ugcn fluoride alkylation eatalyst that ove.~ollles the disadvantages of both pure hydrogen fluoride and the prior art compl~Y~s~
Description of the Invention and Prcfc. l ~d Embo~
This invention provides an alkylation process that uses l.~diugcn ~uoride-30 cor.~ 8 alkylation catalysts, in both solid and liquid forms. The catalysts of the WO 97/32834 P~1/U~7IO3269 invention are less hazardous than pure hydrogen fluoride and can be safely and easily stored, handled and transported. In addition, methods for p. ~a- aLion of the hydrogen fluoride-cQn~ ing alkyation catalysts are provided.
S The alkylation process ofthe invention con~p,i~es: (A) cont~ing a hydrogen fluoride-cG~ ;n~ alkylation catalyst, coc~Jlia;n~ an effective amount of a carrier and a catalytic amount of hydrogen fluoridc, with a fee~sto.~ under cor~ t-sns suitable to form a reaction rnixture cG~ J.iaill~ a h~-l.u-,a.l,on phase and a catalyst phase; ~B) sep~dling the reaction mLlcture into its hydrocarbon and catalyst phases; and (C) ~.oce~i.,g the hydrocarbon phase to recover the alkylate.
By hydrogen fluoride-co~.lA;~ allylation catalyst is meant an ally~ation catalyst c~sn,p,;:,ing hydrogen fluoride and a carrier.
A carrier, as that term is used for purposes of this invention, is a material that is not itself a l~ct~nt in thc alkylation reaction _nd that does not forrn a cG.~.pl~ with i.~u~ell lluolidc. Further, when co-,-bined with hydrogen fiuoride, the carrier serves to lower the vapor pressure of the l,y.l, u~,e.l fluoride below that of pure hydrogen fluoride without altenng the hydrogen fluoride's rh~m;~
PIO~CI;eS. S~ carriers for use in this invention include acid salts and polymers.
The acid salts useful as carriers are salts of acids which have a pKa value of about 7 or less, prcfe.~l~ about 4 or less, more p~,f.,.~bly about 0 or less, and are soluble in hydrogen fluoride. F~.nr!~Y acids include, wi~ L ~ jt5-ti~n, C~ UA~LC acids such as formic, propionic, and trifluof~c ~c ~ acids, sulfonic acids such as .I,rlh~ ulfon;c and trifluolo...~.h~n~ lfor-ic acids, and inol~&~c acidssuch as phosphoric, nitric, and sulfuric acids. ~I~.f~ .~bly, strong acids such as trifluoroacetic, sulfilric or 5~lfonic are used. The acid salt counterion may be any counterion that forms a salt with the acid s~kctcd which salt is soluble in hydrogen W O 97/32834 PCT~US97/03269 -3- .
fluoride. By soluble in hydrogen fluoride is meant that the acid salt dissolves, or forms a homog~neovs solution, in about ten times its weight or less of hydrogen fluoride. The counterion may be ammoruum, alkyl ~.. nni~l~ such as te.la~llethyl-~, or tetraethyl~mmon;~lm or an alkali metal (Group IA~ cation. Illustrative salts S inr~ ie~ without limit~t;on, ~l~onium sulfate, pot~Cs;~m formate, sodium p,.,~.3nate, a~ trifluor~ac~ and a-,~monium m~lh~nF, ~ifonate.
P~fe.ably~ ~mmoni~-m sulfatc, ~monillm ".~ fonate, or ~"."oruum trifluoro~cct~; is used.
Alternatively, the carrier may be a polymer. By the term polymer is meant homopolyrners, copolymers, and "~lur~ s therco~ Generally, the polymers used in the invention have molec~ r weights of from about 5,000 to 10,000,000.
f~,.~ly, polymers with moiecu1~r weights of from about 5,000 to about 1,000,000 are used.
The polymers useful in the hydrogen fluoride-co~ alkylation cataiysts of the invention are water-soluble polymers. By "water-soluble polymer" is meantany high molecular weight compound that swells, to about twice its dry volume, or dissolves with the ~J~i~ion of water at room te~ Jc.al~le. Pl.,f~,.ably, the polyrners 20 used in the cataiysts are polymers that swell to about twice their dry volume on the addition of water.
Water-soluble polymer is meant to include semi-synthetic water-soluble polymers, synthetic water-soluble polyrners, and rnixtures thereof. Serru-synthetic 25 water-soluble polymers are natural water-soluble polymer derivatives. Synthetic water-soluble polymers are not natural water-solubie polymer derivatives and areformed only through chen7ic~1 reactions.
J
W O 97/32834 PCTrUS97/03269 _4_ .
Exemplary semi-synthetic water-soluble polymers include, without limitation~ cellulose ethers, modified starches, starch derivatives, natural gumderivatives, and mixtures thereo~ Illustrative synthetic water-soluble polymers incllldr, without l;...;l~l;Qn, polymers, related polymers, and poiymer salts of5 acrylamide, acrylic acid, ethylene oxide, methacrylic acid, poiyethyi~ ;nç
polyvinyl alcohol, polyvinyl pyrrolidone, and mixtures thereo~ By re~ated polymer is meant that the polyrner repeat unit, or a branch thereof, is extended by carbon atoms, ~l~fe.ably from one to four carbon atoms. For .~ le a related polymer of acrylic acid is one in which the vinyl group is ~ e~-ded by one carbon to forrn an 10 allyl group.
Preferably, a synthetic water-soluble polyrner is used. More pl ~f. l ably, polyacrylic acid or one of its salts is used. Most p, ~f~.. ~Iy, the water-soluble polymer is sodium polyacrylate.
To prepare the catalyst of the invention, an effective arnount of carrier is mixed with a catalytic amount of hydrogen fluoride. Mixing may be p.,.Ç~,r"led in any suitable corrosion r ~ vessel. If the carrier selecte~l is an acid salt, theacid salt is mixed and dissolved in the hydrogen fluoride. If the carrier is a water 20 soluble polymer, the water-soluble polymer is n~ixed with l,~ u~n fluonde to form an ;.~ e mixture. The polyrner may be in any form for mixing with hydrogen fluoride inr~ ling without limitafion, granules, beads, pellets, fibers, or mats. Mixing may be accolllplished by any means convenient, inrll~ling without limit~tiQn stirring or dis~,c. ~;~13, the polyrner into a pool of hydro~,e.l fluoridc or
ALKYLATION CATALYSTS
Field of the Invention This invention relates to eatalysts for aikylation l~ . tionc and their p~c~alion. More pa~ uLul~ the invention reiates to an aikylation process using a l.~d,u~n fluo,ide con~ alkylation cataiyst, whieh catalyst may be safely and 10 easiiy h~n~ .~sl,o-led, and stored.
Bacl~o~.ld ofthe Llve.~tion AL~cylation .en~il;o~c are aeid cataiyzed re~ct;onC in which an alkyl group is inco.~ol~ed into an organic r~e _'e~ The aikylated organic ~ ~le ~ c, or 15 aikylates, ~c~ u~ from the l~ tion may be used as oetane number cnk ~ g co,.lponcnls for gPC~ C or in det~ ellt forrn~ tioT-~
A widdy used cataiyst in aikylation re~tionC is hydrogen fluoride.
IIydlo4e~l fl--ori~ is adv~ntzg~o~c in that its cl~ 1 stability makes it suitable 20 for use over a wide range of cQ~ Ho~vever, h~/dlu2~l fiuoride is disad~ A~eu~, in that it is a volatile s ~l.,j~... ~ United States Patent No.
