CN1083417A - The renovation process of alkylation catalyst - Google Patents

Abstract

A kind of new technological process is disclosed, it utilizes a kind of reversible alkali to be contact substance, remove at ASO by a part of contamination level that contains in sulfone component and the mixture that hydrogen halide becomes to be grouped into, obtain one handled contain the sulfone mixture, that handled contains the sulfone mixture and can further process by contacting with a kind of sorbing material.

Description

The renovation process of alkylation catalyst

The present invention relates to the renovation process of the catalyst composition that in the conversion process of hydrocarbon, uses.More particularly, the present invention relates to a kind of renovation process that contains the catalyst mixture of a kind of sulphones and a kind of hydrogen halide compound, this mixture is used for alkene by isoparaffin alkylation.

Recent findings, the mixture that contains a kind of sulphones and a kind of hydrogen halide compound are a kind of being used for alkene by isoparaffin alkylation to produce the effective catalyzer of a kind of alkylation reaction product or alkylide.This finds open or/and claim in several patent applications.For example, the application 07/877338 that proposed on May 1st, 1992 of people such as the application 07/877,336 that proposed on May 1st, 1992 of people such as Abbott and Randolph and Abbott.Alkylation reaction product contains the hydrocarbon with 7 or 7 above carbon atoms usually.Because its octane value height, as automobile fuel, it is an ideal gasoline mixing element.

Yet, when the explained hereafter that utilization contains the catalyst composition of sulfone component and hydrogen halide component goes out utmost point fine alkylation products, this technology also side reaction can occur, promptly generates some polyreaction byproduct, for example those persons that are referred to as the acid soluble oil or claim ASO.These polymeric byproducts of reaction are called acid soluble oil, be because they are dissolved in the catalyzer that uses in the alkylation process, and when hydrocarbon mixture contacts the alkylation products that produces and alkylation catalyst and separates with alkylation catalyst, they still be retained in catalyzer mutually in.Be beneficial to mutually in the alkylation process that reaction zone is reused isolating catalyzer continuously from alkylation products, ASO can accumulate in catalyzer.If do not remove ASO, above behind the certain hour, its concentration will rise to unacceptable level.In the alkylation catalyst that contains sulfone component and hydrogen halide component, the ASO that contains lower concentration it is believed that and helps alkylation process and products thereof.But in the alkylation catalyst, the ASO of higher concentration can produce adverse influence to catalyst activity and last alkylation finished product.In the alkylation catalyst, the concentration of ASO has surpassed a certain acceptable boundary, will cause the reduction of octane value in the alkylation finished product.Because alkylation octane content reduces gradually with the progressively raising of ASO concentration.

Conventional alkylation process uses hydrogen fluoride (HF) as catalyzer.Compare with the raw catalyst of hydrogen halide component with the aforementioned sulfone component that contains, have some known methods to be used in the successive alkylation process and in the HF catalyzer, get rid of ASO.Specifically, be used for the HF catalyzer of alkylation process, enough ratios arranged through handling or regeneration; Therefore can with alkylation catalyst in the proximate speed of ASO cumulative speed remove an amount of ASO.This can be by finishing a part of HF catalyzer through the stripping container.By steam state hydrocarbon (as Trimethylmethane) HF and ASO branch are opened, HF flows out from the stripping container as the part of overhead streams, and ASO then flows out to treat further processing as tower bottom flow.

Though conventional alkylation catalyst regeneration techniques can be finished the regeneration of conventional HF catalyzer satisfactorily, ordinary method can not be used to regenerate and contain the alkylation catalyst mixture of sulfone component.This is because the boiling point of the boiling range of ASO and some sulfone compound (for example tetramethylene sulfone) overlaps.So the simple distillation technique that uses when separating HF and ASO just can not be regenerated effectively and be contained the alkylation catalyst of sulfone.In addition, reuse with catalyzer, also sulfone and ASO branch must be opened as alkylation in order to reclaim sulfone.

Therefore, an object of the present invention is to provide a kind of novel method of the alkylation catalyst of regenerating.

Another object of the present invention provides a kind of method that ASO is removed from the alkylation catalyst that contains the sulfone component.

Thereby method of the present invention relates to utilizes a kind of catalyst mixture that contains the sulfone component to make alkene pass through alkylation of paraffines.The sulfone mixture that contains that contains sulfone and ASO contacts with a kind of reversible alkali under appropriate condition, removes a part of ASO component at least from contain the sulfone mixture, and produce one handled contain the sulfone mixture.

In the accompanying drawing:

Figure one is the schematic diagram of the embodiment of the inventive method.

