CA2119144A1 - Method of regenerating certain acidic hydrocarbon conversion catalysts by solvent extraction - Google Patents
Method of regenerating certain acidic hydrocarbon conversion catalysts by solvent extractionInfo
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- CA2119144A1 CA2119144A1 CA002119144A CA2119144A CA2119144A1 CA 2119144 A1 CA2119144 A1 CA 2119144A1 CA 002119144 A CA002119144 A CA 002119144A CA 2119144 A CA2119144 A CA 2119144A CA 2119144 A1 CA2119144 A1 CA 2119144A1
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- lewis acid
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/32—Regeneration or reactivation of catalysts comprising compounds of halogens
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
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- 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
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- 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
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
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- 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
- C07C2/60—Catalytic processes with halides
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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- C07C2527/08—Halides
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- C07C2527/06—Halogens; Compounds thereof
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- C07C2527/10—Chlorides
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- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
- C07C2527/1213—Boron fluoride
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- C07C2527/06—Halogens; Compounds thereof
- C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
- C07C2527/126—Aluminium chloride
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- C07C2527/14—Phosphorus; Compounds thereof
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Abstract
This invention is a process for the regeneration of solid acidic hydrocarbon conversion catalysts, but particularly certain transition aluminas and zeolites promoted with Lewis acids (preferably BF3) which have been used in the alkylation of isoparaffins with olefins. The process involves the removal of some portion of the reaction product residue adhering to the solid catalyst by contact with a solvent to partially recover the catalyst's initial activity.
Description
/ v `~ -- -21~.91,~ 3Rec'dPCT/P~O O2GEC19~:
A METHOD FOR REGENERATING CERTAIN ACIDIC HYDROCARBON
CON\IERSION CATALYSTS BY SOLVENT EXTRACTION
FIELD OF THE INVENTION
This invention is a process for tha regeneration of solid acidic hydrocarbon conversion catalysts, but particularly certain transition aluminas and zeolites promoted with Lewis acids (preferably BF3) which have besn us~d in the alkylation of isoparaffin with olefins. The proc~ss involves th~
removal of some portion of the reaction product residue adhering to the solid cata~yst by contact with a solvent to partially recover the catalyst's initial activity.
~UND OF THE INVENTIC)N
There are a wide variety of hy.drocarbon conversion processes using strongly acidic solid acid catalysts at temperatures low enough to maintain the SUBSTlTUTE SHEEr 2`11~144 . PCr/US92/10095 reaction medium in a liquid phase. These processes include oligomer,_.tion, alkylation, isomerization, hydroisomerkation, etc. The catalysts for these processes include such disparate acidic materials as acidic zeolites, alumina, silica-alumina, silica, boron oxides, phosphorus oxides, titanium oxide, zirconium oxide, chromia, zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, chromia-alumina, alumina-boria, silica-zirconia,aluminum phosphate molecular sieves, silicoaluminophosphate molecular sieves, solid polymeric ion exchange resins, tetravalent metal phosphonates with pendent acid groups, sulfated metal oxides (such as alumina), and the like. These catalysts may be treated with or complexed with Lewis acids. A side reaction in many of these processes produces what appears to be a low level polymer or oligomer.
Unlike many higher temperature processes, the side prodllcts are not cok~
like in nature. These poorly characterized side reaction products, or "gunk~, may be at least partially removed using solvent sxtraction procedures and carefuliy chosen solvents. One process, with its concomitant catalyst, to which solvent extraction is especially applicable is isoparaffin/olefin alkylation using solid acid catalysts particularly zeolites or aluminas which have been . - ~
treated with Lewis acids.
The preparation of high octane blending components for motor fuels using strong acid alkylation processes (notably where the acid is hydrofluoric ~ -acid or sulfuric acid) is well-known. Alkylation is the reaction in which an alkyl group is added to an organic molecule (typically an aromatic or olefin). For production of gasoline blending stocks, the reaction is b~tween an isoparaffin and an olefin. Alkylation proces~es have been in wide use since World War ll when high octane gasolines were needed to satisfy demands from high compression ratio or supercharged aircra~t engines. The early alkylation units were built in conjunction with fluid catalytic cracking units to take advantage of the light end by-products of the cracking units: isoparamns and olefins.
Fluidized catalytic cracking units still constitute the major source of feedstocks for gasoline alkylation units. In spite of the mature state of strong acid alkylation technology, existing problems with the hydrofluoric and sulfuric acidtechnologies continue to be severe: disposal of the used acid, unintentional -, 211314403 Re~'~l P~/?~ EC ~ J
emission of the acids during use or storage, substantial corrosivity ~f the acidcatalyst systems, and other environmental concerns.
Although a practical alkylation process using solid acid catalysts having little or no corrosive components has long been a goal, commercially viable processes do not exist.
The open literature shows several systems used to alkylate various hydrocarbon feedstocks.
The American Oil Company obtained a series of patents in the mid-1950's on alkylation processes involving C2-C,2 (preferably C2 or C3) olefins and C4-Ca isoparaffins. The catalysts used were BF3-treated solids and the catalyst system (as used in the alkylation process) also contained free BF3. A
summary of those patents is found in the following lis~:
.
Patent No. Inventor BF3-Treated Catalvst~ (with free BF~) 2,804,491 May et a!- SiO2 stabilized Al2O3 (10%-60% by weight BF3) 2,824,146 Kelly et al. metal pyrophosphate hydrate 2,824,150 Knight et al. metal sulfate hydrate 2,824,151 Kelly et al. metal stannate hydrate 2,824,152 Knight et al. metal silicate hydrate 2,824,153 K~lly et al. metai orthophosphate hydrate 2,824,154 Knight et al. m~tal tripolyphosphate hydrate 2,824,155 Knight et al. matal pyroarsenate hydrate 2,824,156 Kelly et al. Co or Mg arsenate hydrate 2,824,157 Knight et al. Co, Al, or Ni borate hydrate 2,824,1~8 Kelly et al. metal pyroantimonate hydrate salt 2,824,159 K~lly et al~ Co or Fe molybdat~ hydrats 2,824,160 Knight,et al. Al, Co, or Ni tungstate hydrats 2,824,161 Knight et al. borotungstic acid hydrate or Ni or Cd borotungstate hydrate 2,824,162 Knight et al. phosphomolybdic acid hydrate 2,945,907 Knight 3. solid 9~1 alumina (~%-100% by weight of Zn or Cu fluoborate, preferably anhydrous) ~may be supported on Al2O3 None of these disclose a process for regenerating an alkylation catalyst using SUBSTITUTE SHEEr WO93/1006~ 9~ 4~ PCI/US92/10095 a solvent extraction process for regenerating the catalyst.
Acid catalysts used to oligomerize olefins are known. U.S. Patent No.
2,748,090 to Watkins suggests the use of a catalyst made up of a Group vîli metal (preferably nickel), a phosphoric acid (preferably containing phosphoruç
5 pentoxide), plac~d on an alumina adsorbent, and pretreated with BF3.
Alkylation of aromatics is suggested.
U.S. Patent No. 2,976,338 to Thomas suggests a polymerization catalyst comprising a compiex of BF3 or H3PO~ optionally on an adsorbent (such as activated carbon) or a molecular sEeve optionaily containing 10 potassium acid fluoride.
Certain references suggest the use of alumina-containing catalysts for alkylation of aromatic compounds. U.S. Patent No. 3,068,301 to Hervert*t al.
suggests a catalyst for alkylating aromatics usîng ~olefi~acting compounds~
The catalyst is a solid, silica-stabilked alumina up to 10% SiO2, all of which has been modified with up to 100% by of weight BF3. `Other BF3-treated aluminas are known. For instance, U.S. Patent No. ; ~-3,114,785 to Hervert et al. suggests the use of a BF3-modified, substantially -~ .
anhydrous alumina to shift the double bond of 1-butens to produce 2-butene.
The preferred alumina is substantially anhydrous gamma-alumina, eta-alumina, 20 or theta-alumina. The v~rious aluminas will adsorb or complex with up to about 19% by weight fluorins depending upon the typ~ of alumina and the temperature of treatment.
In U.S. Patent No. 4,407,731 to Imai 8 high surface area metal oxide such as alumina (particularly garnma-alumina, e~a-alumina, ~heta-alumina, 25 silica, or a siliea-alumina) is used as a base or support for BF3. The BF3 treated me~al oxide is used for generic oligomerization and alkylation reactions. The metal oxide is tr~atad in a complicated fashion prior to bein~
treated with BF3. The first step entails treating the metal oxids with an acid solution and with a basic aqueous solution. Th~ support is washed with an 30 aqusous decomposable sait such as ammonium nitrate. The support is washed using deionized H2O until the wash water shows no alkali or alkaline earth metal cations in the filtrate. The support is dried and calcined. 1 he WO 93/10065 PCI/US92/1009~
211914~
disclosure suggests generically that BF3 is then introduced to the treated metal oxide support. The examples show introduction of the BF3 at elevated temperatures, e.g, 300 C or 350 C.
Similarly, U.S. Patent No. 4,427,791 to Miale ~I- suggests the S enhancement of the acid catalytic activity of inorganic oxide materials (such as alumina or gallia) by contacting the material with ammonium fluoride or boron fluoride, contacting the treated inorganic oxide with an aqueous ammonium hydroxide or salt solution, and calcining the resulting material. The inorganic oxides treated in this way are said to sxhibit enhanced Bronsted addity and, ~^
10 therefore, is said to have improved acid activity towards the catalysis of numerous and several reactions (such as alkylation and isomerization of various hydrocarbon compounds). A specific suggested use tor the treated ~ ;
inorganic oxide is as a matrix or SUppOft tor various zsolite materials ultimately used in acid catalyzed organic compound cor~rsion processes.
U.S. Patent No. 4,75t,341 to Rodewald shows a process for treating a ZSM-5 type zeolne with BF3 to reduce its pore ske, enhance its shape selectivity, and increase ns activity towards the reaction of oligomerking olefins. The patent also suggests using these materials for alkylation of afomatic compounds.
~0 Certain Soviet publications suggest the use of A12O3 cata~sts for alkylation processes. Benzene alkylation using those catalysts (with 3 ppm to 5 ppm water and periodic additions of BF~ is shown in Yagubov, Kh. M. ~
al., Azerb. Khim. Zh., 1984, (5) p. 58. Similarly, Kozorezov, Yu and Levitskii, E.~, Zh. Print. Khim. (Lenin~rad), 1984, 57 (t2), p. 2681, show the us~ of 25 ~umina which has been treated at relatively high temperaturss and rnodified with BF3 at 100-C. There are no indication~ that BF3 is maintained in excess.
Isobutane alkylation using Al20JBF3 catalysts is suggested in ~leRekhimiya, 1977, 17 (3), p. 396; 1979, 19 (3), P. 385. The olefin is ethylene. There is no indication that BF3 is maintained in excess during the reaction. The crystalline30 form of the alumina is not described nor is any method suggested for regeneration of the catalysts.
U.S. Patent No. 4,918,255 to Chou ~1- suggests a process for the WO93/10065 PCl/US92/10095 2~9~4 6 alkylation of isoparaffins and olefins using a composite described as "comprising a Lewis acid and a large pore zeolite and/or a non-zeolitic inorganic oxide~. The process disclosed requires isomerization of the olefin feed to reduce substantially the content of alpha-olefin and further suggests 5 that water addition to the alkylation process improves the operation of the process.
U.S. Patent No. 4,992,616 to Chou ~. deals with the process noted above for alkylation of isoparaffins and olefins using a composite described as ~comprising a Lewis acid and a large pore zeolite~ but requires addition of 10 water for improving the operation of the process. The best Research Octane Number (RON) product shown in tho examples and made using the disclosed invention is 86.0 (Table 2). ~` -Similarly, PCT published applicaUons WO 90/00533 and 90/00534 ` ~
(which are based in part on the U.S. patent to Chou et al. noted above) ~; `
suggest the same process as does Chou ~1. WO 90/00534 is specific to a -process using boron trifluoride-treated inorganic oxides including ~alumina, silica, boria, oxides of phosphorus, titanium oxide, zirconium oxide, chromia, `
zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, chromia-alumina, alumina-boria, silica-zirconia, and the various naturally occurring inorganic 20 oxides of various states of purity such as bauxite, clay and diatomaceous earth. Of special note is the statement that the ~preferred inorganic oxides are amorphous silicon dioxide and aluminum oxide~. The examples show the use of amorphous silica (and BF~) to produce alkylates having an RON of no greater than 94. U.S. Pat. Number 4,935,577 to Huss, Jr. et al. teaches a 25 process for the catalytic distillation of various hydrocarbons by e.g., alkylation or oligomerization, using a catalyst ~consisting essentially of a Lewis acîd promoted inorganic oxide." The inorganic oxide may be selected from the non-zeolitic materials discussed above with regard to the Chou.ç~l.
published PCT applications. Additionally, the inorganic oxide may be a large 30 pore crystalline molecular sieve.
There are a variety of disclosed ways to regenerate catalysts used in alkylation processes or using Lewis acids. Typical of such processes are the 27l131 4~
following.