5,073,674 ~iic~lo~s a method for dccl~ g hydrogen fluoride volatility by using co.. ~p1~e5 of z-.. ,~i~ or amine polyh~.llugen fluoride. This method is u.,d~s~ tue to the toxicity of the Cc.~ 5 Thus, a need exists for a 25 lly~l~ugcn fluoride alkylation eatalyst that ove.~ollles the disadvantages of both pure hydrogen fluoride and the prior art compl~Y~s~
Description of the Invention and Prcfc. l ~d Embo~
This invention provides an alkylation process that uses l.~diugcn ~uoride-30 cor.~ 8 alkylation catalysts, in both solid and liquid forms. The catalysts of the WO 97/32834 P~1/U~7IO3269 invention are less hazardous than pure hydrogen fluoride and can be safely and easily stored, handled and transported. In addition, methods for p. ~a- aLion of the hydrogen fluoride-cQn~ ing alkyation catalysts are provided.
S The alkylation process ofthe invention con~p,i~es: (A) cont~ing a hydrogen fluoride-cG~ ;n~ alkylation catalyst, coc~Jlia;n~ an effective amount of a carrier and a catalytic amount of hydrogen fluoridc, with a fee~sto.~ under cor~ t-sns suitable to form a reaction rnixture cG~ J.iaill~ a h~-l.u-,a.l,on phase and a catalyst phase; ~B) sep~dling the reaction mLlcture into its hydrocarbon and catalyst phases; and (C) ~.oce~i.,g the hydrocarbon phase to recover the alkylate.
By hydrogen fluoride-co~.lA;~ allylation catalyst is meant an ally~ation catalyst c~sn,p,;:,ing hydrogen fluoride and a carrier.
A carrier, as that term is used for purposes of this invention, is a material that is not itself a l~ct~nt in thc alkylation reaction _nd that does not forrn a cG.~.pl~ with i.~u~ell lluolidc. Further, when co-,-bined with hydrogen fiuoride, the carrier serves to lower the vapor pressure of the l,y.l, u~,e.l fluoride below that of pure hydrogen fluoride without altenng the hydrogen fluoride's rh~m;~
PIO~CI;eS. S~ carriers for use in this invention include acid salts and polymers.
The acid salts useful as carriers are salts of acids which have a pKa value of about 7 or less, prcfe.~l~ about 4 or less, more p~,f.,.~bly about 0 or less, and are soluble in hydrogen fluoride. F~.nr!~Y acids include, wi~ L ~ jt5-ti~n, C~ UA~LC acids such as formic, propionic, and trifluof~c ~c ~ acids, sulfonic acids such as .I,rlh~ ulfon;c and trifluolo...~.h~n~ lfor-ic acids, and inol~&~c acidssuch as phosphoric, nitric, and sulfuric acids. ~I~.f~ .~bly, strong acids such as trifluoroacetic, sulfilric or 5~lfonic are used. The acid salt counterion may be any counterion that forms a salt with the acid s~kctcd which salt is soluble in hydrogen W O 97/32834 PCT~US97/03269 -3- .
fluoride. By soluble in hydrogen fluoride is meant that the acid salt dissolves, or forms a homog~neovs solution, in about ten times its weight or less of hydrogen fluoride. The counterion may be ammoruum, alkyl ~.. nni~l~ such as te.la~llethyl-~, or tetraethyl~mmon;~lm or an alkali metal (Group IA~ cation. Illustrative salts S inr~ ie~ without limit~t;on, ~l~onium sulfate, pot~Cs;~m formate, sodium p,.,~.3nate, a~ trifluor~ac~ and a-,~monium m~lh~nF, ~ifonate.
P~fe.ably~ ~mmoni~-m sulfatc, ~monillm ".~ fonate, or ~"."oruum trifluoro~cct~; is used.
Alternatively, the carrier may be a polymer. By the term polymer is meant homopolyrners, copolymers, and "~lur~ s therco~ Generally, the polymers used in the invention have molec~ r weights of from about 5,000 to 10,000,000.
f~,.~ly, polymers with moiecu1~r weights of from about 5,000 to about 1,000,000 are used.
The polymers useful in the hydrogen fluoride-co~ alkylation cataiysts of the invention are water-soluble polymers. By "water-soluble polymer" is meantany high molecular weight compound that swells, to about twice its dry volume, or dissolves with the ~J~i~ion of water at room te~ Jc.al~le. Pl.,f~,.ably, the polyrners 20 used in the cataiysts are polymers that swell to about twice their dry volume on the addition of water.
Water-soluble polymer is meant to include semi-synthetic water-soluble polymers, synthetic water-soluble polyrners, and rnixtures thereof. Serru-synthetic 25 water-soluble polymers are natural water-soluble polymer derivatives. Synthetic water-soluble polymers are not natural water-solubie polymer derivatives and areformed only through chen7ic~1 reactions.
J
W O 97/32834 PCTrUS97/03269 _4_ .
Exemplary semi-synthetic water-soluble polymers include, without limitation~ cellulose ethers, modified starches, starch derivatives, natural gumderivatives, and mixtures thereo~ Illustrative synthetic water-soluble polymers incllldr, without l;...;l~l;Qn, polymers, related polymers, and poiymer salts of5 acrylamide, acrylic acid, ethylene oxide, methacrylic acid, poiyethyi~ ;nç
polyvinyl alcohol, polyvinyl pyrrolidone, and mixtures thereo~ By re~ated polymer is meant that the polyrner repeat unit, or a branch thereof, is extended by carbon atoms, ~l~fe.ably from one to four carbon atoms. For .~ le a related polymer of acrylic acid is one in which the vinyl group is ~ e~-ded by one carbon to forrn an 10 allyl group.
Preferably, a synthetic water-soluble polyrner is used. More pl ~f. l ably, polyacrylic acid or one of its salts is used. Most p, ~f~.. ~Iy, the water-soluble polymer is sodium polyacrylate.
To prepare the catalyst of the invention, an effective arnount of carrier is mixed with a catalytic amount of hydrogen fluoride. Mixing may be p.,.Ç~,r"led in any suitable corrosion r ~ vessel. If the carrier selecte~l is an acid salt, theacid salt is mixed and dissolved in the hydrogen fluoride. If the carrier is a water 20 soluble polymer, the water-soluble polymer is n~ixed with l,~ u~n fluonde to form an ;.~ e mixture. The polyrner may be in any form for mixing with hydrogen fluoride inr~ ling without limitafion, granules, beads, pellets, fibers, or mats. Mixing may be accolllplished by any means convenient, inrll~ling without limit~tiQn stirring or dis~,c. ~;~13, the polyrner into a pool of hydro~,e.l fluoridc or
2~ passing hydrogen fluoride gas over the polymer. Typically mixing is p.,.~~-l,1ed at te.~ res from about 0 to about 100~ C., p.c~.~ly from about 10 to abûut 40~ C. Pl~s~ ¢ is not critical.
-W O 97/32834 PCTrUS97/03269 When the carrier is an acid salt, an effective amount of acid salt is an amount both capable of de~ i"g, the volati}ity of the hydrogen fluoride to the desired level below that of pure hydrogen fluoride and which is dissolvable in the '' catalytic amount of hydrogen fluoride used. An effective amount of polymer is an 5 amount capable of de~asi-,~ the volatility and inclc,asing the surface tension of the catalytic amount of hydrogen fluoride used to the desired extent. The specific amount of acid salt or polymer used will depend on both the acid salt or polyrner s~lected and the catalytic amount of hydrogen fluoride used.
A catalytic amount of hydrogen fluoride is an amount of hydrogen fluoride s~ffit~i~nt to ...~ Ai-~ the desired level of catalytic activity in the specific alkylation reaction in which it is used. If the carrier is an acid salt, the ~nininlllm amount of hydrogen fluoride used is an amount effective both to dissolve the acid salt and to ,~2;~IA;~ the desircd level of catalytic activity. For polymer carriers, the miniml-m 15 arnount of hydrogen fluoride is an amount effect*e to form an i--1;. . ,al e mixture ~,vith the polymer and to ,..~;nlA;.. the desired catalytic activity.