Figure two is one and is illustrated in and contains in the sulfone mixture, and charcoal absorption is the curve of the funtcional relationship of the ability of ASO and contained HF weight percent wherein.

Other purpose of the present invention and advantage will be very clear from following detailed description and claims.

Acid soluble oil of the present invention, in alkylation process, produce as byproduct of reaction, this processing step comprise the hydrocarbon mixture that will contain alkene and isoparaffin with a kind of contain, form be or composition is that the alkylation catalyst of hydrogen halides component and sulfone component contacts substantially. Employed " acid soluble oil " or " ASO " this term refer in the present specification and claims Be the polymer of those mixing, they are the height olefinic oils that is produced by acid catalyzed hydrocarbon reaction. " molecular structure of the mixed polymer " literary composition that is entitled as that Miron and Lee deliver has been made widely explanation and performance specification to the mixed polymer oil of some type, this article is stated from the 8th volume first phase of Joarnal of Chemical and Engineering Data, 150-160 page or leaf. This article is incorporated herein by reference. The physical property of ASO depends on handled concrete hydrocarbon feed. The catalyst that uses in the alkylation process, the pollutant in the raw material (for example hydrogen sulfide, butadiene, oxide and other compound), and alkylation reaction condition. Therefore, when more narrow sense ground defined this term, ASO referred to the mixed polymer that those generate as accessory substance in the catalytic reaction of monoolefine and isoparaffin. This reaction adopts to contain, form to be or to form to be the catalyst mixture catalysis of sulfone component and hydrogen halides component substantially. For well, isoparaffin is to have 4 to 6 carbon atom persons for well with those monoolefines with 3 to 5 carbon atoms for the monoolefine that is used for catalytic reaction; The sulfone component with tetramethylene sulfone for well; Hydrogen halides with hydrogen fluoride for well.

The ASO accessory substance that generates through the hydrocarbon reaction that contains the catalysis of sulfone alkylation catalyst also has following properties usually: the water with 60 °F is made benchmark, and specific gravity range is about 0.8～1.0; Average molecular weight range is about 250-350; The bromine number scope is about 40-350.

Hydrogen halide composition in catalyst composition or the catalyst mixture can be selected from hydrogen fluoride (HF), hydrogenchloride (HCl), and hydrogen bromide (HBr) reaches by two in them or two mixtures that above composition is formed.Yet the halocarbon composition of preferentially selecting for use is a hydrogen fluoride, and it can be used for catalyst composition with anhydrous form, but in general, the hydrogen fluoride composition that uses in the technology can contain less water.In the catalyst composition that contains hydrogen fluoride and tetramethylene sulfone, the content of water in no instance must be greater than about 30% of the hydrogen fluoride component gross weight that comprises water.The content of water is lower than the about 10% better of gross weight in the hydrogen fluoride, preferably is lower than 7%.Hydrogen halide composition in the mentioned catalyst composition of the present invention, or when more specifically referring to the hydrogen fluoride composition, these terms can be understood as, and the hydrogen halide composition both can refer to anhydrous mixture, also can refer to non-anhydrous mixture.Here aqueous weight percentage in the hydrogen halide composition of mentioning, the weight that is meant water multiply by 100 with the ratio of water and hydrogen halide gross weight, so that ratio is converted into percentage ratio.

The sulfone that the present invention is suitable for, its general formula is

R-SO ₂-R′

Here, R and R ' are monovalence hydrocarbon alkyl or aryl substituting groups, all contain 1-8 carbon atom.The substituent example of this class comprises: dimethyl sulfone, two positive third sulfones, sulfobenzide, methylethyl sulfone and its SO ₂Group becomes the alicyclic sulfone of key with the hydrocarbon ring, in such cases, R and R ' form one jointly and preferably contain the branching of 3-12 carbon atom or the bivalent hydrocarbon radical of non-branching.Under latter event, tetramethylene sulfone or tetramethylene sulfone, 3-methyl tetramethylene sulfone and 2,4-dimethyl tetrahydro thiophene sulfone is especially suitable, because they are liquid under the related processing condition of this paper, this is very helpful.These sulfones also can have substituting group, especially one or more halogen atom substituting groups, for example chloromethyl ethyl sulfone.These sulfones can use easily with the form of mixture.