U.S. Patent No. 3,647,916, to Caesar et al. shows a process for isoparaffin-olefin alkylation using crystalline zeolite cata~sts at low isoparamn to olefin ratios. The zeolite is first steamed to reduce the number of acid sites ``
5 and so reduce the amount of olefin polymerization which occurs. The isoparaffin is added to the catalyst before the olefin is introduced to further limR the amount of polymerization. There is no discussion of the use of auxiliary Lewis acids in conjunction with the zeolites. Nevertheless, the catalysts are susceptible to deactivation due to the ~accumulation in the pores ~
10 thereof of olefin polymerization products~. The regeneration is carried out by - -buming ths surface residue ~in an oxygen-containing atmosphere at an elevated temperature in the range of about 800 to 1400- P followed by a step in which the catalyst is contacted with an aromatic or polar solvent.
U.S. Patent No. 3t833.679 to Gardner et al. shows a paraffin 15 isomerization process using an HSbF" catalyst sùpported on a fluorided alumina. The catalyst was regenerated by introducbon of an HF strearn sumcient to convert to any SbF5 to HSbF,s. No mention is made of removal of any hydrocarbonaceous materials from the catalyst using this treatrnent.
U.~. Patent No. 3,893,942 t~ Yang also shows a process for 20 isoparamn-olefin alkylation using crystalline zeolite cat~ysts. A small amount of a hydrogenation catalyst (Group Vlll m~tal) is included in the zeolite.
Hydrogen gas is periodically introduced into the zeolite (apparently after the catalyst has been partially deactivated) and restores the ac~y of the catalyst.
Yang indicates that the n~ture of the chemical reaction between the 25 hydrocarbonaceous deposit and the hydrogen is not clear but hydrogen is consumed and the alkylation activity is restored. This procedure is said to avoid ~refractory coke deposits" formed when using high temp~rature inert gas regeneration treatments. Oxidative treatments are then said to be necessary. A paramnic wash is desirably first applied to the catalyst to assist 30 in the following hydrogenation step.
U.S. Patent No. 3,855,343 to Huang et aî. teaches an isoparamn-olefin aîkylation process in which the cata~st is a combination of a macroreticular WO93/10065 ~ ~-4~ 8 PCI/US92/10095 acid cation exchange resin and boron trifluoride. The boron trifluoride is present in an amount in excess of that needed to saturate the resin. This catalyst is said to "age" and after some period of time must be regenerated.
The catalyst is regenerated by solvent extraction wi~h a polar solvent, ~ ~;
preferably a low molecular weight alcohol. ~;
The process disclosed in U.S. Patent No. 4,05~,~75 to C:ahn.~. is a method of converting hydrocarbons, e.g., by alkylating them, in the pres~nce of a Lewis acid and a strong Bronsted acid. Partially deacti~rated catalytic materials are pretreated with a hydrocarbon to remove contaminants and deactivated catalyst species.
The U.S. Patent No. 4,308,414 to Madgavkar shows a process for - oligomerizing longer alpha-olefins using a particulate adsorbent (preferably SiO~) and adsorbed boron trifluoride and water. The catalyst is regenerated by the procedure of adding a small amount of water with the feed olefin.
~ The U.~. Patent Nos. 4,914,256 and 4,992,614 to Rodewald sugg~st the reactivation of catalysts (particularly supportsd boron trifluoride-containing alkylation catalysts) used in a variety of hydrocar~on conversion catalys~ by application of ultrasonic energy to the partially deactivated catalyst. Th~
procsss is said to eliminate th~ need for separation of the catalyst from Ule feedstock nor to subject the catalyst to a "burn-of~ operation. ;
One disclosure showing thc us8 of SO2 to regenerate catalysts is Ssapan et~!, "Decoking and Regeneration of a I Iydrotreating Catalyst by Supercr~ical Extraction~, ACS Symposium Series 411, American Chemical Sociaty, Washington, D.C., 1989. This disclosure shows the use of SO2 (and other solvents) a~ pressures above their critical pressures to r0movs coke-type carbon spscies from hydrotrsating catal~sts. The use of SO2 above 1200 psig is shown. The disclosure does not suggest th~ treatment of any ca~alysts which have non-ooke residue.
These disclosures do not show the use of our liquid solvent extraction process to r~vive acidic catalysts having non-coke residue and especially those which are promoted with a Lewis acid (preferably BF3) and which havs been used in the alkylation of isoparaffin with olefins.
` W O 93/10065 21191A4 PC'r/US92/1~095 SUMMARY OF THE INVENTlON
This invention is a solvent extraction process for the regeneration of solid acidic hydrocarbon conversion catalysts but particularly those acidic csta~ such as aluminas or zeolites which have been promoted with Lewis acids (preferably BF3) and used in the alkylation of isoparaffins with olefins.
The process involves contacting the solid acidic catalyst with a liquid solutioncomprising a solvent selected from SO2; oxygenates such as C,-C4 alcohols, ketones, and aldehydes; nitriles such as acetonitrile; and phenolics such as anisole and phenol. When the solid acidic catalyst additionally comprises a Lewis acid the process involves contacting the combination catalyst with a liquid solution comprising a sotvent selected from SO2 or from aromatic ethers and phenolics such as anisole and phenol.
The catalysts for these processes include such disparate acidic materials as acidic zeolites, alumina, silica-alumina, silica, boron oxides, phosphorus oxides, titanium oxide, zirconium oxide, chromia, zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, chromia-alumina, alumina-boria, silica-zirconia, aluminum phosphate molecular sieves, silicoaluminophosphate molecular sieves, solid polymeric ion exchange resins, tetravalent metal phosphonates with pendent acid groups, sulfatsd metal oxides (such as alumina), and the like. These catalysts may be treated with or complexed with Lewis acids. They are all acidic in their functionality as hydrocarbon conversion catalysts.
The alkylation process in which certain of the candidate catalysts are used produces alkylates suitable for use as very high octane, non-aromatic blending components in rnotor fuels. The alkylates are produced from olefins and isoparamns. The cata ys~ used comprises on~ or more transitionaJ
aluminas which are treated with at least one Lewis acid, preferably BF3. The process optimally utilizes an amount of free Lewis acid and produces high octane alkylate.
The regeneration process includes the steps of separating the solid component from the liquid reaction medium (but preferab~ maintaining it in the substantial absence of oxygen and water) and contacting the solid with an -WO 93/1006~ 9~4 PCl/I,'S92/10095 excess of the liquid solvent. The catalyst may be heated at a lower temperature prior to the solvent contact step so to volatilize certain hydrocarbons and to recover any complexed Lewis acid or may be washed with an inert solvent such as isobutane or other branched alkane.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph of the results of the regeneration procedure of the invention as practiced in Example 1 upon an alumina-based alkylation catalyst i~over several liquid S2 regeneration cycles.
Flgure 2 is an 1'B NMR graph of the catalyst used in Example 1 following several regeneration cycles.
DESCRIPTION OF THE INVENTION ;
This invention is a solvent extraction process for the regeneration of 15 solid~acidic hydrocarbon conversion catalysts but particularly those aadic catalysts such as aluminas or zeolites which have been promoted w~ Lewis acids (preferably BF3) and used in the alkylation of isoparamns with olefins.
The process involves contacting the solid acidic cata~st (which does not contain a significant Lewis add component) with a liquid solution comprising a 20 solvent selected from SO2; oxygenates such as C,-C~ alcohols, keton~s, and aldehydes; nitriles such as acetonitrile; and phenolics such as anisole and phenol. When the solid aoidic c~talyst additionally compnses a Lewis acid, the process involves contacting ~he combination catalyst with a liquid solution comprising a solvent s~lected from SO2 or from aromatic ethers and phenolics 25 such as anisole and phenol.
The solid acid ca~alysts suitable for ragen0ra~0n using these prncesses include such disparate acidic matsrials as acidic z~olites, alumina, silica-alumina, silica, boron oxides, phosphorus oxides, titanium oxlde, zirconium oxide, chromia, zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, 30 chromia-alumina, alumina-boria, silica-zirconia, aluminum phosphate molecularsieves, silicoaluminophosphate molecular sieves, solid polymeric ion exd~ange resins, tetravalent metal phosphates with pendent acid groups, su~ated metal WO 93/10065 PCl'/US92/10095 '. , '':' 21191~
oxides (such as alumirla), snd the lik~. In particular, the zeolites are preferably large pore zeolitic materials such as zeolite L, zeolite X, zeolite Y, ZSM4, ZSM-5, ZSM-11, ZSM-12, zeolite ~, zeolite n, mordenite, and faujasite.
The zeolites must be acidic but may be natural, synthetic, or may have 5 framework substitutions of other metals. These catalysts may be treated with or complexed with Lewis acids. They are all acidic in their functionality as hydrocarbon conversion catalysts.
The preferred cata yst system for this regeneration process comprises certain transition aluminas which have been treated with one or more Lewis 10 acdds in combination with a minor amount of free Lewis add. The alumina ca~alyst component is made by contacting free Lewis acid with certain transition alumina substrates.
The Alumina Catalyst Component ~ The preferred alumina catatyst component comprises or consists essentialty of a major amount of transition aluminas (preferably eta- or gamma-alumina) which has been treated with a Lewis acid, preferably BF3.
The catalyst component is acidic in nature and contains substantially no metals (except, of course, aluminum and the semi-metal boron) in cataqf~c amounts except as may be present in trace amounts in the BF3 or alumina.
Alumina Aluminum oxide (alumina) occurs abundantly in nature, usually in th~
form of a hydroxide in the minsral bauxite, atong with other oxidic impurities such as r~O2, Fe203, and SiO2. The Bayer process is used to produce a reasonably pure At203 ha~Jing a minor amount of Na20. The Bayer process AJ2O3 iS further trsatsd to produce a variety of alumina hydroxides:
: . ..
21 1~1 ~ 4 1~d3 Rec'd P~T/PTO O 2 DEC 199~
Com mon % H2O/ CAS
Material Name H2O ~!~ Index No.
a-trihydrate hygrargillite/gibbsite 35 3.0 14762-493 ~-trihydrate bayerite 35 3.0 20257-20-9 or ~-trihydrate nordstrandite 35 3.0 13840-05-6 oc-monohydrate boehmite 15 1.0 1318-23-6 - hydrate psuedoboehmite 26 2.0 ~ ;-The aluminum hydroxides may then be treated by heating to produce various activated or transition aluminas. For instance, the aluminum hydroxide known as boehmite may be heated to form a sequence of transition phase aluminas: gamma, delta, theta, and finally, alpha (see Wefers et al., NOxides 15 and Hydroxides ot Alumina", Technical Paper No. 19, Aluminum Company of America, Pittsburgh, PA, 1972, pp.1-51).
Transition aluminas (and their crystalline forms) include~
gamma tetragonal delta orthorhombic/tetragonal ` ;~-eta cubic theta monoclinic ~
chi cubic/hexagonal ~ -kappa hexagonal lambda orthorhombic Activated aluminas and aluminum hydroxides are used in various chemical processss as catalyst and adsorbents. The aluminas suitable for use in this process include the noted transition aluminas: gamma, delta, eta, theta, chi, kappa, rho or lambda. Especially preferred ar~ gamma and eta-aluminas.
Mixtures of the two are also desirable.
Sincs it is difficult to produce a substantially pur~ singls phase transition alumina, mixtures of various aluminas are tolerabls. For instance, in th~
production of eta-alumina, gamma-alumina is oftsn concurrsntly present in the resulting product. Indeed, x-ray diffraction analysis can only detect the SUBSTITU~E SHEET
WO 93/1006~ 21 i ~ ~ ~ 4 PCI`/US92/10095 difference between the h~o phases with some difficulty. Aluminum hydroxides (boehmite, gibbs~te, etc.) may be present in the predominately transition phase product in more than trivial amounts so long as they do not substan~ally affect the desired alkylation reaction.
The catalyst may be found in any appropriate form such as pellet, granules, bead, sphere, powder, or other shape to facilitate ts use in fixed beds, moving beds, or fluidked beds.
Lewis Acids 1~ the cat~lyst system of the regeneration process uses one or more Lewis acids in conjunction ~nth the acidic catalyst noted above, then the Lewis acids may one of those described below.
A Lewis acid is a molecule which can form another molecule or an ion by forming a oomplex in which it accepts two electrons from a second molecule or ion. Typical strong Lewis acids include boron halides such as BF3, BCI3, BBr3, and Bl3; antimony pentachloride (SbFS); aluminum halides (AICI3 and AlBr~); titanium halides such as TiBr~, r~CI4, and TiCI3; zirconium tetrachloride (ZrCI~; phosphorus pentafluorids (PFd; iron halides such as FCI3 and FeBr3; and the like. Weaker Lewis acids such as tin, indium, bismuth, zinc, or mercury halides are also acc~ptable.