Generally, regardless of the carrier s~lected the amount of hydrogen fluoride used is from about 20 to about 99, p.e~.dbly from about 30 to 20 about 98, weight percent based on the total weight of the alkylation catalyst. For HF/polymer catalysts, more p~ er. . ably from about 60 to about 99 weight percent and most p.~,fe.~ from about 70 to about 99 weight percent of hydrogen fl~uoride is used. For HF/acid salt catalysts, more prefe.~bly from about 50 to about 80 weight percent, most preferably from about 60 to about 75 weight 25 percent, hydrogen fluoride is used. If a very small amount of hydrogen fluoride is used, the vapor pressure will be very low, but so too the catalytic activity. If a large amount of hydrogen fluoride is used, the vapor phase reduction will be less, but the catalytic activity high. One ordinarily skilled in the art will recognize that a W O 97/32834 PCTrUS97/03269 balance p~ ably is achieved between using too little and too great an amount of hydrogen fluoride.
Without dep~- ling from the scope of the invention, it will be recognized S that other components may be inr~lld~d in the catalysts ofthe invention. In general, any co-"~onel-t that does not deleteriously effect the catalytic action or undc~ abl~ incl~a5e the volatility of the hydrogen fluoride may be used The hydrogen fluoride may be cG,.u-ler,;ally available a~ iroLIs hydrogen 10 fluoride having a water content of 0.1 % or less or aqueous hydrogen fluoride.
Preferably, anhydrous hydrogen fluoride is used. The acid salt is p~,~,ably .- ibs~ y anhydrous having a water content of less than about 1 %. A number of su~sl~lL;ally anhydrous acid salts are co.. -,. c;ally available or such salts may be produced by using any of the well known drying te~hniques such as desiccant or 15 vacuum drying.
If the desired acid salt is not readily available or is ~ e, the acid salt may be p,.,p&~,d by mixing the acid with a bifluoride salt to form the acid salt.
Alternatively, the acid salt may be formed in ~ by mixing together the acid, 20 bifluoride salt and hydrogen fluoride.
The Cala~ may be in liquid, gel-like sol;d or, solid form. The hydrogen fluoride weight ~_.c~ age over which the catalyst will be liquid depends upon the carrier used. Generally, for a~u~G~ùum salts of acids having pKa's of about 3 or2~ less, the h~.l.oge., fluoride/acid salt alkylation catalyst may be liquid even with an acid salt content of from about 20 to about 30 weight percent. Within the range of from about ~ to about 30 weight percent hydrogen fluoride, the hydrogen fluonde polymer alkylation catalyst will be a solid or gel-like solid, while at higher hydrogen fluoride conc~,,.llalions, the catalyst most likely will be a liquid.
W 097132834 PCTrUS97103269 The choice of solid, gel-like solid, or liquid catalyst will depend on a number of factors inel~ ing the specific alkylation reaction used, the scale of the reaction, and the desired pr~cescing of the product mixture. The solid alkylation catalysts are adv~nt~gPo~c in that they may be removed from an alkylated product5 by simple filtration or decA~ ;on Alkylations using the solid catalysts also may be ~ P-~hlc to a flow system in which the liquid feed materials to be alkylated are allowed to flow down a column conl~in;.-l3 the catalyst.
The catalysts ofthe invention may be used in conj~nrtion with a solid lû support that is inert to the reaction condition ofthe specific alkylation reaction chosen. Suit~hle inert supports include, without l;n~;L~I;on, carbon, fluorine treated or coated resins, metal c~ ;lr c or halides inert to h~.l,o~,e.l fluoride or that can be converted to h~drogcn fluoride-inert compounds, and acid-~ slu~l mol~CIll9r sieves. Alle.l-ali~ely, an inert support may be ~p~d by coating a non-inert 15 support with any suitable inert .nat~,.ial such as antimony trifluoride or ~ mimlm trifluoride. The suppolle~ catalyst may be pl~ arcd by any method known in the art.
The aLtcylation catalysts of the invention may be used in any of the well 2û known all~ldtion~ nC, which reactions are con~ cted over a wide range of conrlition~c The alkylation catalyst may be used in both liquid and vapor phase aL~cylation r~i ~ion~ P~.,fe,ably, the catalyst is used in its liquid or solid form for liquid phase reactit~r~e and in its solid phase for vapor phase reactior c The alkylation r~a~l;onC may be carried out in batch, U~t~.llUUe.lt, or contin~lo--e mode.
In the process to produce an alkylate, a feedstoclc is cQI-t~cted with the alkylation catalyst in step (A). The feedstock or feedctorl-e used will depend on the desired alkylate. Suitable fee~ctorL- include, without limit~tiQn, pa,~l, ic or isop~ilfic h~,-llo~ l,ons, aromatic hydro~ ons, olefins and ,,u~lul~,s thereof.
W O 97/32834 PCTrUS97/03269 Exemplary p~,nlc or isoparaffinic hydrocarbons include, without limjt~tion~
m~th~n-o, butane, icobut~ne, isopcn~ane, and the like. Aromatic hydrocarbons include, without limitAtion, b~n7~nç alkyl b~ -7~ s, alkylene bF-~7~ , and the like. Olefins suitable for use include both olefinie hydroearbons and olefin-acting 5 agents in.~ ling without l;;l,~l;on, C3to C5 alkyl halides, C3 to C6 mono-olefins, and the iike. Ln the ease of paraffln-olefin alkylation, the molar ratio of paraffinie, isop&~l.lie, or aromatie hydroearbon to olefin used is from about 1:1 to about 1:200, p~efe.~bly from about 1:3 to about 1:50, more p-~f~"dl,ly from about 1:5 to about 1:25. The feedstock may contain any eraeking inhibitor or moderator known in the art.
In step (A), the fee~ctocl~ and eataiyst are co ~ ~e d and thoroughly rnixed in an alkylation reaetor made of any suitable ~l~ate.idl sueh as TEFLON~-lined earbon steel under co~ ;l;Qnc suitable to forrn a reaetion n~ibcture having hydroearbon and catalyst phases. The eor~ tions~ i e., time, tel"~_.aL~re, and pressure, are those suitable for pro~uGing the desired alkylate. The preeise conditions will depend upon the phase of reaetion, feedstock s~k~led as well as the desired allylate and are readily dl,te.-,linable by one oldinal-ly skilled in the art. In general, the eont~ctin~ step may be earried out at a tcmp.,.aLure from about -100~
C to about 150~ C, pr~,f~.abl~ from about -30~ C to about 100~ C, more p.~.ably from about -10~ C to about 80~ C. and at pressures from about 15 psia to about 315 psia. Contaet, or rPci~ence times, will be from about 0.05 seeonds to about several hours.
The reaetion mixture formed in step (A) is s~,dldte~d into its hydroearbon phase, conl~;t~;ng the alkylate produet, and eatalyst phases in step (B). The separation may be aeeomplished by any eonvenient method known in the art such as ~ ti~l~tion. The eatalyst phase may be recycled baelc to contaet step (A).
W O 97/32834 PCTrUS97/03269 _9_ Following separation, the hydrocarbon phase may be ~.~,cessed in a step (C) to recover the alkylate product as well as any le ~ g catalyst and unreactedhydrocarbon or olefin. The catalyst and unreacted hydrocarbon or olefin may be recycled to step (A). Typically, the processing is accomplished by any of the well S known fractionation methods.
The invention will be clarified further by a consideration of the following le s that are meant to be purely exemplary.