Cat~t ~r~paratiQn The preferred alurnina catalyst system may b~ pr~pared in situ in an alkylation rsactor by passing the Lewis acid in gas~ous form through the vessel containing ths transition alumina. Alterna~ively, the alumina may be c~ntacted with the Lewis acid and later introduc~d in~o the reactor. In any case, the alumina should b~ substantially d~ prior to contact ~nth the L0wis acid and maintained in that state. Contact temperatures behv~en -25 C and about 100-C are acceptable; a ~emperature between 25 C and 30 C is preferred. The partial pressure of gaseous Lewis acid added to the alumina is not particu~arly important so long as a sufficient amount of Lewis acid is added to the alumina. ~JVe have found that treatrnent of the alumina with BF3 WO93tlO06~ 9~ ~ PCI~/US92/1009 at the noted temperatures will result in an alumina-BF3 complex containing BF3 sufficient to carry o~ the alkyl~tion. The alumina contains between o.~% and 30% by weight of BF3.
Obviously, the alumina or other catalyst n ay be incorporated into a 5 binder prior to its treatment with Lewis acid. The binders may be clays (such as montmorillonite and kaolin) or silica based materials (such as gels or other gelatinous precipitates). Other binder materials include carbon and meW
oxidss such as alumina, silica, titania, zirconia, and mixtures of those metal oxides. The composition of the binders is not particularly critical but care 10 must be taken that they not substantially in~erfere with the operation of the alkylation reaction.
Alkylation Pr~ces~
The alkylation process used in on~ aspect of the invention involves 15 cor~tacting an isoparamn with an olefin in tha presenc~ of ~he alumina-based catalyst discussed above and in the presence of some excess free Lewis acid.
Specffically, the catalyst of this invention is active at low temperatures (as low as -30 C) as well as at higher temperatures (nearing 50-C). Lower 20 temperatures (-5-C to 15-C) are preferred because of the enhanced octane of the alkylate produeed and are particularly preferred if the feeds~ream contains more than about 1% isobutylene. Higher temperatures also tend to produce larger arT-ounts of polymeric materials. The pr~ssure used in the alkylation process is not particularly cFitical. In general1 ths pressure must be 25 kept high enough to maintain the reactants and products in the liquid phase, although the catalyst will produce alkylation products when the feedstock is gassous. As a practical guideline, the process may be operat0d at atmospheric pressur~ to about 750 psig. The amount of catalyst used in the alkylation process depends upon a wids variety of disparate variables.
30 Never~heless, we have found that ths Weight Hourly Space Veloc~y ("WHSV~
= wcight of olefin feed/hour . weight of catalyst) may effective~ be between 0.1 and 120, especially between 0.5 and 30. The overall molar ratio of WO 93/1006S 2 i 1 ~ 1 ~ 4 PCI`/US92/10095 : .
isoparamn to olefin is between about 1.0 and 50Ø Preferred ranges include 2.0 and 25.0; the more preferred include 3.0 and 12Ø
The feedstreams introduced into the catalyst desirably comprise isoparaffins having from four to ten carbon atoms and, most preferably, four 5 to six carbon atoms. Isobutane is most preferred because of its ability to make high octane alkylate. The olefins desirably contain from three to five `
carbon atoms, i.e., propylene, cis- and trans-butene-2, butene-1, and amylenes.
The products of this alkylation process typically contain a complex 10 mixture of highly branchad alkanes. For instance, when using isobutane as the alkane and n-bu~ylene as thc olsfin, a mixture of 2,2,~; 2,2,4-; 2,3,3-; and2,3,4-trimethylpentane tTMP) will result often with minor amounts of other isomeric or polymeric products.
The process involved may utilke the catalyst in a fixed bed using single 15 or multiple feeds. That is to say, the feedstocks may be independently introduced at one or more points throughout the bed or between multiple beds. Desirably, the catalyst is contacted with the feedstocl(s in one or more of continuously stirred r~actors, preferably with feed to each reactor.
Re~eneration Step As w~ have discussed abovs, the regeneration step involves the steps of separating the solid cat~lytic material from the product of the hydrocarbon conversion process by us~ of a liquid-solid separation t~chnique and followed by tha st8p of contacting the catalytic material with a solvent capabl~ of regensrating ~he material. The solvent desirably is selectsd from SO2;
oxygenates such as C,-C" alcohols, ketones, and aldehydes; alkylnitriles such as acetonitrile; and phenolics and aromatic ethers such as anisole and phenol. Most pr~ferably, the solvent comprises SO2.
The catalyst may b~ first contacted with an inert gas to strip any excess gaseous Lewis acid and light hydrocarbons ~rom the solid cata~st component. The catalyst may also be treated using a mild heating step (e.g., 50- to 75 C) prior to the solvent contact step to further strip hydrocarbons from the solid. Addnionauy~ the removal of hydrocarbons and excess Lewis WO 93~10065 PCr/US92/10095 9~L4 15 acid may acilitated by contact with an inert gas such as helium, nitrogen, etc. The hydrocarbons and Lewis acid may be recycled as appropriate.
The process involves contacting the soîid addic catalyst with a liquid solution comprising a solvent selected from SO2; oxygenates such as C,-C~
5 alcohols, ketones, and aldehydes; nitriles such as acetonitrile; and phenolics such as anisole and phenol. When the solid acddic catalyst additionally comprises a Lewis acid the process involves contacting the combination catalyst with a liquid solution comprising a solvent selected from SO2 or from -aromatic ethers and phenolics such as anisols and phenol.
Specifically, the regeneration step involves the contacting of the solid ~;
catalyst component with the liquid solvent stream. Clearly, the choice made ~ -for the step of physically contacting the catalyst is dependent in large part upon the specifics of the catalyst component itseH. For instance, .f the ~ `
catalyst is in the form of tablets or extrudates or Pall rings (or the like) and are -~
15 found in a fixed bed, the most appropriate way to contact the catalyst would be to pass the liquid solvent over the catalyst in the catalyst's fixed bed. If,the catalyst is used as a slurry, the catalyst may be transported to a vessel suitable for contacting the alumina component with a liquid stream and then separating the solid from the liquid. rne reactor in such a process would 20 likely be a good choice for such a vessel. We have found it to be desirable that the catalyst be kept out of contact with water and ~nth oxygen.
The amount of solvent used should be sufficient to remove at least a portion of the resction rssidue found on the catalyst component. The residue is ill-defined but often appears to be a moderately long-chained or polymeric 25 materi~ largely alkane in nature but with a minor olefinic character. The residues also often contain polyolefins and aromatic components in small concentrations. We do not consider this regeneration process to b~
appropriate for residue caused as a result of high t~mperature hydrocarbon conversion processes, a~ least those which produce graphitic or 30 carbonaceous residues on the catalyst. Such residues typically havc H/C
ratios less ~an one. Atthough the amount is not believed to be critical, we have found that for most alumina-based alkylation catalysts, an amount of WO 93/10065 2 1~ Pcr/US92/10095 17 :
about 100 gm. of solvent per gm. of catalyst is sufficient to regenerate the catalyst to at least 40 % of the prior activ~y.
The temperature of the contact step is also not critical but for alkylation catalysts, treatment in the range of 0-C to 50-C is appropriate.
When a solvent comprising SO2 is utilized in the corltact step to regenerate catalysts containing Lewis acids, the solvent should be generally dry; preferably it is substantially free of organic and inorganic bases and SO3 and H2SO~. The level of these contarninants may be such that they do not substantially affect the level of catalyst act~ity upon return to the hydrocarbon conversion medium. Hydrocarbonaceous diluents, such as are the products `
of the accompanying hydrocarbon conversion process often make suitable diluents for the solvent used to regenerate the catalyst.
Once the steps outlined above are completed, the solid catalyst component may be again be treated with one or more Lewis acids as specified above and returned to th~ hydrocarbon conversion step. It may be desirable when using SO2 as the solvent and a gaseous Lewis acid to ~`
overpressure the gaseous Lewis acid te.g., at a pressure above the pressure at which the reaction and/or the solvent treatment step is carried out) before returning the catalyst to service; although we do not wish to be bound by this theory, we believe that the overpressure aids in sweeping or displacing the solvent from the catalyst surface.
The inven~ion has been disclosed by direct description. Below may be found examples showing various aspects of the invention. The examples are only examples of the invention and are not to be used to lim~ the scope of the invention in any way.
EXAMPLES
Example 1 This example shows the regeneration of an alumina-based catalyst which had been treated with BF3 and then used wi~h excess BF3 in an WO 93/10065 ~ 2~-9~4 PCI/US92/10095 :~
alkylation reaction. The feedstream to the alkylation step was a synthe-,cally prepared feed simulating the hydroisomerized C" emuent from an MTBE unit (MTBE emuent).
The olsfinic feedstock was prepared containing (by weight) 94% trans-and cis-2-butene, 5% buten~1, and 1% isobutylene. The feedstock was prepared by mixJng the olefinic feedstock with isobutane such that the final molar ratio of isobutane to olefin was 6/1. This was fed to the alkylation reactor at a weight hourly space velocity CVVHSV ~ based on olefin) was 10.7.
The reaction temperature was held to O C. Samples were periodically removed from the reactor for analysis by gas-liquid chromatography.
During each reaction step, the alkylation reaction was run until approximately 85 gm of olefin per gram of catalyst ~I~e., the catalyst ~age~) had been processed. At that point, there was some indication of a loss of ac~vity ~
of the catalyst as evidenced by a decreasing amount of product C8 content ; -and a concomitant increase in the product C12~ content. Additionally, a ,~
decrease in the (R+ M)/2 as calculated from the gas-liquid chromatography data using well-known correlations (Hutson and Logan, ~Estimate Alky ~leld and Ouality~, Hydrocarbon Processing, September, 1975, pp. 107-108) was ~ -noted at about that catalyst age.
The catalyst was then regenerated using the following procedure:
1. 50 cc of isobutane were added to the alkylation reactor primarily to raise the liquid level to assist in washing back into solution any oa~alyst that had accurnulated at the top of the reactor, 2. the liquid product and isobutane were removed from the reactor through a filtering frit using pressurized inert gas, 3. the reactor containing the spent catalyst was purged with inert gas at 15 cc/min for thirty minutes until the cata~st had the consistency of a free-flowing powder, 4. 150 ml. SO2 were added to thc reactor and the contents stirred WO 93~10065 2 1 1 9 1 ~ 4 PCr/U!~92/10095 for 20 minLnes, 5. SO2 was withdrawn from the r~actor using pressurized inert gasand recovered in a collection vessel. The flow of in~rt gas was continued until no liquid was presant in the reactor, 6. steps 4 and 5 were repeated hvice, 7. the system was flushed w~h flowing inert gas fw 15 minu~es at 15 cc/rnin., 8. BF3 was added to the reactor vessel containing the reganeratedcatalyst and pressurked to a total pressure of 60 psig of 8F3.
This pressure was held for 15 minutes. The reactor was then ~ depressurized and purged with inert gas for five minutes, and 9. step 8 was repeated with the exception that follo~nng the depressurization of the BF3, the inert gas was allowed to purge the system for 20 minutes. The system was then ready for the next alkylation cycle.
Following regeneration, the same procedure to initiate the alkylation reac~ion was followed as with a fresh catalyst, with the exception that isobutane was added to the reactor con~aining the catalyst and stirred for 25 approximateiy 30 minu~es prier to addition of the BF3. This was to insure th~t the catalyst was well mixed in~o ~he liquid medium.
~ he described procedures of alkylation followed by regeneration were repeated for a total of nine cycles.
The results of the product analysis from each cycle are summarized in Table 1 30 and Figure 1, indicating initial and final performance as m~asured by gas chrom~tographic analysis of the hydrocarbon effluent. The data clearly show that the full activity of the ca~alyst is restored using the regeneration WO93/10065 21~9~44 PCI/US92/1009S
procedure. 2 0 Following ths final alkylation cycle, the catalyst was again regenerated with SO2 using the noted procedure. Analysis of the recovered catalyst by elemental analysis gave the following results:
Carbon, wPh 0.3 Boron, wP~ 1.9 Fluorine, wt96 11.1 Suifur, wt% (below detection limits) The low carbon and sulfur content of the catalyst show that the SO2 regeneration procedur~ is very efficient~ The S2 does not accumulate on the surface of the catalyst a~ter regeneration. The boron and fluorine contents of the catalyst are very similar to that found on a fresh catalyst. Analysis of 15 the boron-containing species by solid state NMR of boron (Fig. 2) shows a single resonance peak at about -21 ppm, indicating ths presence of a sole active boron species and the absence of any decomposition products arising ~rom the regeneration procedure. Thus, the regeneration procedure is believed to remove contaminating carbon residues while maintaining intact the 20 important species on the catalyst surface.
WO 93/10065 PCl`/US92/10095 21~144 . _ -- -, .
Cycle # C8,wt.% I C,2 ,wt~ Octane, l (R+ M)/2 _ ~ ,, 1 initial 95.3 2.4 _ 97.6 ~
final 92.2 4.9 96.1 _ 2 initial 95~3 2.6 97.6 final 85.8 9.8 94.6 initial 96.8 2.0 _ 75 . _ final 87.4 8.9 _94.9 4 inibal 95.4 2.2 97.7 final 9 6.5 95.7 initial 96.1 1.7 97.8 I ~.~
hnal 92.4 5.0 96.1 6 initial 95.8 2.1 97.8 final 93.5 4.4 96.2 I
7 initial 95.1 2.8 97.7 I _ final 93.4 4.5 96.3 8 initial 94.9 2.9 97.7 `` `
final 93.4 4.3 96.3 I , , 9 initial 94.3 3.1 97.5 :
, _ . . . . , . .. ., . __ ~
ample 2 --lllis example demonstrates the SO2 regeneration step using a commercial MTBE raffinate feedstock which had been hydroisomerized to remove butadiene and to convert a portion of the butene-1 to cis- and trans-2-butene-2. This feedstock has the following composition ~In wt% on a total olefin basis): 4.3% isobutene, 4.9% butene-1, 87.2% cis- and trans-buten~2, 1.996 2-methyl butene-1 and 2-methyl butene-2, and 1.7% pentene-æ
WO 93/10065 ~ 4 4 PCI /US92/ 10095 This olefinic feedstock was blended with isobutane to a final isobutane/olefin ratio of 6. Normal butane was added to produce a level of 18% in the total feed. This feedstock was fed to the catalyst at 0 C at a WHSV (on olefin) of 7.2. Samples were taken periodically and analyzed by 5 ~as chromatography.
The catalyst was run for a total of five cycles with regeneration between cycles using liquid SO2 in the procedure shown in Exampb 1. The C8, C~2~, and (R+ M)/2 values measured at the beginning and at the end of each cycle are shown in Table 2. This example shows that the rsgeneration step using 10 SO2 performs well on an alkylation catalyst which has been used on a commercial feed.
. _ _ ~Cycle # ¦ ¦ C8 ¦ C~z+ ¦ Octane (R+ M)/2 _ , 1 initial 77.0 6.6 _95.3 final 40.4 26.4 85.9 _ . . I
2 ir~itial 79.7 6.8 9!;.6 ~ .
final 37.9 22.3 8~.1 _ _ 3 initial 81.5 6.0 95.5 _ final _ 60.5 15.3 91.5 4 initial 79.7 5.5 95.7 _ _ .
final 67.7 17.2 92.2 _ .
inRial 82.8 4.5 95.8 _ _ _. , ~ . . . , .
~5 It should be elear that one h~ing ordinary skill in this art would envision equivalents to the processes found in th~ claims that follow and that those equivalents would be within the scope and spirit of the claimed invention.
A METHOD FOR REGENERATING CERTAIN ACIDIC HYDROCARBON
CON\IERSION CATALYSTS BY SOLVENT EXTRACTION
FIELD OF THE INVENTION
This invention is a process for tha regeneration of solid acidic hydrocarbon conversion catalysts, but particularly certain transition aluminas and zeolites promoted with Lewis acids (preferably BF3) which have besn us~d in the alkylation of isoparaffin with olefins. The proc~ss involves th~
removal of some portion of the reaction product residue adhering to the solid cata~yst by contact with a solvent to partially recover the catalyst's initial activity.
~UND OF THE INVENTIC)N
There are a wide variety of hy.drocarbon conversion processes using strongly acidic solid acid catalysts at temperatures low enough to maintain the SUBSTlTUTE SHEEr 2`11~144 . PCr/US92/10095 reaction medium in a liquid phase. These processes include oligomer,_.tion, alkylation, isomerization, hydroisomerkation, etc. The catalysts for these processes include such disparate acidic materials as acidic zeolites, alumina, silica-alumina, silica, boron oxides, phosphorus oxides, titanium oxide, zirconium oxide, chromia, zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, chromia-alumina, alumina-boria, silica-zirconia,aluminum phosphate molecular sieves, silicoaluminophosphate molecular sieves, solid polymeric ion exchange resins, tetravalent metal phosphonates with pendent acid groups, sulfated metal oxides (such as alumina), and the like. These catalysts may be treated with or complexed with Lewis acids. A side reaction in many of these processes produces what appears to be a low level polymer or oligomer.
Unlike many higher temperature processes, the side prodllcts are not cok~
like in nature. These poorly characterized side reaction products, or "gunk~, may be at least partially removed using solvent sxtraction procedures and carefuliy chosen solvents. One process, with its concomitant catalyst, to which solvent extraction is especially applicable is isoparaffin/olefin alkylation using solid acid catalysts particularly zeolites or aluminas which have been . - ~
treated with Lewis acids.
The preparation of high octane blending components for motor fuels using strong acid alkylation processes (notably where the acid is hydrofluoric ~ -acid or sulfuric acid) is well-known. Alkylation is the reaction in which an alkyl group is added to an organic molecule (typically an aromatic or olefin). For production of gasoline blending stocks, the reaction is b~tween an isoparaffin and an olefin. Alkylation proces~es have been in wide use since World War ll when high octane gasolines were needed to satisfy demands from high compression ratio or supercharged aircra~t engines. The early alkylation units were built in conjunction with fluid catalytic cracking units to take advantage of the light end by-products of the cracking units: isoparamns and olefins.
Fluidized catalytic cracking units still constitute the major source of feedstocks for gasoline alkylation units. In spite of the mature state of strong acid alkylation technology, existing problems with the hydrofluoric and sulfuric acidtechnologies continue to be severe: disposal of the used acid, unintentional -, 211314403 Re~'~l P~/?~ EC ~ J
emission of the acids during use or storage, substantial corrosivity ~f the acidcatalyst systems, and other environmental concerns.
Although a practical alkylation process using solid acid catalysts having little or no corrosive components has long been a goal, commercially viable processes do not exist.
The open literature shows several systems used to alkylate various hydrocarbon feedstocks.
The American Oil Company obtained a series of patents in the mid-1950's on alkylation processes involving C2-C,2 (preferably C2 or C3) olefins and C4-Ca isoparaffins. The catalysts used were BF3-treated solids and the catalyst system (as used in the alkylation process) also contained free BF3. A
summary of those patents is found in the following lis~:
.
Patent No. Inventor BF3-Treated Catalvst~ (with free BF~) 2,804,491 May et a!- SiO2 stabilized Al2O3 (10%-60% by weight BF3) 2,824,146 Kelly et al. metal pyrophosphate hydrate 2,824,150 Knight et al. metal sulfate hydrate 2,824,151 Kelly et al. metal stannate hydrate 2,824,152 Knight et al. metal silicate hydrate 2,824,153 K~lly et al. metai orthophosphate hydrate 2,824,154 Knight et al. m~tal tripolyphosphate hydrate 2,824,155 Knight et al. matal pyroarsenate hydrate 2,824,156 Kelly et al. Co or Mg arsenate hydrate 2,824,157 Knight et al. Co, Al, or Ni borate hydrate 2,824,1~8 Kelly et al. metal pyroantimonate hydrate salt 2,824,159 K~lly et al~ Co or Fe molybdat~ hydrats 2,824,160 Knight,et al. Al, Co, or Ni tungstate hydrats 2,824,161 Knight et al. borotungstic acid hydrate or Ni or Cd borotungstate hydrate 2,824,162 Knight et al. phosphomolybdic acid hydrate 2,945,907 Knight 3. solid 9~1 alumina (~%-100% by weight of Zn or Cu fluoborate, preferably anhydrous) ~may be supported on Al2O3 None of these disclose a process for regenerating an alkylation catalyst using SUBSTITUTE SHEEr WO93/1006~ 9~ 4~ PCI/US92/10095 a solvent extraction process for regenerating the catalyst.
Acid catalysts used to oligomerize olefins are known. U.S. Patent No.
2,748,090 to Watkins suggests the use of a catalyst made up of a Group vîli metal (preferably nickel), a phosphoric acid (preferably containing phosphoruç
5 pentoxide), plac~d on an alumina adsorbent, and pretreated with BF3.
Alkylation of aromatics is suggested.
U.S. Patent No. 2,976,338 to Thomas suggests a polymerization catalyst comprising a compiex of BF3 or H3PO~ optionally on an adsorbent (such as activated carbon) or a molecular sEeve optionaily containing 10 potassium acid fluoride.
Certain references suggest the use of alumina-containing catalysts for alkylation of aromatic compounds. U.S. Patent No. 3,068,301 to Hervert*t al.
suggests a catalyst for alkylating aromatics usîng ~olefi~acting compounds~
The catalyst is a solid, silica-stabilked alumina up to 10% SiO2, all of which has been modified with up to 100% by of weight BF3. `Other BF3-treated aluminas are known. For instance, U.S. Patent No. ; ~-3,114,785 to Hervert et al. suggests the use of a BF3-modified, substantially -~ .
anhydrous alumina to shift the double bond of 1-butens to produce 2-butene.
The preferred alumina is substantially anhydrous gamma-alumina, eta-alumina, 20 or theta-alumina. The v~rious aluminas will adsorb or complex with up to about 19% by weight fluorins depending upon the typ~ of alumina and the temperature of treatment.
In U.S. Patent No. 4,407,731 to Imai 8 high surface area metal oxide such as alumina (particularly garnma-alumina, e~a-alumina, ~heta-alumina, 25 silica, or a siliea-alumina) is used as a base or support for BF3. The BF3 treated me~al oxide is used for generic oligomerization and alkylation reactions. The metal oxide is tr~atad in a complicated fashion prior to bein~
treated with BF3. The first step entails treating the metal oxids with an acid solution and with a basic aqueous solution. Th~ support is washed with an 30 aqusous decomposable sait such as ammonium nitrate. The support is washed using deionized H2O until the wash water shows no alkali or alkaline earth metal cations in the filtrate. The support is dried and calcined. 1 he WO 93/10065 PCI/US92/1009~
211914~
disclosure suggests generically that BF3 is then introduced to the treated metal oxide support. The examples show introduction of the BF3 at elevated temperatures, e.g, 300 C or 350 C.
Similarly, U.S. Patent No. 4,427,791 to Miale ~I- suggests the S enhancement of the acid catalytic activity of inorganic oxide materials (such as alumina or gallia) by contacting the material with ammonium fluoride or boron fluoride, contacting the treated inorganic oxide with an aqueous ammonium hydroxide or salt solution, and calcining the resulting material. The inorganic oxides treated in this way are said to sxhibit enhanced Bronsted addity and, ~^
10 therefore, is said to have improved acid activity towards the catalysis of numerous and several reactions (such as alkylation and isomerization of various hydrocarbon compounds). A specific suggested use tor the treated ~ ;
inorganic oxide is as a matrix or SUppOft tor various zsolite materials ultimately used in acid catalyzed organic compound cor~rsion processes.
U.S. Patent No. 4,75t,341 to Rodewald shows a process for treating a ZSM-5 type zeolne with BF3 to reduce its pore ske, enhance its shape selectivity, and increase ns activity towards the reaction of oligomerking olefins. The patent also suggests using these materials for alkylation of afomatic compounds.
~0 Certain Soviet publications suggest the use of A12O3 cata~sts for alkylation processes. Benzene alkylation using those catalysts (with 3 ppm to 5 ppm water and periodic additions of BF~ is shown in Yagubov, Kh. M. ~
al., Azerb. Khim. Zh., 1984, (5) p. 58. Similarly, Kozorezov, Yu and Levitskii, E.~, Zh. Print. Khim. (Lenin~rad), 1984, 57 (t2), p. 2681, show the us~ of 25 ~umina which has been treated at relatively high temperaturss and rnodified with BF3 at 100-C. There are no indication~ that BF3 is maintained in excess.
Isobutane alkylation using Al20JBF3 catalysts is suggested in ~leRekhimiya, 1977, 17 (3), p. 396; 1979, 19 (3), P. 385. The olefin is ethylene. There is no indication that BF3 is maintained in excess during the reaction. The crystalline30 form of the alumina is not described nor is any method suggested for regeneration of the catalysts.
U.S. Patent No. 4,918,255 to Chou ~1- suggests a process for the WO93/10065 PCl/US92/10095 2~9~4 6 alkylation of isoparaffins and olefins using a composite described as "comprising a Lewis acid and a large pore zeolite and/or a non-zeolitic inorganic oxide~. The process disclosed requires isomerization of the olefin feed to reduce substantially the content of alpha-olefin and further suggests 5 that water addition to the alkylation process improves the operation of the process.
U.S. Patent No. 4,992,616 to Chou ~. deals with the process noted above for alkylation of isoparaffins and olefins using a composite described as ~comprising a Lewis acid and a large pore zeolite~ but requires addition of 10 water for improving the operation of the process. The best Research Octane Number (RON) product shown in tho examples and made using the disclosed invention is 86.0 (Table 2). ~` -Similarly, PCT published applicaUons WO 90/00533 and 90/00534 ` ~
(which are based in part on the U.S. patent to Chou et al. noted above) ~; `
suggest the same process as does Chou ~1. WO 90/00534 is specific to a -process using boron trifluoride-treated inorganic oxides including ~alumina, silica, boria, oxides of phosphorus, titanium oxide, zirconium oxide, chromia, `
zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, chromia-alumina, alumina-boria, silica-zirconia, and the various naturally occurring inorganic 20 oxides of various states of purity such as bauxite, clay and diatomaceous earth. Of special note is the statement that the ~preferred inorganic oxides are amorphous silicon dioxide and aluminum oxide~. The examples show the use of amorphous silica (and BF~) to produce alkylates having an RON of no greater than 94. U.S. Pat. Number 4,935,577 to Huss, Jr. et al. teaches a 25 process for the catalytic distillation of various hydrocarbons by e.g., alkylation or oligomerization, using a catalyst ~consisting essentially of a Lewis acîd promoted inorganic oxide." The inorganic oxide may be selected from the non-zeolitic materials discussed above with regard to the Chou.ç~l.
published PCT applications. Additionally, the inorganic oxide may be a large 30 pore crystalline molecular sieve.