E~c~r.. ~les Example I
10 g of sodium polyacrylate, m. wt. 1,000,000 was weiglled in a TEFLON~-lined autoclave at room tc,..pe.alu~e and, after cooling ofthe autoclave with dry ice, 34.7 g HF were loaded into the autoclave to form a gel-like solid alkylating catalyst. The catalyst forrned was 78 weight percent ~: and 22 weight percent sodium polyacrylate. .SI~bsequrntly the autoclave was wa~ ed to room t~ ,.al-lre and then 40.1 g of i~obut~ne and 20.7 g of isobutylene were added to the autoclave and heated to, and held at, 85~ C for 1 hour during which~ the mixture was stirred. The reactor was then cooled and the organic liquid 20 analyzed by gas ~ ...a~ography and mass spectography. Analysis int~ir~ted C5 to Cl3 saturated l.~ uc~bons, inclu~iing isooctane.
Example 2 The procedure of Example I was used except that the catalyst was 95 weight percent HF and 5 weight percent sodium polyacrylate. The resulting catalyst was liquid phase. 29.5 g Isobutane and 20 g isobutylene were added and reacted with the catalyst as in FY~mrle I . Analysis of the organic liquid in~lic~trd J C5 to Cl3 saturated hydrocarbons, inrlu~ing isooctane.
W O 97/32834 PCT~US97/03269 Example 3 36 g of ~ and 4 g of polyacrylic acid copolyrnerized with 50 weight percent maieic acid, m. wt. 50,000 and available from Aldrich Chemicals were loaded into an autoclave and mixed to form a catalyst of 90 weight percent HF and 5 10 weight percent polymer. To the reSI~lting liquid phase catalyst was added 40 g icobllt~n~ and 20 g isobutylene and the mixture heated to and held at 75~ C and stirred. The reactor was cooled and the liquid phase co~ ;..g Ol~iUCS was analyzed by GC and MS and found to contain typical alkylation products, inclll~ling isooctane.
FY~mple 4 The procedure of FY~mrle 3 was used except that a catalyst that was 90 weight percent ~ and 10 weight percent sodium polyacrylate copoly,.,e.i~ed with methyl methacrylate, m. wt. 15,000 and available from Aldrich Ch~ c was substituted for the catalyst of FY~mple 3 . GC and MS analysis of the liquid phase co.~ g or~ cs found it to contain typieal all~lation products, .nrl~ling isooctane.
FY~rnrle 5 The procedure of Examplc 3 was followed except that a 95 weight percent HF and 5 weight percent sodium polya_lylate, m. wt. 1,000,000, catalyst was usedand 20. 5 g of propylene was substituted for the isobutylene of Example 3 . Analysis of the liquid phase co.~ g organics by GC and MS found it to contain typical alkylation products, inclll-ling isooctane.
Example 6 The procedure of Example 3 was used except that a catalyst of 95 weight percent HF and 5 weight percent sodium polyacrylate, m. wt. 1,000,000, was used and 20.2 g of amylene was substituted for the isobutylene of FY~nrle 3 . Analysis W O 97/32834 PCT~US97/03269 _ I I _ of the liquid phase containing organics by GC and MS found it to contain typicalalkylation products, incl~- in~ isooctane.
Example 7 The procedure of Example 3 was used except that a catalyst that was 70 weight percent HF and 30 weight percent ~.~....O~ m sulfate was used and 20 g ofamylene were used for the isobutylene of Example 3 . Analysis of the liquid phase co..l~;..;.~g organics by GC and MS found it to contain typical alkylation products, 0 inr.~ ng isooctane.
Fy~mple 8 10 g sodium polyacrylate are w ei~31.ed in a TEFI~ON~-lined autoclave at room t~..,.p~ L~Ire and, after cooling of the autoclave with dry ice, 30 g H~ are 15 loaded into the aulocld-re to form a solid a~ lalh~g catalyst. The catalyst is 7S
weight percent E~ and 25 weight percent sodium pol~..cl~late. Subsequently~ the autoclave is ~allned to room t~.l.p~,.dl,lre and then a g~ceo~C 2:1 mixture of ob~lt~n~ and isobutylene is drawn through the solid catalyst in the autoclave. The effluent from the autoclave is CO~ f ~-~ed in a trap chilled with acetone and dry ice and the collectec~ organic liquid is analyzed by GC and MS. Analysis inAi~tes C5to Cl3 saturated hydrocall,ol~s are present, in~ ng isooctane.
F.x~mple 9 Sodium acrylate is polyll.e. ~ed in the pl csellce of the following solid inert supports: carbon, ~IIlmimlm trifluoride and calcium fluoride. This results in the solid water-soluble polyrner grafted, or SuppolLCd, on the inert supports. 50 g of each of these catalysts are weighed in TEFI.ON~9-lined autoclaves at room J t~,.lll,c.al~lre and, after cooling of the autoclaves with dry ice, 30 g H~ is loaded into each of the autoclaves to form solid alkylating catalysts. Subsequently, the W097/32834 PCTrUS97/03269 autoclaves are warmed to room temperature and then a gaseous 2:1 mixture of isobutane and isobutylene is drawn through the solid catalysts in the autoclaves.
The effluent ~om the each of the autoclaves is con~lr ~ed in a trap chilled withacetone and dry ice and the collected organic liquid is analyzed by GC and MS.
Analysis demrJnctrates the prescnce of C5 to Cl3 saturated hydrocarbons, inclufling isooctane.
Exampie 10 The procedure of Example 1 is used except that the catalyst is 95 weight percent HF and 5 weight percent acrylic acid copol~l.,e,.Led with lO % acrylamide, 200,000 m. wt. available from Aldrich Chf~mic~c The resulting catalyst is liquidphase. 29.5 g icobut~n~ and 20 g isobutylene are added and reacted with the catalyst as in FY~rnple 1. Analysis ofthe organic liquid in~iC~fÇS C5 to Cl3 saturated hydrocarbons inr~ ing isooctane.
Examplc 1 1 The procedure of FY~mrle 1 is used except that a catalyst that is 60 weight percent HF and 40 weight percent mPth~rrylic acid, m. wt. 200,000 is used. 30 g Isobutane and 20 g isobutylene are added and reacted with the catalyst as in EY~mrle 1. Analysis ofthe organic liquid in-lir~fes C5 to Cl3 saturated l"~d.oc~l,ons in.-l~-Aing isooctane.
FY~mrle 12 The procedure of F~ le 1 is used except that the catalyst used is 70 weight percent HF and 30 weight percent polyvinyl alcohol, m. wt. 5,000. 30 g Isobutane and 20 g isobutylene are added and reacted with the catalyst as in Example 1. Analysis ofthe organic liquid in~ic~t~s C~ to Cl3 saturated hydrocarbons inrlu~ling isooctanc.
W O 97/32834 PCTrUS97/03269 Example 13 The procedure of Exampie 1 is used except that the catalyst used is 99 weight percent E~ and I weight percent polyvinyl pyrrolidone, m. wt. 1,000,000.
The res~-lting catalyst is liquid phase. 30 g Isobutane and 20 g isobutylene are5 added and reacted with the catalyst as in Example 1. Analysis of the organic liquid inriiC~t-os C5 to Cl3 saturated hydrocarbons in~lurling isooctane.
Example 14 The procedure of Example 1 is used except that the catalyst is 95 weight percent HF and S weight percent sodium polyethylene oxide, M. wt 250,000 is used. The resulting catalyst is liquid phase. 29.5 g Isobutane and 20 g isobutylene is added and reacted with the catalyst as in Exarnple 1. Analysis of the organicliquid indir~t.oS C5 to Cl3 saturated hydrocarbons inrll-ding isoocl~ne.
Exarnple 15 The procedure of FY~mrle 3 is used except that a catalyst that is 80 weight percent H~ and 20 weight percent sodium fluoride is used and 20 g amylene is used for the isobutylene. Analysis of the liquid phase co~ g organics finds it to contain G~8~cs inrhl-~ing isooctane.
FY~mple 16 The procedure of Exampie 3 is used except that the catalyst used is 20 weight percent HF and 80 weight percent sodium p~c,piona~e. Analysis of the liquid phase cG~ n;-~g organics by GC and MS shows it to contain typical 25 alkylationproducts, inr~ iing isooctane.
Exarnple 17 ~' The procedure of Example 3 is used except that the catalyst used is 40 weight percent HF and 60 weight percent ~ ",..o..;~lm trifluoro~cet~te. Analysis of W097t32834 PCTrUS97/03269 -14_ the liquid phase co-~Laining organics by GC and MS shows it to contain typical alkylation produc~s, in~ ing isooctane.
Example 18 S The procedure of Examp}e 3 is used except that the catalyst used is 60 weight percent HF and 40 weight percent a~ on.~m ...~ Ih~ 5 ~Ifonate. Analysis of the liquid phase conf ~ g organics by GC and MS shows it to contain typical alkylation products, incl~ ing isooctane.
-W O 97/32834 PCTrUS97/03269 When the carrier is an acid salt, an effective amount of acid salt is an amount both capable of de~ i"g, the volati}ity of the hydrogen fluoride to the desired level below that of pure hydrogen fluoride and which is dissolvable in the '' catalytic amount of hydrogen fluoride used. An effective amount of polymer is an 5 amount capable of de~asi-,~ the volatility and inclc,asing the surface tension of the catalytic amount of hydrogen fluoride used to the desired extent. The specific amount of acid salt or polymer used will depend on both the acid salt or polyrner s~lected and the catalytic amount of hydrogen fluoride used.
A catalytic amount of hydrogen fluoride is an amount of hydrogen fluoride s~ffit~i~nt to ...~ Ai-~ the desired level of catalytic activity in the specific alkylation reaction in which it is used. If the carrier is an acid salt, the ~nininlllm amount of hydrogen fluoride used is an amount effective both to dissolve the acid salt and to ,~2;~IA;~ the desircd level of catalytic activity. For polymer carriers, the miniml-m 15 arnount of hydrogen fluoride is an amount effect*e to form an i--1;. . ,al e mixture ~,vith the polymer and to ,..~;nlA;.. the desired catalytic activity.
Generally, regardless of the carrier s~lected the amount of hydrogen fluoride used is from about 20 to about 99, p.e~.dbly from about 30 to 20 about 98, weight percent based on the total weight of the alkylation catalyst. For HF/polymer catalysts, more p~ er. . ably from about 60 to about 99 weight percent and most p.~,fe.~ from about 70 to about 99 weight percent of hydrogen fl~uoride is used. For HF/acid salt catalysts, more prefe.~bly from about 50 to about 80 weight percent, most preferably from about 60 to about 75 weight 25 percent, hydrogen fluoride is used. If a very small amount of hydrogen fluoride is used, the vapor pressure will be very low, but so too the catalytic activity. If a large amount of hydrogen fluoride is used, the vapor phase reduction will be less, but the catalytic activity high. One ordinarily skilled in the art will recognize that a W O 97/32834 PCTrUS97/03269 balance p~ ably is achieved between using too little and too great an amount of hydrogen fluoride.
Without dep~- ling from the scope of the invention, it will be recognized S that other components may be inr~lld~d in the catalysts ofthe invention. In general, any co-"~onel-t that does not deleteriously effect the catalytic action or undc~ abl~ incl~a5e the volatility of the hydrogen fluoride may be used The hydrogen fluoride may be cG,.u-ler,;ally available a~ iroLIs hydrogen 10 fluoride having a water content of 0.1 % or less or aqueous hydrogen fluoride.
Preferably, anhydrous hydrogen fluoride is used. The acid salt is p~,~,ably .- ibs~ y anhydrous having a water content of less than about 1 %. A number of su~sl~lL;ally anhydrous acid salts are co.. -,. c;ally available or such salts may be produced by using any of the well known drying te~hniques such as desiccant or 15 vacuum drying.
If the desired acid salt is not readily available or is ~ e, the acid salt may be p,.,p&~,d by mixing the acid with a bifluoride salt to form the acid salt.
Alternatively, the acid salt may be formed in ~ by mixing together the acid, 20 bifluoride salt and hydrogen fluoride.
The Cala~ may be in liquid, gel-like sol;d or, solid form. The hydrogen fluoride weight ~_.c~ age over which the catalyst will be liquid depends upon the carrier used. Generally, for a~u~G~ùum salts of acids having pKa's of about 3 or2~ less, the h~.l.oge., fluoride/acid salt alkylation catalyst may be liquid even with an acid salt content of from about 20 to about 30 weight percent. Within the range of from about ~ to about 30 weight percent hydrogen fluoride, the hydrogen fluonde polymer alkylation catalyst will be a solid or gel-like solid, while at higher hydrogen fluoride conc~,,.llalions, the catalyst most likely will be a liquid.
W 097132834 PCTrUS97103269 The choice of solid, gel-like solid, or liquid catalyst will depend on a number of factors inel~ ing the specific alkylation reaction used, the scale of the reaction, and the desired pr~cescing of the product mixture. The solid alkylation catalysts are adv~nt~gPo~c in that they may be removed from an alkylated product5 by simple filtration or decA~ ;on Alkylations using the solid catalysts also may be ~ P-~hlc to a flow system in which the liquid feed materials to be alkylated are allowed to flow down a column conl~in;.-l3 the catalyst.
The catalysts ofthe invention may be used in conj~nrtion with a solid lû support that is inert to the reaction condition ofthe specific alkylation reaction chosen. Suit~hle inert supports include, without l;n~;L~I;on, carbon, fluorine treated or coated resins, metal c~ ;lr c or halides inert to h~.l,o~,e.l fluoride or that can be converted to h~drogcn fluoride-inert compounds, and acid-~ slu~l mol~CIll9r sieves. Alle.l-ali~ely, an inert support may be ~p~d by coating a non-inert 15 support with any suitable inert .nat~,.ial such as antimony trifluoride or ~ mimlm trifluoride. The suppolle~ catalyst may be pl~ arcd by any method known in the art.
The aLtcylation catalysts of the invention may be used in any of the well 2û known all~ldtion~ nC, which reactions are con~ cted over a wide range of conrlition~c The alkylation catalyst may be used in both liquid and vapor phase aL~cylation r~i ~ion~ P~.,fe,ably, the catalyst is used in its liquid or solid form for liquid phase reactit~r~e and in its solid phase for vapor phase reactior c The alkylation r~a~l;onC may be carried out in batch, U~t~.llUUe.lt, or contin~lo--e mode.
In the process to produce an alkylate, a feedstoclc is cQI-t~cted with the alkylation catalyst in step (A). The feedstock or feedctorl-e used will depend on the desired alkylate. Suitable fee~ctorL- include, without limit~tiQn, pa,~l, ic or isop~ilfic h~,-llo~ l,ons, aromatic hydro~ ons, olefins and ,,u~lul~,s thereof.
W O 97/32834 PCTrUS97/03269 Exemplary p~,nlc or isoparaffinic hydrocarbons include, without limjt~tion~
m~th~n-o, butane, icobut~ne, isopcn~ane, and the like. Aromatic hydrocarbons include, without limitAtion, b~n7~nç alkyl b~ -7~ s, alkylene bF-~7~ , and the like. Olefins suitable for use include both olefinie hydroearbons and olefin-acting 5 agents in.~ ling without l;;l,~l;on, C3to C5 alkyl halides, C3 to C6 mono-olefins, and the iike. Ln the ease of paraffln-olefin alkylation, the molar ratio of paraffinie, isop&~l.lie, or aromatie hydroearbon to olefin used is from about 1:1 to about 1:200, p~efe.~bly from about 1:3 to about 1:50, more p-~f~"dl,ly from about 1:5 to about 1:25. The feedstock may contain any eraeking inhibitor or moderator known in the art.