There are a variety of disclosed ways to regenerate catalysts used in alkylation processes or using Lewis acids. Typical of such processes are the 27l131 4~
following.
U.S. Patent No. 3,647,916, to Caesar et al. shows a process for isoparaffin-olefin alkylation using crystalline zeolite cata~sts at low isoparamn to olefin ratios. The zeolite is first steamed to reduce the number of acid sites ``
5 and so reduce the amount of olefin polymerization which occurs. The isoparaffin is added to the catalyst before the olefin is introduced to further limR the amount of polymerization. There is no discussion of the use of auxiliary Lewis acids in conjunction with the zeolites. Nevertheless, the catalysts are susceptible to deactivation due to the ~accumulation in the pores ~
10 thereof of olefin polymerization products~. The regeneration is carried out by - -buming ths surface residue ~in an oxygen-containing atmosphere at an elevated temperature in the range of about 800 to 1400- P followed by a step in which the catalyst is contacted with an aromatic or polar solvent.
U.S. Patent No. 3t833.679 to Gardner et al. shows a paraffin 15 isomerization process using an HSbF" catalyst sùpported on a fluorided alumina. The catalyst was regenerated by introducbon of an HF strearn sumcient to convert to any SbF5 to HSbF,s. No mention is made of removal of any hydrocarbonaceous materials from the catalyst using this treatrnent.
U.~. Patent No. 3,893,942 t~ Yang also shows a process for 20 isoparamn-olefin alkylation using crystalline zeolite cat~ysts. A small amount of a hydrogenation catalyst (Group Vlll m~tal) is included in the zeolite.
Hydrogen gas is periodically introduced into the zeolite (apparently after the catalyst has been partially deactivated) and restores the ac~y of the catalyst.
Yang indicates that the n~ture of the chemical reaction between the 25 hydrocarbonaceous deposit and the hydrogen is not clear but hydrogen is consumed and the alkylation activity is restored. This procedure is said to avoid ~refractory coke deposits" formed when using high temp~rature inert gas regeneration treatments. Oxidative treatments are then said to be necessary. A paramnic wash is desirably first applied to the catalyst to assist 30 in the following hydrogenation step.
U.S. Patent No. 3,855,343 to Huang et aî. teaches an isoparamn-olefin aîkylation process in which the cata~st is a combination of a macroreticular WO93/10065 ~ ~-4~ 8 PCI/US92/10095 acid cation exchange resin and boron trifluoride. The boron trifluoride is present in an amount in excess of that needed to saturate the resin. This catalyst is said to "age" and after some period of time must be regenerated.
The catalyst is regenerated by solvent extraction wi~h a polar solvent, ~ ~;
preferably a low molecular weight alcohol. ~;
The process disclosed in U.S. Patent No. 4,05~,~75 to C:ahn.~. is a method of converting hydrocarbons, e.g., by alkylating them, in the pres~nce of a Lewis acid and a strong Bronsted acid. Partially deacti~rated catalytic materials are pretreated with a hydrocarbon to remove contaminants and deactivated catalyst species.
The U.S. Patent No. 4,308,414 to Madgavkar shows a process for - oligomerizing longer alpha-olefins using a particulate adsorbent (preferably SiO~) and adsorbed boron trifluoride and water. The catalyst is regenerated by the procedure of adding a small amount of water with the feed olefin.
~ The U.~. Patent Nos. 4,914,256 and 4,992,614 to Rodewald sugg~st the reactivation of catalysts (particularly supportsd boron trifluoride-containing alkylation catalysts) used in a variety of hydrocar~on conversion catalys~ by application of ultrasonic energy to the partially deactivated catalyst. Th~
procsss is said to eliminate th~ need for separation of the catalyst from Ule feedstock nor to subject the catalyst to a "burn-of~ operation. ;
One disclosure showing thc us8 of SO2 to regenerate catalysts is Ssapan et~!, "Decoking and Regeneration of a I Iydrotreating Catalyst by Supercr~ical Extraction~, ACS Symposium Series 411, American Chemical Sociaty, Washington, D.C., 1989. This disclosure shows the use of SO2 (and other solvents) a~ pressures above their critical pressures to r0movs coke-type carbon spscies from hydrotrsating catal~sts. The use of SO2 above 1200 psig is shown. The disclosure does not suggest th~ treatment of any ca~alysts which have non-ooke residue.
These disclosures do not show the use of our liquid solvent extraction process to r~vive acidic catalysts having non-coke residue and especially those which are promoted with a Lewis acid (preferably BF3) and which havs been used in the alkylation of isoparaffin with olefins.
` W O 93/10065 21191A4 PC'r/US92/1~095 SUMMARY OF THE INVENTlON
This invention is a solvent extraction process for the regeneration of solid acidic hydrocarbon conversion catalysts but particularly those acidic csta~ such as aluminas or zeolites which have been promoted with Lewis acids (preferably BF3) and used in the alkylation of isoparaffins with olefins.
The process involves contacting the solid acidic catalyst with a liquid solutioncomprising a solvent selected from SO2; oxygenates such as C,-C4 alcohols, ketones, and aldehydes; nitriles such as acetonitrile; and phenolics such as anisole and phenol. When the solid acidic catalyst additionally comprises a Lewis acid the process involves contacting the combination catalyst with a liquid solution comprising a sotvent selected from SO2 or from aromatic ethers and phenolics such as anisole and phenol.
The catalysts for these processes include such disparate acidic materials as acidic zeolites, alumina, silica-alumina, silica, boron oxides, phosphorus oxides, titanium oxide, zirconium oxide, chromia, zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, chromia-alumina, alumina-boria, silica-zirconia, aluminum phosphate molecular sieves, silicoaluminophosphate molecular sieves, solid polymeric ion exchange resins, tetravalent metal phosphonates with pendent acid groups, sulfatsd metal oxides (such as alumina), and the like. These catalysts may be treated with or complexed with Lewis acids. They are all acidic in their functionality as hydrocarbon conversion catalysts.
The alkylation process in which certain of the candidate catalysts are used produces alkylates suitable for use as very high octane, non-aromatic blending components in rnotor fuels. The alkylates are produced from olefins and isoparamns. The cata ys~ used comprises on~ or more transitionaJ
aluminas which are treated with at least one Lewis acid, preferably BF3. The process optimally utilizes an amount of free Lewis acid and produces high octane alkylate.
The regeneration process includes the steps of separating the solid component from the liquid reaction medium (but preferab~ maintaining it in the substantial absence of oxygen and water) and contacting the solid with an -WO 93/1006~ 9~4 PCl/I,'S92/10095 excess of the liquid solvent. The catalyst may be heated at a lower temperature prior to the solvent contact step so to volatilize certain hydrocarbons and to recover any complexed Lewis acid or may be washed with an inert solvent such as isobutane or other branched alkane.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph of the results of the regeneration procedure of the invention as practiced in Example 1 upon an alumina-based alkylation catalyst i~over several liquid S2 regeneration cycles.
Flgure 2 is an 1'B NMR graph of the catalyst used in Example 1 following several regeneration cycles.
DESCRIPTION OF THE INVENTION ;
This invention is a solvent extraction process for the regeneration of 15 solid~acidic hydrocarbon conversion catalysts but particularly those aadic catalysts such as aluminas or zeolites which have been promoted w~ Lewis acids (preferably BF3) and used in the alkylation of isoparamns with olefins.
The process involves contacting the solid acidic cata~st (which does not contain a significant Lewis add component) with a liquid solution comprising a 20 solvent selected from SO2; oxygenates such as C,-C~ alcohols, keton~s, and aldehydes; nitriles such as acetonitrile; and phenolics such as anisole and phenol. When the solid aoidic c~talyst additionally compnses a Lewis acid, the process involves contacting ~he combination catalyst with a liquid solution comprising a solvent s~lected from SO2 or from aromatic ethers and phenolics 25 such as anisole and phenol.
The solid acid ca~alysts suitable for ragen0ra~0n using these prncesses include such disparate acidic matsrials as acidic z~olites, alumina, silica-alumina, silica, boron oxides, phosphorus oxides, titanium oxlde, zirconium oxide, chromia, zinc oxide, magnesia, calcium oxide, silica-alumina-zirconia, 30 chromia-alumina, alumina-boria, silica-zirconia, aluminum phosphate molecularsieves, silicoaluminophosphate molecular sieves, solid polymeric ion exd~ange resins, tetravalent metal phosphates with pendent acid groups, su~ated metal WO 93/10065 PCl'/US92/10095 '. , '':' 21191~
oxides (such as alumirla), snd the lik~. In particular, the zeolites are preferably large pore zeolitic materials such as zeolite L, zeolite X, zeolite Y, ZSM4, ZSM-5, ZSM-11, ZSM-12, zeolite ~, zeolite n, mordenite, and faujasite.
The zeolites must be acidic but may be natural, synthetic, or may have 5 framework substitutions of other metals. These catalysts may be treated with or complexed with Lewis acids. They are all acidic in their functionality as hydrocarbon conversion catalysts.
The preferred cata yst system for this regeneration process comprises certain transition aluminas which have been treated with one or more Lewis 10 acdds in combination with a minor amount of free Lewis add. The alumina ca~alyst component is made by contacting free Lewis acid with certain transition alumina substrates.
The Alumina Catalyst Component ~ The preferred alumina catatyst component comprises or consists essentialty of a major amount of transition aluminas (preferably eta- or gamma-alumina) which has been treated with a Lewis acid, preferably BF3.
The catalyst component is acidic in nature and contains substantially no metals (except, of course, aluminum and the semi-metal boron) in cataqf~c amounts except as may be present in trace amounts in the BF3 or alumina.
Alumina Aluminum oxide (alumina) occurs abundantly in nature, usually in th~
form of a hydroxide in the minsral bauxite, atong with other oxidic impurities such as r~O2, Fe203, and SiO2. The Bayer process is used to produce a reasonably pure At203 ha~Jing a minor amount of Na20. The Bayer process AJ2O3 iS further trsatsd to produce a variety of alumina hydroxides:
: . ..
21 1~1 ~ 4 1~d3 Rec'd P~T/PTO O 2 DEC 199~
Com mon % H2O/ CAS
Material Name H2O ~!~ Index No.
a-trihydrate hygrargillite/gibbsite 35 3.0 14762-493 ~-trihydrate bayerite 35 3.0 20257-20-9 or ~-trihydrate nordstrandite 35 3.0 13840-05-6 oc-monohydrate boehmite 15 1.0 1318-23-6 - hydrate psuedoboehmite 26 2.0 ~ ;-The aluminum hydroxides may then be treated by heating to produce various activated or transition aluminas. For instance, the aluminum hydroxide known as boehmite may be heated to form a sequence of transition phase aluminas: gamma, delta, theta, and finally, alpha (see Wefers et al., NOxides 15 and Hydroxides ot Alumina", Technical Paper No. 19, Aluminum Company of America, Pittsburgh, PA, 1972, pp.1-51).
Transition aluminas (and their crystalline forms) include~
gamma tetragonal delta orthorhombic/tetragonal ` ;~-eta cubic theta monoclinic ~
chi cubic/hexagonal ~ -kappa hexagonal lambda orthorhombic Activated aluminas and aluminum hydroxides are used in various chemical processss as catalyst and adsorbents. The aluminas suitable for use in this process include the noted transition aluminas: gamma, delta, eta, theta, chi, kappa, rho or lambda. Especially preferred ar~ gamma and eta-aluminas.
Mixtures of the two are also desirable.
Sincs it is difficult to produce a substantially pur~ singls phase transition alumina, mixtures of various aluminas are tolerabls. For instance, in th~
production of eta-alumina, gamma-alumina is oftsn concurrsntly present in the resulting product. Indeed, x-ray diffraction analysis can only detect the SUBSTITU~E SHEET
WO 93/1006~ 21 i ~ ~ ~ 4 PCI`/US92/10095 difference between the h~o phases with some difficulty. Aluminum hydroxides (boehmite, gibbs~te, etc.) may be present in the predominately transition phase product in more than trivial amounts so long as they do not substan~ally affect the desired alkylation reaction.
The catalyst may be found in any appropriate form such as pellet, granules, bead, sphere, powder, or other shape to facilitate ts use in fixed beds, moving beds, or fluidked beds.
Lewis Acids 1~ the cat~lyst system of the regeneration process uses one or more Lewis acids in conjunction ~nth the acidic catalyst noted above, then the Lewis acids may one of those described below.