In step (A), the fee~ctocl~ and eataiyst are co ~ ~e d and thoroughly rnixed in an alkylation reaetor made of any suitable ~l~ate.idl sueh as TEFLON~-lined earbon steel under co~ ;l;Qnc suitable to forrn a reaetion n~ibcture having hydroearbon and catalyst phases. The eor~ tions~ i e., time, tel"~_.aL~re, and pressure, are those suitable for pro~uGing the desired alkylate. The preeise conditions will depend upon the phase of reaetion, feedstock s~k~led as well as the desired allylate and are readily dl,te.-,linable by one oldinal-ly skilled in the art. In general, the eont~ctin~ step may be earried out at a tcmp.,.aLure from about -100~
C to about 150~ C, pr~,f~.abl~ from about -30~ C to about 100~ C, more p.~.ably from about -10~ C to about 80~ C. and at pressures from about 15 psia to about 315 psia. Contaet, or rPci~ence times, will be from about 0.05 seeonds to about several hours.
The reaetion mixture formed in step (A) is s~,dldte~d into its hydroearbon phase, conl~;t~;ng the alkylate produet, and eatalyst phases in step (B). The separation may be aeeomplished by any eonvenient method known in the art such as ~ ti~l~tion. The eatalyst phase may be recycled baelc to contaet step (A).
W O 97/32834 PCTrUS97/03269 _9_ Following separation, the hydrocarbon phase may be ~.~,cessed in a step (C) to recover the alkylate product as well as any le ~ g catalyst and unreactedhydrocarbon or olefin. The catalyst and unreacted hydrocarbon or olefin may be recycled to step (A). Typically, the processing is accomplished by any of the well S known fractionation methods.
The invention will be clarified further by a consideration of the following le s that are meant to be purely exemplary.
E~c~r.. ~les Example I
10 g of sodium polyacrylate, m. wt. 1,000,000 was weiglled in a TEFLON~-lined autoclave at room tc,..pe.alu~e and, after cooling ofthe autoclave with dry ice, 34.7 g HF were loaded into the autoclave to form a gel-like solid alkylating catalyst. The catalyst forrned was 78 weight percent ~: and 22 weight percent sodium polyacrylate. .SI~bsequrntly the autoclave was wa~ ed to room t~ ,.al-lre and then 40.1 g of i~obut~ne and 20.7 g of isobutylene were added to the autoclave and heated to, and held at, 85~ C for 1 hour during which~ the mixture was stirred. The reactor was then cooled and the organic liquid 20 analyzed by gas ~ ...a~ography and mass spectography. Analysis int~ir~ted C5 to Cl3 saturated l.~ uc~bons, inclu~iing isooctane.
Example 2 The procedure of Example I was used except that the catalyst was 95 weight percent HF and 5 weight percent sodium polyacrylate. The resulting catalyst was liquid phase. 29.5 g Isobutane and 20 g isobutylene were added and reacted with the catalyst as in FY~mrle I . Analysis of the organic liquid in~lic~trd J C5 to Cl3 saturated hydrocarbons, inrlu~ing isooctane.
W O 97/32834 PCT~US97/03269 Example 3 36 g of ~ and 4 g of polyacrylic acid copolyrnerized with 50 weight percent maieic acid, m. wt. 50,000 and available from Aldrich Chemicals were loaded into an autoclave and mixed to form a catalyst of 90 weight percent HF and 5 10 weight percent polymer. To the reSI~lting liquid phase catalyst was added 40 g icobllt~n~ and 20 g isobutylene and the mixture heated to and held at 75~ C and stirred. The reactor was cooled and the liquid phase co~ ;..g Ol~iUCS was analyzed by GC and MS and found to contain typical alkylation products, inclll~ling isooctane.
FY~mple 4 The procedure of FY~mrle 3 was used except that a catalyst that was 90 weight percent ~ and 10 weight percent sodium polyacrylate copoly,.,e.i~ed with methyl methacrylate, m. wt. 15,000 and available from Aldrich Ch~ c was substituted for the catalyst of FY~mple 3 . GC and MS analysis of the liquid phase co.~ g or~ cs found it to contain typieal all~lation products, .nrl~ling isooctane.
FY~rnrle 5 The procedure of Examplc 3 was followed except that a 95 weight percent HF and 5 weight percent sodium polya_lylate, m. wt. 1,000,000, catalyst was usedand 20. 5 g of propylene was substituted for the isobutylene of Example 3 . Analysis of the liquid phase co.~ g organics by GC and MS found it to contain typical alkylation products, inclll-ling isooctane.
Example 6 The procedure of Example 3 was used except that a catalyst of 95 weight percent HF and 5 weight percent sodium polyacrylate, m. wt. 1,000,000, was used and 20.2 g of amylene was substituted for the isobutylene of FY~nrle 3 . Analysis W O 97/32834 PCT~US97/03269 _ I I _ of the liquid phase containing organics by GC and MS found it to contain typicalalkylation products, incl~- in~ isooctane.
Example 7 The procedure of Example 3 was used except that a catalyst that was 70 weight percent HF and 30 weight percent ~.~....O~ m sulfate was used and 20 g ofamylene were used for the isobutylene of Example 3 . Analysis of the liquid phase co..l~;..;.~g organics by GC and MS found it to contain typical alkylation products, 0 inr.~ ng isooctane.
Fy~mple 8 10 g sodium polyacrylate are w ei~31.ed in a TEFI~ON~-lined autoclave at room t~..,.p~ L~Ire and, after cooling of the autoclave with dry ice, 30 g H~ are 15 loaded into the aulocld-re to form a solid a~ lalh~g catalyst. The catalyst is 7S
weight percent E~ and 25 weight percent sodium pol~..cl~late. Subsequently~ the autoclave is ~allned to room t~.l.p~,.dl,lre and then a g~ceo~C 2:1 mixture of ob~lt~n~ and isobutylene is drawn through the solid catalyst in the autoclave. The effluent from the autoclave is CO~ f ~-~ed in a trap chilled with acetone and dry ice and the collectec~ organic liquid is analyzed by GC and MS. Analysis inAi~tes C5to Cl3 saturated hydrocall,ol~s are present, in~ ng isooctane.
F.x~mple 9 Sodium acrylate is polyll.e. ~ed in the pl csellce of the following solid inert supports: carbon, ~IIlmimlm trifluoride and calcium fluoride. This results in the solid water-soluble polyrner grafted, or SuppolLCd, on the inert supports. 50 g of each of these catalysts are weighed in TEFI.ON~9-lined autoclaves at room J t~,.lll,c.al~lre and, after cooling of the autoclaves with dry ice, 30 g H~ is loaded into each of the autoclaves to form solid alkylating catalysts. Subsequently, the W097/32834 PCTrUS97/03269 autoclaves are warmed to room temperature and then a gaseous 2:1 mixture of isobutane and isobutylene is drawn through the solid catalysts in the autoclaves.
The effluent ~om the each of the autoclaves is con~lr ~ed in a trap chilled withacetone and dry ice and the collected organic liquid is analyzed by GC and MS.
Analysis demrJnctrates the prescnce of C5 to Cl3 saturated hydrocarbons, inclufling isooctane.
Exampie 10 The procedure of Example 1 is used except that the catalyst is 95 weight percent HF and 5 weight percent acrylic acid copol~l.,e,.Led with lO % acrylamide, 200,000 m. wt. available from Aldrich Chf~mic~c The resulting catalyst is liquidphase. 29.5 g icobut~n~ and 20 g isobutylene are added and reacted with the catalyst as in FY~rnple 1. Analysis ofthe organic liquid in~iC~fÇS C5 to Cl3 saturated hydrocarbons inr~ ing isooctane.