A Lewis acid is a molecule which can form another molecule or an ion by forming a oomplex in which it accepts two electrons from a second molecule or ion. Typical strong Lewis acids include boron halides such as BF3, BCI3, BBr3, and Bl3; antimony pentachloride (SbFS); aluminum halides (AICI3 and AlBr~); titanium halides such as TiBr~, r~CI4, and TiCI3; zirconium tetrachloride (ZrCI~; phosphorus pentafluorids (PFd; iron halides such as FCI3 and FeBr3; and the like. Weaker Lewis acids such as tin, indium, bismuth, zinc, or mercury halides are also acc~ptable.
Cat~t ~r~paratiQn The preferred alurnina catalyst system may b~ pr~pared in situ in an alkylation rsactor by passing the Lewis acid in gas~ous form through the vessel containing ths transition alumina. Alterna~ively, the alumina may be c~ntacted with the Lewis acid and later introduc~d in~o the reactor. In any case, the alumina should b~ substantially d~ prior to contact ~nth the L0wis acid and maintained in that state. Contact temperatures behv~en -25 C and about 100-C are acceptable; a ~emperature between 25 C and 30 C is preferred. The partial pressure of gaseous Lewis acid added to the alumina is not particu~arly important so long as a sufficient amount of Lewis acid is added to the alumina. ~JVe have found that treatrnent of the alumina with BF3 WO93tlO06~ 9~ ~ PCI~/US92/1009 at the noted temperatures will result in an alumina-BF3 complex containing BF3 sufficient to carry o~ the alkyl~tion. The alumina contains between o.~% and 30% by weight of BF3.
Obviously, the alumina or other catalyst n ay be incorporated into a 5 binder prior to its treatment with Lewis acid. The binders may be clays (such as montmorillonite and kaolin) or silica based materials (such as gels or other gelatinous precipitates). Other binder materials include carbon and meW
oxidss such as alumina, silica, titania, zirconia, and mixtures of those metal oxides. The composition of the binders is not particularly critical but care 10 must be taken that they not substantially in~erfere with the operation of the alkylation reaction.
Alkylation Pr~ces~
The alkylation process used in on~ aspect of the invention involves 15 cor~tacting an isoparamn with an olefin in tha presenc~ of ~he alumina-based catalyst discussed above and in the presence of some excess free Lewis acid.
Specffically, the catalyst of this invention is active at low temperatures (as low as -30 C) as well as at higher temperatures (nearing 50-C). Lower 20 temperatures (-5-C to 15-C) are preferred because of the enhanced octane of the alkylate produeed and are particularly preferred if the feeds~ream contains more than about 1% isobutylene. Higher temperatures also tend to produce larger arT-ounts of polymeric materials. The pr~ssure used in the alkylation process is not particularly cFitical. In general1 ths pressure must be 25 kept high enough to maintain the reactants and products in the liquid phase, although the catalyst will produce alkylation products when the feedstock is gassous. As a practical guideline, the process may be operat0d at atmospheric pressur~ to about 750 psig. The amount of catalyst used in the alkylation process depends upon a wids variety of disparate variables.
30 Never~heless, we have found that ths Weight Hourly Space Veloc~y ("WHSV~
= wcight of olefin feed/hour . weight of catalyst) may effective~ be between 0.1 and 120, especially between 0.5 and 30. The overall molar ratio of WO 93/1006S 2 i 1 ~ 1 ~ 4 PCI`/US92/10095 : .
isoparamn to olefin is between about 1.0 and 50Ø Preferred ranges include 2.0 and 25.0; the more preferred include 3.0 and 12Ø
The feedstreams introduced into the catalyst desirably comprise isoparaffins having from four to ten carbon atoms and, most preferably, four 5 to six carbon atoms. Isobutane is most preferred because of its ability to make high octane alkylate. The olefins desirably contain from three to five `
carbon atoms, i.e., propylene, cis- and trans-butene-2, butene-1, and amylenes.
The products of this alkylation process typically contain a complex 10 mixture of highly branchad alkanes. For instance, when using isobutane as the alkane and n-bu~ylene as thc olsfin, a mixture of 2,2,~; 2,2,4-; 2,3,3-; and2,3,4-trimethylpentane tTMP) will result often with minor amounts of other isomeric or polymeric products.
The process involved may utilke the catalyst in a fixed bed using single 15 or multiple feeds. That is to say, the feedstocks may be independently introduced at one or more points throughout the bed or between multiple beds. Desirably, the catalyst is contacted with the feedstocl(s in one or more of continuously stirred r~actors, preferably with feed to each reactor.
Re~eneration Step As w~ have discussed abovs, the regeneration step involves the steps of separating the solid cat~lytic material from the product of the hydrocarbon conversion process by us~ of a liquid-solid separation t~chnique and followed by tha st8p of contacting the catalytic material with a solvent capabl~ of regensrating ~he material. The solvent desirably is selectsd from SO2;
oxygenates such as C,-C" alcohols, ketones, and aldehydes; alkylnitriles such as acetonitrile; and phenolics and aromatic ethers such as anisole and phenol. Most pr~ferably, the solvent comprises SO2.
The catalyst may b~ first contacted with an inert gas to strip any excess gaseous Lewis acid and light hydrocarbons ~rom the solid cata~st component. The catalyst may also be treated using a mild heating step (e.g., 50- to 75 C) prior to the solvent contact step to further strip hydrocarbons from the solid. Addnionauy~ the removal of hydrocarbons and excess Lewis WO 93~10065 PCr/US92/10095 9~L4 15 acid may acilitated by contact with an inert gas such as helium, nitrogen, etc. The hydrocarbons and Lewis acid may be recycled as appropriate.
The process involves contacting the soîid addic catalyst with a liquid solution comprising a solvent selected from SO2; oxygenates such as C,-C~
5 alcohols, ketones, and aldehydes; nitriles such as acetonitrile; and phenolics such as anisole and phenol. When the solid acddic catalyst additionally comprises a Lewis acid the process involves contacting the combination catalyst with a liquid solution comprising a solvent selected from SO2 or from -aromatic ethers and phenolics such as anisols and phenol.
Specifically, the regeneration step involves the contacting of the solid ~;
catalyst component with the liquid solvent stream. Clearly, the choice made ~ -for the step of physically contacting the catalyst is dependent in large part upon the specifics of the catalyst component itseH. For instance, .f the ~ `
catalyst is in the form of tablets or extrudates or Pall rings (or the like) and are -~
15 found in a fixed bed, the most appropriate way to contact the catalyst would be to pass the liquid solvent over the catalyst in the catalyst's fixed bed. If,the catalyst is used as a slurry, the catalyst may be transported to a vessel suitable for contacting the alumina component with a liquid stream and then separating the solid from the liquid. rne reactor in such a process would 20 likely be a good choice for such a vessel. We have found it to be desirable that the catalyst be kept out of contact with water and ~nth oxygen.
The amount of solvent used should be sufficient to remove at least a portion of the resction rssidue found on the catalyst component. The residue is ill-defined but often appears to be a moderately long-chained or polymeric 25 materi~ largely alkane in nature but with a minor olefinic character. The residues also often contain polyolefins and aromatic components in small concentrations. We do not consider this regeneration process to b~
appropriate for residue caused as a result of high t~mperature hydrocarbon conversion processes, a~ least those which produce graphitic or 30 carbonaceous residues on the catalyst. Such residues typically havc H/C
ratios less ~an one. Atthough the amount is not believed to be critical, we have found that for most alumina-based alkylation catalysts, an amount of WO 93/10065 2 1~ Pcr/US92/10095 17 :
about 100 gm. of solvent per gm. of catalyst is sufficient to regenerate the catalyst to at least 40 % of the prior activ~y.
The temperature of the contact step is also not critical but for alkylation catalysts, treatment in the range of 0-C to 50-C is appropriate.
When a solvent comprising SO2 is utilized in the corltact step to regenerate catalysts containing Lewis acids, the solvent should be generally dry; preferably it is substantially free of organic and inorganic bases and SO3 and H2SO~. The level of these contarninants may be such that they do not substantially affect the level of catalyst act~ity upon return to the hydrocarbon conversion medium. Hydrocarbonaceous diluents, such as are the products `
of the accompanying hydrocarbon conversion process often make suitable diluents for the solvent used to regenerate the catalyst.
Once the steps outlined above are completed, the solid catalyst component may be again be treated with one or more Lewis acids as specified above and returned to th~ hydrocarbon conversion step. It may be desirable when using SO2 as the solvent and a gaseous Lewis acid to ~`
overpressure the gaseous Lewis acid te.g., at a pressure above the pressure at which the reaction and/or the solvent treatment step is carried out) before returning the catalyst to service; although we do not wish to be bound by this theory, we believe that the overpressure aids in sweeping or displacing the solvent from the catalyst surface.
The inven~ion has been disclosed by direct description. Below may be found examples showing various aspects of the invention. The examples are only examples of the invention and are not to be used to lim~ the scope of the invention in any way.
EXAMPLES
Example 1 This example shows the regeneration of an alumina-based catalyst which had been treated with BF3 and then used wi~h excess BF3 in an WO 93/10065 ~ 2~-9~4 PCI/US92/10095 :~
alkylation reaction. The feedstream to the alkylation step was a synthe-,cally prepared feed simulating the hydroisomerized C" emuent from an MTBE unit (MTBE emuent).
The olsfinic feedstock was prepared containing (by weight) 94% trans-and cis-2-butene, 5% buten~1, and 1% isobutylene. The feedstock was prepared by mixJng the olefinic feedstock with isobutane such that the final molar ratio of isobutane to olefin was 6/1. This was fed to the alkylation reactor at a weight hourly space velocity CVVHSV ~ based on olefin) was 10.7.
The reaction temperature was held to O C. Samples were periodically removed from the reactor for analysis by gas-liquid chromatography.
During each reaction step, the alkylation reaction was run until approximately 85 gm of olefin per gram of catalyst ~I~e., the catalyst ~age~) had been processed. At that point, there was some indication of a loss of ac~vity ~
of the catalyst as evidenced by a decreasing amount of product C8 content ; -and a concomitant increase in the product C12~ content. Additionally, a ,~
decrease in the (R+ M)/2 as calculated from the gas-liquid chromatography data using well-known correlations (Hutson and Logan, ~Estimate Alky ~leld and Ouality~, Hydrocarbon Processing, September, 1975, pp. 107-108) was ~ -noted at about that catalyst age.
The catalyst was then regenerated using the following procedure:
1. 50 cc of isobutane were added to the alkylation reactor primarily to raise the liquid level to assist in washing back into solution any oa~alyst that had accurnulated at the top of the reactor, 2. the liquid product and isobutane were removed from the reactor through a filtering frit using pressurized inert gas, 3. the reactor containing the spent catalyst was purged with inert gas at 15 cc/min for thirty minutes until the cata~st had the consistency of a free-flowing powder, 4. 150 ml. SO2 were added to thc reactor and the contents stirred WO 93~10065 2 1 1 9 1 ~ 4 PCr/U!~92/10095 for 20 minLnes, 5. SO2 was withdrawn from the r~actor using pressurized inert gasand recovered in a collection vessel. The flow of in~rt gas was continued until no liquid was presant in the reactor, 6. steps 4 and 5 were repeated hvice, 7. the system was flushed w~h flowing inert gas fw 15 minu~es at 15 cc/rnin., 8. BF3 was added to the reactor vessel containing the reganeratedcatalyst and pressurked to a total pressure of 60 psig of 8F3.
This pressure was held for 15 minutes. The reactor was then ~ depressurized and purged with inert gas for five minutes, and 9. step 8 was repeated with the exception that follo~nng the depressurization of the BF3, the inert gas was allowed to purge the system for 20 minutes. The system was then ready for the next alkylation cycle.
Following regeneration, the same procedure to initiate the alkylation reac~ion was followed as with a fresh catalyst, with the exception that isobutane was added to the reactor con~aining the catalyst and stirred for 25 approximateiy 30 minu~es prier to addition of the BF3. This was to insure th~t the catalyst was well mixed in~o ~he liquid medium.
~ he described procedures of alkylation followed by regeneration were repeated for a total of nine cycles.
The results of the product analysis from each cycle are summarized in Table 1 30 and Figure 1, indicating initial and final performance as m~asured by gas chrom~tographic analysis of the hydrocarbon effluent. The data clearly show that the full activity of the ca~alyst is restored using the regeneration WO93/10065 21~9~44 PCI/US92/1009S
procedure. 2 0 Following ths final alkylation cycle, the catalyst was again regenerated with SO2 using the noted procedure. Analysis of the recovered catalyst by elemental analysis gave the following results:
Carbon, wPh 0.3 Boron, wP~ 1.9 Fluorine, wt96 11.1 Suifur, wt% (below detection limits) The low carbon and sulfur content of the catalyst show that the SO2 regeneration procedur~ is very efficient~ The S2 does not accumulate on the surface of the catalyst a~ter regeneration. The boron and fluorine contents of the catalyst are very similar to that found on a fresh catalyst. Analysis of 15 the boron-containing species by solid state NMR of boron (Fig. 2) shows a single resonance peak at about -21 ppm, indicating ths presence of a sole active boron species and the absence of any decomposition products arising ~rom the regeneration procedure. Thus, the regeneration procedure is believed to remove contaminating carbon residues while maintaining intact the 20 important species on the catalyst surface.
WO 93/10065 PCl`/US92/10095 21~144 . _ -- -, .
Cycle # C8,wt.% I C,2 ,wt~ Octane, l (R+ M)/2 _ ~ ,, 1 initial 95.3 2.4 _ 97.6 ~
final 92.2 4.9 96.1 _ 2 initial 95~3 2.6 97.6 final 85.8 9.8 94.6 initial 96.8 2.0 _ 75 . _ final 87.4 8.9 _94.9 4 inibal 95.4 2.2 97.7 final 9 6.5 95.7 initial 96.1 1.7 97.8 I ~.~
hnal 92.4 5.0 96.1 6 initial 95.8 2.1 97.8 final 93.5 4.4 96.2 I
7 initial 95.1 2.8 97.7 I _ final 93.4 4.5 96.3 8 initial 94.9 2.9 97.7 `` `
final 93.4 4.3 96.3 I , , 9 initial 94.3 3.1 97.5 :
, _ . . . . , . .. ., . __ ~
ample 2 --lllis example demonstrates the SO2 regeneration step using a commercial MTBE raffinate feedstock which had been hydroisomerized to remove butadiene and to convert a portion of the butene-1 to cis- and trans-2-butene-2. This feedstock has the following composition ~In wt% on a total olefin basis): 4.3% isobutene, 4.9% butene-1, 87.2% cis- and trans-buten~2, 1.996 2-methyl butene-1 and 2-methyl butene-2, and 1.7% pentene-æ
WO 93/10065 ~ 4 4 PCI /US92/ 10095 This olefinic feedstock was blended with isobutane to a final isobutane/olefin ratio of 6. Normal butane was added to produce a level of 18% in the total feed. This feedstock was fed to the catalyst at 0 C at a WHSV (on olefin) of 7.2. Samples were taken periodically and analyzed by 5 ~as chromatography.
The catalyst was run for a total of five cycles with regeneration between cycles using liquid SO2 in the procedure shown in Exampb 1. The C8, C~2~, and (R+ M)/2 values measured at the beginning and at the end of each cycle are shown in Table 2. This example shows that the rsgeneration step using 10 SO2 performs well on an alkylation catalyst which has been used on a commercial feed.
. _ _ ~Cycle # ¦ ¦ C8 ¦ C~z+ ¦ Octane (R+ M)/2 _ , 1 initial 77.0 6.6 _95.3 final 40.4 26.4 85.9 _ . . I
2 ir~itial 79.7 6.8 9!;.6 ~ .
final 37.9 22.3 8~.1 _ _ 3 initial 81.5 6.0 95.5 _ final _ 60.5 15.3 91.5 4 initial 79.7 5.5 95.7 _ _ .
final 67.7 17.2 92.2 _ .
inRial 82.8 4.5 95.8 _ _ _. , ~ . . . , .
~5 It should be elear that one h~ing ordinary skill in this art would envision equivalents to the processes found in th~ claims that follow and that those equivalents would be within the scope and spirit of the claimed invention.
Claims (30)
WE CLAIM AS OUR INVENTION:
1. A method for regenerating an acidic alumina, solid, hydrocarbon conversion catalyst which has been used in the alkylation of isoparaffin with olefins, wherein said hydrocarbon conversion catalyst does not contain a significant Lewis acid component, the method comprising the steps of:
a. separating the acidic alumina, solid, hydrocarbon conversion catalyst from a hydrocarbon conversion reaction medium, b. contacting the acidic alumina, solid, hydrocarbon conversion catalyst with a liquid solution comprising a solvent selected from the group consisting of SO2, C1-C4 alcohols, C1-C4 ketones, C1-C4 aldehydes, acetonitrile, anisole, and phenol, and c. separating the catalyst component from the solvent.
a. separating the acidic alumina, solid, hydrocarbon conversion catalyst from a hydrocarbon conversion reaction medium, b. contacting the acidic alumina, solid, hydrocarbon conversion catalyst with a liquid solution comprising a solvent selected from the group consisting of SO2, C1-C4 alcohols, C1-C4 ketones, C1-C4 aldehydes, acetonitrile, anisole, and phenol, and c. separating the catalyst component from the solvent.
2. The process of claim 1 where the solvent comprises SO2.
3. The process of claim 1 additionally comprising the step of heating the solid catalyst to a temperature of up to about 75°C after the separation step to substantially remove volatile hydrocarbons.
4. A method for regenerating an acidic, solid, hydrocarbon conversion catalyst additionally containing a Lewis acid component comprising the steps of:
a. separating the acidic, solid, hydrocarbon catalyst from a hydrocarbon conversion reaction medium, b. contacting the acidic, solid, hydrocarbon conversion catalyst with a liquid solution comprising a solvent selected from the group consisting of SO2, anisole, and phenol, and c. separating the catalyst component from the solvent.
??????? ?????
a. separating the acidic, solid, hydrocarbon catalyst from a hydrocarbon conversion reaction medium, b. contacting the acidic, solid, hydrocarbon conversion catalyst with a liquid solution comprising a solvent selected from the group consisting of SO2, anisole, and phenol, and c. separating the catalyst component from the solvent.
??????? ?????
5. The process of claim 4 where the catalyst is selected from acidic zeolites, alumina, silica-alumina, silica, aluminum phosphate molecular sieves, silicoaluminophosphate molecular sieves, solid polymeric ion exchange resins, tetravalent metal phosphonates with pendent acid groups, and sulfated metal oxides.
6. The process of claim 5 where the catalyst is selected from zeolites, alumina, silica-alumina, and silica.
7. The process of claim 6 where the catalyst is alumina.
8. The process of claim 5 where the catalyst comprises a strong Lewis acid selected from BF3, BCl3, BBr3, Bl3, SbF5, AlCl3, AlBr3, TiBr4, TiCl4, TiCl3, ZrCl4, PF5, FeCl3, and FeBr3.
9. The process of claim 8 where the strong Lewis acid is selected from SbF5, AlCl3, and BF3.
10. The process of claim 9 where the strong Lewis acid is BF3.
11. The process of claim 5 where the solvent comprises SO2-
12. The process of claim 4 additionally comprising the step of heating the solid catalyst to a temperature of up to about 75°C after the separation step to substantially remove volatile hydrocarbons.
13. A method for regenerating an alkylation catalyst component which component comprises a major amount of a transition alumina which has been contacted with a strong Lewis acid to produce an alkylation catalyst component containing between 0.5% and 30% by weight of Lewis acid and has been partially deactivated by use in an alkylation reaction medium, comprising the steps of:
PCT/US92/?0095 a. separating the alkylation catalyst from the alkylation reaction medium, b. contacting the alkylation alumina catalyst component with a solvent comprising SO2, and c. separating the alkylation alumina catalyst component from the SO2 solvent.
PCT/US92/?0095 a. separating the alkylation catalyst from the alkylation reaction medium, b. contacting the alkylation alumina catalyst component with a solvent comprising SO2, and c. separating the alkylation alumina catalyst component from the SO2 solvent.
14. The process of claim 13 where the transition alumina is selected from gamma-alumina, eta-alumina, theta-alumina, chi-alumina, kappa-alumina, lambda-alumina, rho-alumina, and mixtures.
15. The process of claim 14 where the transition alumina is selected from gamma-alumina, eta-alumina, and mixtures.
16. The process of claim 13 where the strong Lewis acid is selected from BF3, BCl3, BBr3, Bl3, SbF5, AlCl3, AlBr3, TiBr4, TiCl4, TiCl3, ZrCl4, PF5, FeCl3, and FeBr3.
17. The process of claim 16 where the strong Lewis acid is selected from SbF5, AlCl3, and BF3.
18. The process of claim 17 where the strong Lewis acid is BF3.
19. The process of claim 16 additionally comprising the step of heating the alkylation catalyst component to a temperature of up to about 75°C after the separation step to substantially remove volatile hydrocarbons.
20. An alkylation process comprising the steps of:
a. contacting a mixture comprising isoparaffins and n-olefins with an acidic alkylation catalyst system comprising a catalyst system comprising i.) a solid catalyst component of a transition alumina or zeolite which has been previously 2?
contacted with a Lewis acid, and ii.) free Lewis acid, under alkylation conditions to produce an alkylate stream, b. separating the alkylate stream from the solid alkylation catalyst system, c. contacting the solid alkylation catalyst with a solvent comprising SO2, d. separating the solid alkylation catalyst component from the SO2 solvent, and e. recycling the solid alkylation catalyst component to the alkylation step.
a. contacting a mixture comprising isoparaffins and n-olefins with an acidic alkylation catalyst system comprising a catalyst system comprising i.) a solid catalyst component of a transition alumina or zeolite which has been previously 2?
contacted with a Lewis acid, and ii.) free Lewis acid, under alkylation conditions to produce an alkylate stream, b. separating the alkylate stream from the solid alkylation catalyst system, c. contacting the solid alkylation catalyst with a solvent comprising SO2, d. separating the solid alkylation catalyst component from the SO2 solvent, and e. recycling the solid alkylation catalyst component to the alkylation step.
21. The process of claim 20 where the transition alumina is selected from gamma alumina, eta-alumina, theta-alumina, chi-alumina, kappa-alumina, lambda-alumina, rho-alumina, and mixtures.
22. The process of claim 21 where the transition alumina is gamma-alumina, eta-alumina, or mixtures.
23. The process of claim 20 where the strong Lewis acid is selected from BF3, BCl3, BBr3, Bl3, SbF5, AlCl3, AlBr3, TiBr4, TiCl4, TiCl3, ZrCl4, PF5, FeCl3, and FeBr3.
24. The process of claim 23 where the strong Lewis acid is selected from SbF5, AlCl3, and BF3.
25. The process of claim 24 where the strong Lewis acid is BF3.
26. The process of claim 25 where the BF3 is contacted with the solid alkylation catalyst at a pressure above the pressure of the reaction before the catalyst is recycled.
27. The process of claim 20 additionally comprising the step of heating the solid alkylation catalyst component to a temperature of up to about 75°C after the separation step to substantially remove volatile hydrocarbons