Examplc 1 1 The procedure of FY~mrle 1 is used except that a catalyst that is 60 weight percent HF and 40 weight percent mPth~rrylic acid, m. wt. 200,000 is used. 30 g Isobutane and 20 g isobutylene are added and reacted with the catalyst as in EY~mrle 1. Analysis ofthe organic liquid in-lir~fes C5 to Cl3 saturated l"~d.oc~l,ons in.-l~-Aing isooctane.
FY~mrle 12 The procedure of F~ le 1 is used except that the catalyst used is 70 weight percent HF and 30 weight percent polyvinyl alcohol, m. wt. 5,000. 30 g Isobutane and 20 g isobutylene are added and reacted with the catalyst as in Example 1. Analysis ofthe organic liquid in~ic~t~s C~ to Cl3 saturated hydrocarbons inrlu~ling isooctanc.
W O 97/32834 PCTrUS97/03269 Example 13 The procedure of Exampie 1 is used except that the catalyst used is 99 weight percent E~ and I weight percent polyvinyl pyrrolidone, m. wt. 1,000,000.
The res~-lting catalyst is liquid phase. 30 g Isobutane and 20 g isobutylene are5 added and reacted with the catalyst as in Example 1. Analysis of the organic liquid inriiC~t-os C5 to Cl3 saturated hydrocarbons in~lurling isooctane.
Example 14 The procedure of Example 1 is used except that the catalyst is 95 weight percent HF and S weight percent sodium polyethylene oxide, M. wt 250,000 is used. The resulting catalyst is liquid phase. 29.5 g Isobutane and 20 g isobutylene is added and reacted with the catalyst as in Exarnple 1. Analysis of the organicliquid indir~t.oS C5 to Cl3 saturated hydrocarbons inrll-ding isoocl~ne.
Exarnple 15 The procedure of FY~mrle 3 is used except that a catalyst that is 80 weight percent H~ and 20 weight percent sodium fluoride is used and 20 g amylene is used for the isobutylene. Analysis of the liquid phase co~ g organics finds it to contain G~8~cs inrhl-~ing isooctane.
FY~mple 16 The procedure of Exampie 3 is used except that the catalyst used is 20 weight percent HF and 80 weight percent sodium p~c,piona~e. Analysis of the liquid phase cG~ n;-~g organics by GC and MS shows it to contain typical 25 alkylationproducts, inr~ iing isooctane.
Exarnple 17 ~' The procedure of Example 3 is used except that the catalyst used is 40 weight percent HF and 60 weight percent ~ ",..o..;~lm trifluoro~cet~te. Analysis of W097t32834 PCTrUS97/03269 -14_ the liquid phase co-~Laining organics by GC and MS shows it to contain typical alkylation produc~s, in~ ing isooctane.
Example 18 S The procedure of Examp}e 3 is used except that the catalyst used is 60 weight percent HF and 40 weight percent a~ on.~m ...~ Ih~ 5 ~Ifonate. Analysis of the liquid phase conf ~ g organics by GC and MS shows it to contain typical alkylation products, incl~ ing isooctane.
Claims (10)
1. An alkylation process comprising the steps of:
(A) contacting a feedstock and a hydrogen fluoride-containing alkylation catalyst, the catalyst comprising an effective amount of a carrier and a catalytic amount of hydrogen fluoride, under conditions suitable to form a reaction mixture comprising a hydrocarbon phase, the hydrocarbon phase comprising an alkylate product, and a catalyst phase:
(B) separating the hydrocarbon phase and the catalyst phase; and (C) processing the hydrocarbon phase to recover the alkylate product.
(A) contacting a feedstock and a hydrogen fluoride-containing alkylation catalyst, the catalyst comprising an effective amount of a carrier and a catalytic amount of hydrogen fluoride, under conditions suitable to form a reaction mixture comprising a hydrocarbon phase, the hydrocarbon phase comprising an alkylate product, and a catalyst phase:
(B) separating the hydrocarbon phase and the catalyst phase; and (C) processing the hydrocarbon phase to recover the alkylate product.
2. The process of claim 1 wherein the catalytic amount of hydrogen fluoride is from about 20 to about 99 weight percent based on the total weight of the alkylation catalyst.
3. The process of claim 1 wherein the catalytic amount of hydrogen fluoride is from about 30 to about 98 weight percent based on the total weight of the alkylation catalyst.
4. The process of claim 1 wherein the carrier is a synthetic water soluble polymer.
5. The process of claim 4 wherein the synthetic water-soluble polymer is sodium polyacrylate.
6. The process of claim 1 wherein the carrier is a salt of an acid, the acid having a pKa of about 4 or less.
7. The process of claim 6 wherein the acid salt is ammonium trifluoroacetate, ammonium sulfate, or ammonium methanesulfonate.
8. The process of claim 1 wherein the feedstock comprises at least one hydrocarbon selected from the group consisting of paraffinic hydrocarbon, isoparaffinic hydrocarbon, aromatic hydrocarbons, and mixtures thereof and at least one olefin selected from the group consisting of olefinic hydrocarbons, olefin-acting agents, and mixtures thereof.
9. An alkylation process comprising the steps of:
(A) contacting a feedstock, comprising at least one hydrocarbon selected from the group consisting of paraffinic hydrocarbon, isoparaffinic hydrocarbon, aromatic hydrocarbon, and mixtures thereof and at least one olefin selected fromthe group consisting of olefinic hydrocarbons, olefin-acting agents, and mixtures thereof, and a hydrogen fluoride-containing alkylation catalyst comprising from about 40 to about 1 weight percent sodium polyacrylate and from about 60 to about 99 weight percent hydrogen fluoride, at a temperature from about -30°C to about 100° C and a pressure of from about 15 psia to about 315 psia fro a contact time suitable to form a reaction mixture comprising a hydrocarbon phase, the hydrocarbon phase comprising an alkylate product, and a catalyst phase;
(B) separating the hydrocarbon phase and the catalyst phase; and (C) processing the hydrocarbon phase to recover the alkylate product.
(A) contacting a feedstock, comprising at least one hydrocarbon selected from the group consisting of paraffinic hydrocarbon, isoparaffinic hydrocarbon, aromatic hydrocarbon, and mixtures thereof and at least one olefin selected fromthe group consisting of olefinic hydrocarbons, olefin-acting agents, and mixtures thereof, and a hydrogen fluoride-containing alkylation catalyst comprising from about 40 to about 1 weight percent sodium polyacrylate and from about 60 to about 99 weight percent hydrogen fluoride, at a temperature from about -30°C to about 100° C and a pressure of from about 15 psia to about 315 psia fro a contact time suitable to form a reaction mixture comprising a hydrocarbon phase, the hydrocarbon phase comprising an alkylate product, and a catalyst phase;
(B) separating the hydrocarbon phase and the catalyst phase; and (C) processing the hydrocarbon phase to recover the alkylate product.
10. An alkylation process comprising the steps of:
(A) contacting a feedstock, comprising at least one hydrocarbon selected from the group consisting of paraffinic hydrocarbon. isoparaffinic hydrocarbon, aromatic hydrocarbon, and mixtures thereof and at least one olefin selected fromthe group consisting of olefinic hydrocarbons, olefin-acting agents, and mixtures thereof, and a hydrogen fluoride-containing alkylation catalyst comprising from about 50 to about 20 weight percent of an acid salt selected from the group consisting of ammonium trifluoroacetate, ammonium sulfate, ammonium methanesulfonate, and mixtures thereof and from about 50 to about 80 weight percent hydrogen fluoride, at a temperature from about -30° C to about 100° C
and a pressure of from about 15 psia to about 315 psia for a contact time suitable to form a reaction mixture comprising a hydrocarbon phase, the hydrocarbon phasecomprising an alkylate product, and a catalyst phase;
(B) separating the hydrocarbon phase and the catalyst phase; and (C) processing the hydrocarbon phase to recover the alkylate product.
(A) contacting a feedstock, comprising at least one hydrocarbon selected from the group consisting of paraffinic hydrocarbon. isoparaffinic hydrocarbon, aromatic hydrocarbon, and mixtures thereof and at least one olefin selected fromthe group consisting of olefinic hydrocarbons, olefin-acting agents, and mixtures thereof, and a hydrogen fluoride-containing alkylation catalyst comprising from about 50 to about 20 weight percent of an acid salt selected from the group consisting of ammonium trifluoroacetate, ammonium sulfate, ammonium methanesulfonate, and mixtures thereof and from about 50 to about 80 weight percent hydrogen fluoride, at a temperature from about -30° C to about 100° C
and a pressure of from about 15 psia to about 315 psia for a contact time suitable to form a reaction mixture comprising a hydrocarbon phase, the hydrocarbon phasecomprising an alkylate product, and a catalyst phase;
(B) separating the hydrocarbon phase and the catalyst phase; and (C) processing the hydrocarbon phase to recover the alkylate product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/612,041 US5663474A (en) | 1996-03-07 | 1996-03-07 | Alkylation process using hydrogen fluoride-containing alkylation catalysts |
| US08/612,041 | 1996-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2248039A1 true CA2248039A1 (en) | 1997-09-12 |
Family
ID=24451468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002248039A Abandoned CA2248039A1 (en) | 1996-03-07 | 1997-03-05 | Alkylation process using hydrogen fluoride-containing alkylation catalysts |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5663474A (en) |
| EP (1) | EP0885181B1 (en) |
| JP (1) | JP2000506164A (en) |
| AU (1) | AU1984197A (en) |
| CA (1) | CA2248039A1 (en) |
| DE (1) | DE69716245T2 (en) |
| ES (1) | ES2184994T3 (en) |
| TW (1) | TW419448B (en) |
| WO (1) | WO1997032834A1 (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6177058B1 (en) * | 1996-03-07 | 2001-01-23 | Alliedsignal Inc. | Hydrogen fluoride compositions |
| US5983476A (en) * | 1998-06-09 | 1999-11-16 | Uop Llc | Conversion of an HF alkylation unit |
| US6670281B2 (en) | 1998-12-30 | 2003-12-30 | Honeywell International Inc. | HF etching and oxide scale removal |
| US6677269B2 (en) | 2001-05-17 | 2004-01-13 | George A Olah | Environmentally safe alkylation of aliphatic and aromatic hydrocarbons with olefins using solid HF-equivalent catalysts |
| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| WO2005021468A1 (en) | 2003-07-15 | 2005-03-10 | Grt, Inc. | Hydrocarbon synthesis |
| US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| US8329603B2 (en) * | 2003-09-16 | 2012-12-11 | Uop Llc | Isoparaffin-olefin alkylation |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| MY153701A (en) | 2006-02-03 | 2015-03-13 | Grt Inc | Separation of light gases from halogens |
| EA020442B1 (en) | 2006-02-03 | 2014-11-28 | ДжиАрТи, ИНК. | Process for converting hydrocarbon feedstock (embodiments) and system therefor |
| NZ581216A (en) | 2007-05-24 | 2011-06-30 | Grt Inc | Zone reactor incorporating reversible hydrogen halide capture and release |
| US8067660B2 (en) * | 2007-06-08 | 2011-11-29 | Honeywell International Inc. | Method and system for restraining a chemical discharge |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| AU2009270801B2 (en) | 2008-07-18 | 2014-04-24 | Reaction 35, Llc | Continuous process for converting natural gas to liquid hydrocarbons |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1470772A (en) * | 1922-08-21 | 1923-10-16 | Henry L Greenbaum | Paste for etching glass |
| US2430181A (en) * | 1941-12-29 | 1947-11-04 | Universal Oil Prod Co | Alkylation of isoparaffinic hydrocarbons |
| US2903345A (en) * | 1957-11-15 | 1959-09-08 | American Cyanamid Co | Etching of barium glass |
| US4373050A (en) * | 1966-06-01 | 1983-02-08 | Amchem Products, Inc. | Process and composition for coating metals |
| US3591432A (en) * | 1968-05-08 | 1971-07-06 | Bell Telephone Labor Inc | Process for surface treatment of lead and its alloys |
| US3635836A (en) * | 1969-11-10 | 1972-01-18 | Gen Mills Inc | Thickened compositions and the process of preparing same |
| US3928486A (en) * | 1973-06-04 | 1975-12-23 | Universal Oil Prod Co | Alkylation process with fluorination step utilizing HF catalyst and hydrocarbon polymer |
| US4210460A (en) * | 1975-10-22 | 1980-07-01 | J. T. Baker Chemical Company | Spill control composition and use thereof |
| GB1572032A (en) * | 1977-01-31 | 1980-07-23 | Hoechst Uk Ltd | Gels comprising silica and an aqueous acid |
| US4383868A (en) * | 1979-05-02 | 1983-05-17 | Braley Gordon K | Treatment of spillages of hazardous chemicals |
| US4297257A (en) * | 1980-04-17 | 1981-10-27 | Dart Industries Inc. | Metal stripping composition and method |
| DD271324A1 (en) * | 1988-04-05 | 1989-08-30 | Petrolchemisches Kombinat | METHOD FOR THE HF-CATALYZED ALKYLATION OF BUTENS WITH ISOBUTANE |
| US5073363A (en) * | 1989-10-06 | 1991-12-17 | Pellico Michael A | Foamable fluoride gels and method |
| US5073674A (en) * | 1990-04-20 | 1991-12-17 | Olah George A | Environmentally safe catalytic alkyation using liquid onium poly (hydrogen fluorides) |
| US5277881A (en) * | 1992-09-14 | 1994-01-11 | Texaco Inc. | Hydrogen fluoride alkylation apparatus and vapor recovery method |
| DK171639B1 (en) * | 1993-08-05 | 1997-03-03 | Topsoe Haldor As | Process for alkylating aliphatic hydrocarbons |
| WO1995016740A1 (en) * | 1993-12-16 | 1995-06-22 | Mobil Oil Corporation | Hydrogen fluoride composition |
-
1996
- 1996-03-07 US US08/612,041 patent/US5663474A/en not_active Expired - Lifetime
-
1997
- 1997-03-05 AU AU19841/97A patent/AU1984197A/en not_active Abandoned
- 1997-03-05 WO PCT/US1997/003269 patent/WO1997032834A1/en active IP Right Grant
- 1997-03-05 JP JP9531865A patent/JP2000506164A/en not_active Ceased
- 1997-03-05 ES ES97907982T patent/ES2184994T3/en not_active Expired - Lifetime
- 1997-03-05 EP EP97907982A patent/EP0885181B1/en not_active Expired - Lifetime
- 1997-03-05 CA CA002248039A patent/CA2248039A1/en not_active Abandoned
- 1997-03-05 DE DE69716245T patent/DE69716245T2/en not_active Expired - Fee Related
- 1997-03-10 TW TW086102954A patent/TW419448B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0885181B1 (en) | 2002-10-09 |
| JP2000506164A (en) | 2000-05-23 |
| AU1984197A (en) | 1997-09-22 |
| WO1997032834A1 (en) | 1997-09-12 |
| EP0885181A1 (en) | 1998-12-23 |
| US5663474A (en) | 1997-09-02 |
| TW419448B (en) | 2001-01-21 |
| ES2184994T3 (en) | 2003-04-16 |
| DE69716245D1 (en) | 2002-11-14 |
| DE69716245T2 (en) | 2003-09-25 |
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