28. The process of claim 20 where alkylation conditions include a temperature in the range of -30°C to 50°C.
29. The process of claim 20 where the mixture comprises 2-butene and isoparaffin.
30. The process of claim 20 including the step of mixing the alkylate stream with other hydrocarbons to produce a gasoline blending component or gasoline.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/796,940 US5326923A (en) | 1990-09-26 | 1991-11-22 | Method for regenerating certain acidic hydrocarbon conversion catalysts by solvent extraction |
| US07/796,940 | 1991-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2119144A1 true CA2119144A1 (en) | 1993-05-27 |
Family
ID=25169451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002119144A Abandoned CA2119144A1 (en) | 1991-11-22 | 1992-11-23 | Method of regenerating certain acidic hydrocarbon conversion catalysts by solvent extraction |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5326923A (en) |
| EP (1) | EP0625133A4 (en) |
| JP (1) | JPH07502928A (en) |
| CN (1) | CN1076386A (en) |
| AU (1) | AU3222493A (en) |
| BR (1) | BR9206790A (en) |
| CA (1) | CA2119144A1 (en) |
| CZ (1) | CZ114594A3 (en) |
| FI (1) | FI941792A (en) |
| MX (1) | MX9206669A (en) |
| NO (1) | NO941751D0 (en) |
| WO (1) | WO1993010065A1 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2719504B1 (en) * | 1994-05-04 | 1996-06-21 | Inst Francais Du Petrole | C4-C5 isoparaffin alkylation catalyst with at least one C2-C6 olefin. |
| FR2719579B1 (en) * | 1994-05-05 | 1996-06-21 | Inst Francais Du Petrole | Paraffin alkylation process. |
| US6015485A (en) * | 1994-05-13 | 2000-01-18 | Cytec Technology Corporation | High activity catalysts having a bimodal mesopore structure |
| US6133386A (en) | 1997-01-08 | 2000-10-17 | Hercules Incorporated | Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins |
| US6316379B1 (en) * | 1998-06-15 | 2001-11-13 | Concordia University | ZSM-5 zeolite materials doped with fluorine species for the synthesis of MTBE and other acido-catalyzed reactions |
| US7132582B2 (en) * | 2003-05-30 | 2006-11-07 | Council Of Scientific And Industrial Research | Catalytic process for the preparation of isolongifolene |
| DE19859262A1 (en) * | 1998-12-22 | 2000-07-06 | Krupp Uhde Gmbh | Process for the evaporation of 1,2-dichloroethane (EDC) |
| CN1100028C (en) * | 1999-07-22 | 2003-01-29 | 中国石油化工集团公司 | Isoalkane and alkylation method of olefine |
| US6448197B1 (en) * | 2000-07-13 | 2002-09-10 | Exxonmobil Chemical Patents Inc. | Method for making a metal containing small pore molecular sieve catalyst |
| US6498120B1 (en) * | 2000-04-26 | 2002-12-24 | Exxonmobil Chemical Patents Inc. | Rejuvenating SAPO molecular sieve with anhydrous liquid or vapor |
| US6579821B1 (en) * | 2000-06-14 | 2003-06-17 | Bechtel Bwxt Idaho, Llc | Method for reactivating solid catalysts used in alkylation reactions |
| US7407905B2 (en) * | 2000-06-14 | 2008-08-05 | Battelle Energy Alliance, Llc | Method for reactivating catalysts and a method for recycling supercritical fluids used to reactivate the catalysts |
| ITMI20011143A1 (en) | 2001-05-30 | 2002-11-30 | Enitecnologie Spa | PROCESS FOR THE PREPARATION OF BISPHENOLS WITH ZEOLITES |
| US7199068B2 (en) * | 2002-03-05 | 2007-04-03 | Sasol North America Inc. | Reactive distillation alkylation process including in situ catalyst regeneration |
| ITMI20022521A1 (en) * | 2002-11-28 | 2004-05-29 | Enitecnologie Spa | PROCESS FOR THE PREPARATION OF BISPHENOLS. |
| US7036587B2 (en) * | 2003-06-27 | 2006-05-02 | Halliburton Energy Services, Inc. | Methods of diverting treating fluids in subterranean zones and degradable diverting materials |
| US6987078B2 (en) * | 2003-10-03 | 2006-01-17 | Fina Technology, Inc. | Alkylation and catalyst regenerative process |
| US7195068B2 (en) * | 2003-12-15 | 2007-03-27 | Halliburton Energy Services, Inc. | Filter cake degradation compositions and methods of use in subterranean operations |
| US20050277542A1 (en) * | 2004-06-14 | 2005-12-15 | Kaminsky Mark P | Catalyst regeneration process |
| US7592282B2 (en) * | 2004-11-11 | 2009-09-22 | Battelle Energy Alliance, Llc | Enhancement of alkylation catalysts for improved supercritical fluid regeneration |
| JP4769085B2 (en) * | 2006-01-13 | 2011-09-07 | Ｊｘ日鉱日石エネルギー株式会社 | Method for hydrotreating wax |
| MY154431A (en) * | 2008-06-02 | 2015-06-15 | Exxonmobil Upstream Res Co | Monetizing remote gas using high energy materials |
| US20100197977A1 (en) * | 2009-02-05 | 2010-08-05 | Harris Stephen H | Allyl diacetate decomposition |
| US8309758B2 (en) * | 2009-12-17 | 2012-11-13 | Lyondell Chemical Technology, L.P. | Allyl acetate purification |
| US20140243563A1 (en) * | 2011-09-01 | 2014-08-28 | Guradoor, S.L. | Method for the alkylation of residual hydrocarbons obtained from pyrolytic processes |
| EP3585822A4 (en) | 2017-02-21 | 2021-03-03 | NTP Tec, LLC | Processes for making polyisobutylene compositions |
| MX2017010801A (en) | 2017-08-23 | 2019-03-07 | Mexicano Inst Petrol | Non-destructive method for removing metals, metal ions and metal oxides from alumina-based materials. |
| BR112020026773A2 (en) | 2018-06-29 | 2021-04-06 | Ntp Tec, Llc | PROCESSES FOR THE MANUFACTURE OF ISOBUTYLENE, POLY-ISOBUTYLENE AND THEIR DERIVATIVES |
| CN113019472A (en) * | 2019-12-24 | 2021-06-25 | 中国石油天然气股份有限公司 | Regeneration method and application of deactivated transalkylation catalyst |
| CN112387314A (en) * | 2020-10-23 | 2021-02-23 | 茂名实华东油化工有限公司 | Regeneration method of catalyst for preparing isobutene through skeletal isomerization of inactivated n-butene |
Family Cites Families (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2284156A (en) * | 1938-01-28 | 1942-05-26 | Resinous Prod & Chemical Co | Esters of terpene phenols |
| US2406869A (en) * | 1942-08-18 | 1946-09-03 | Phillips Petroleum Co | Catalyst preparation |
| US2405565A (en) * | 1943-04-23 | 1946-08-13 | Anglo Iranian Oil Co Ltd | Synthesis of hydrocarbons |
| USRE24568E (en) * | 1955-02-28 | 1958-11-18 | Manufacture of solid catalysts | |
| US2824150A (en) * | 1956-04-30 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824151A (en) * | 1956-04-30 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824152A (en) * | 1956-05-07 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824154A (en) * | 1956-05-22 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824156A (en) * | 1956-05-22 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824155A (en) * | 1956-05-22 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824153A (en) * | 1956-05-22 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824157A (en) * | 1956-05-29 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824161A (en) * | 1956-06-13 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824159A (en) * | 1956-06-13 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824158A (en) * | 1956-06-13 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824160A (en) * | 1956-06-13 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824162A (en) * | 1956-07-06 | 1958-02-18 | American Oil Co | Alkylation process |
| US2824146A (en) * | 1956-07-16 | 1958-02-18 | American Oil Co | Alkylation process using metal pyrophosphate hydrate-bf3 catalyst |
| US2804491A (en) * | 1956-09-14 | 1957-08-27 | American Oil Co | Ethylation process |
| US2972649A (en) * | 1958-01-31 | 1961-02-21 | Sinclair Refining Co | Process for alkylating paraffinic hydrocarbons |
| US2939890A (en) * | 1958-03-18 | 1960-06-07 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
| US2971037A (en) * | 1958-12-01 | 1961-02-07 | Exxon Research Engineering Co | Gamma alumina promoted paraffin alkylation process |
| US2976338A (en) * | 1958-12-08 | 1961-03-21 | Exxon Research Engineering Co | Process and catalyst for polymerization |
| US2945907A (en) * | 1958-12-12 | 1960-07-19 | American Oil Co | Olefin conversion process |
| US3068301A (en) * | 1959-10-15 | 1962-12-11 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
| US3054835A (en) * | 1959-10-15 | 1962-09-18 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
| US3054836A (en) * | 1959-12-21 | 1962-09-18 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
| US3114785A (en) * | 1960-07-21 | 1963-12-17 | Universal Oil Prod Co | Process for shifting the double bond in an olefinic hydrocarbon |
| US3220958A (en) * | 1960-09-12 | 1965-11-30 | Universal Oil Prod Co | Conversion catalyst preparation |
| US3217063A (en) * | 1962-12-04 | 1965-11-09 | Universal Oil Prod Co | Process for shifting the double bond in an olefinic hydrocarbon |
| US3217062A (en) * | 1962-12-04 | 1965-11-09 | Universal Oil Prod Co | Process for shifting the double bond in an olefinic hydrocarbon |
| FR1346135A (en) * | 1963-01-31 | 1963-12-13 | Universal Oil Prod Co | Polymerization process of olefinic hydrocarbons |
| US3433747A (en) * | 1966-11-04 | 1969-03-18 | Grace W R & Co | Method of preparing petroleum cracking catalysts |
| US3647916A (en) * | 1969-10-08 | 1972-03-07 | Mobil Oil Corp | Isoparaffin-olefin alkylation with crystalline zeolite catalysts at low isoparaffin to olefin ratios |
| US3833679A (en) * | 1972-07-20 | 1974-09-03 | Phillips Petroleum Co | Paraffin isomerization utilizing hf to change the selectivity of hsbf6 catalyst |
| US3893942A (en) * | 1973-09-27 | 1975-07-08 | Union Carbide Corp | Isoparaffin alkylation process with periodic catalyst regeneration |
| US3855343A (en) * | 1973-11-29 | 1974-12-17 | Mobil Oil Corp | Isoparaffin-olefin alkylation with regeneration of resin/boron trifluoride catalyst |
| SU614079A1 (en) * | 1974-02-19 | 1978-07-05 | Предприятие П/Я В-8376 | Method of obtaining isoparaffin hydrocarbons |
| US4058575A (en) * | 1975-06-12 | 1977-11-15 | Exxon Research & Engineering Co. | Catalyst pretreatment with hydrocarbon feedstock |
| US4028430A (en) * | 1975-06-16 | 1977-06-07 | Universal Oil Products Company | Simulated moving bed reaction process |
| US4066716A (en) * | 1975-08-14 | 1978-01-03 | Texaco Inc. | Alkylation process of alkanes with olefins utilizing chlorided alumina catalyst |
| US4243550A (en) * | 1976-06-14 | 1981-01-06 | Atlantic Richfield Company | Catalyst demetallization with a reductive SO2 wash |
| US4308414A (en) * | 1979-12-17 | 1981-12-29 | Gulf Research & Development Company | Oligomerizing alpha-olefins with a heterogeneous catalyst |
| FR2504121A1 (en) * | 1981-04-15 | 1982-10-22 | Raffinage Cie Francaise | Light olefin oligomerisation - using boron tri:fluoride catalyst on alumina support |
| US4407731A (en) * | 1982-11-08 | 1983-10-04 | Uop Inc. | Preparation of metal oxide-supported boron fluoride catalysts |
| US4751341A (en) * | 1983-08-15 | 1988-06-14 | Mobil Oil Corporation | Oligomerization of olefins with BF3 treated zeolite |
| US4427791A (en) * | 1983-08-15 | 1984-01-24 | Mobil Oil Corporation | Activation of inorganic oxides |
| US4550090A (en) * | 1983-08-26 | 1985-10-29 | Mobil Oil Corporation | Regeneration of ZSM-5 type catalyst with a source of alkali or alkaline earth metal cations or ammonia |
| US4914256A (en) * | 1988-06-30 | 1990-04-03 | Mobil Oil Corp. | Reactivation of partially deactivated catalyst employing ultrasonic energy |
| US4992614A (en) * | 1988-06-30 | 1991-02-12 | Mobil Oil Corp. | Reactivation of partially deactivated catalyst employing ultrasonic energy |
| WO1990000534A1 (en) * | 1988-07-15 | 1990-01-25 | Mobil Oil Corporation | Heterogeneous isoparaffin/olefin alkylation process |
| US4992616A (en) * | 1988-07-15 | 1991-02-12 | Mobil Oil Corporation | Heterogeneous isoparaffin/olefin aklylation process |
| EP0424445B1 (en) * | 1988-07-15 | 1995-09-06 | Mobil Oil Corporation | Heterogeneous isoparaffin/olefin alkylation process |
| US4918255A (en) * | 1988-07-15 | 1990-04-17 | Mobil Oil Corp. | Heterogeneous isoparaffin/olefin alkylation with isomerization |
| US4935577A (en) * | 1988-07-15 | 1990-06-19 | Mobil Oil Corp. | Hydrocarbon processes comprised of catalytic distillation using Lewis acid promoted inorganic oxide catalyst systems |
| US5043518A (en) * | 1989-07-31 | 1991-08-27 | Exxon Chemical Patents Inc. | Process for regenerating a catalyst and resultant regenerated catalyst and production of olefins by catalytic ether decomposition using regenerated catalyst |
| US4992615A (en) * | 1990-01-25 | 1991-02-12 | Mobil Oil Corp. | Isoparaffin-olefin alkylation process |
| US4999326A (en) * | 1990-06-18 | 1991-03-12 | Amoco Corporation | Palladium catalyst reactivation |
-
1991
- 1991-11-22 US US07/796,940 patent/US5326923A/en not_active Expired - Fee Related
-
1992
- 1992-11-19 MX MX9206669A patent/MX9206669A/en unknown
- 1992-11-21 CN CN92114842A patent/CN1076386A/en active Pending
- 1992-11-23 CA CA002119144A patent/CA2119144A1/en not_active Abandoned
- 1992-11-23 EP EP93900631A patent/EP0625133A4/en not_active Ceased
- 1992-11-23 CZ CZ941145A patent/CZ114594A3/en unknown
- 1992-11-23 JP JP5509557A patent/JPH07502928A/en active Pending
- 1992-11-23 BR BR9206790A patent/BR9206790A/en not_active Application Discontinuation
- 1992-11-23 WO PCT/US1992/010095 patent/WO1993010065A1/en not_active Application Discontinuation
- 1992-11-23 AU AU32224/93A patent/AU3222493A/en not_active Abandoned
-
1994
- 1994-04-18 FI FI941792A patent/FI941792A/en not_active Application Discontinuation
- 1994-05-10 NO NO941751A patent/NO941751D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0625133A4 (en) | 1995-04-05 |
| FI941792A0 (en) | 1994-04-18 |
| EP0625133A1 (en) | 1994-11-23 |
| WO1993010065A1 (en) | 1993-05-27 |
| NO941751L (en) | 1994-05-10 |
| US5326923A (en) | 1994-07-05 |
| CZ114594A3 (en) | 1994-12-15 |
| NO941751D0 (en) | 1994-05-10 |
| BR9206790A (en) | 1995-11-07 |
| MX9206669A (en) | 1993-07-01 |
| AU3222493A (en) | 1993-06-15 |
| FI941792A (en) | 1994-04-18 |
| JPH07502928A (en) | 1995-03-30 |
| CN1076386A (en) | 1993-09-22 |
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