Employed alkylation catalyst in the alkylation process that produces the ASO by product can contain, form to be or to form to be hydrogen halide component described herein and sulfone component basically.The ASO by product preferably results from such alkylation process, and promptly hydrocarbon mixture and one are its sulfone component with tetramethylene sulfone, is the alkylation catalyst contact of its hydrogen halide component with hydrogen fluoride.The weight ratio of hydrogen fluoride in the alkylation catalyst and tetramethylene sulfone in this case, contains tetramethylene sulfone and hydrogen fluoride in the alkylation catalyst, as long as in about 1: 1 to 40: 1 scope, can obtain satisfied alkylation result.Better proportional range is 2.3: 1 to 19: 1, preferably between 3: 1 to 9: 1.

In order to improve the selectivity of alkylated reaction of the present invention, produce our desirable highly branched aliphatic hydrocrbon with 7 or 7 above carbon atoms, need in reaction zone, have to substantially exceed stoichiometric isoparaffin.The isoparaffin that the present invention is contemplated and the molar ratio range of alkene were from about 2: 1 to 25: 1, and this scope is better at about 5: 1 to 20: 1, and the scope of being preferably is 8: 1 to 15: 1.Yet it is emphasized that the above isoparaffin of enumerating is the industrial actually operating scope that has been found that to the molar ratio range of alkene, but in general, in alkylated reaction, this ratio is big more, the alkylation products quality is good more.

The temperature range of its alkylated reaction that the present invention is contemplated is between 0 °F-Yue 150 °F.Lower temperature helps the alkylated reaction of isoparaffin and alkene, and is unfavorable for paying reaction with the alkene of its competition, for example polyreaction.Yet total reaction rate will reduce with the reduction of temperature.Temperature preferably sets the temperature range between about 30-Yue 130 giving scope, for alkene and isoparaffin provide good selectivity with the speed of reaction alkylation with commercial appeal.But optimum alkylation temperature should be between 50 °F-120 °F.

The scope of the reaction pressure that the present invention is contemplated is retained in pressure the liquid phase to about 15 normal atmosphere from being enough to make reactant.Under the alkylated reaction temperature, the hydrocarbon reaction thing can be gas usually, therefore, reaction pressure in 40 pounds of gauge pressures (psig) per square inch to about 160psig for well.When all reactants were in liquid state, pressurize had no significant effect alkylated reaction.

Under the situation of using the said alkylation catalyst of the present invention, the duration of contact of hydrocarbon reaction thing in alkylation reaction zone, generally should be enough to make this alkylation zone olefin reactant to transform fully basically.Duration of contact scope at about 0.05 minute to about 60 minutes for well.In alkylation process of the present invention, use about 2: 1 to the molar ratio range of about 25: 1 isoparaffin to alkene, in this scope, alkylation reaction mixture contains the 40-90%(volume of having an appointment) catalyzer mutually and account for about 60-10%(volume) hydrocarbon phase, like this, alkene and isoparaffin can keep excellent contact at reaction zone, and space velocity scope that can the about 0.1-200 volume of per hour every volume of catalyst (v/v/hr) alkene reaches alkene and transforms completely basically.Best space velocity will depend on the type of used isoparaffin and olefin reactant.The concrete composition and the alkylation reaction condition of the agent of contracting of alkylation.Therefore, should be enough to provide about 0.1-200(v/v/hr preferred duration of contact) space velocity of the alkene of scope, and the olefin reactant of alkylation reaction zone can be transformed basically fully.

Alkylation process both can be a batch operation, also can be the continous way operation, but consider from economic aspect, preferably selected the operate continuously mode for use.Verified, in alkylation process, the contact between raw material and the catalyzer is tight more, and the alkylation products quality that obtains is just good more.Consider these, when batch operation, this technology is characterised in that to have adopted carries out the violent mechanical stirring or the method for concussion to reactant and catalyzer.

In the operate continuously mode, reactant can remain under enough temperature and pressures so that they are in liquid state substantially, constantly is pressed into reaction zone by diverting device then.Diverting device can be a jet, nozzle, porous casing or the like.Reactant subsequently with catalyzer by conventional mixing device, mix as mechanical stirrer or eddying flow system.After the enough time, product just can constantly be separated from catalyzer, and discharges from reactive system, and simultaneously, the part used catalyst then is recycled in the reactor.The part catalyzer can be as described herein make it cyclic regeneration like that or reactivate, also available other any suitable treatment process makes it get back to alkylation reactor.

One embodiment of the invention comprise a kind of technology of removing ASO from contain the sulfone mixture, it comprises a kind of sulfone mixture that contains that contains sulfone component and ASO is suitable for getting rid of this contact material that contains at least a portion ASO component in sulfone mixture step that contacts with a kind of, to produce a kind of treated sulfone mixture that contains.Containing the sulfone mixture and also can contain a kind of sulfone component, a kind of hydrogen halide component and ASO in the technology of the present invention.Contact material can be the material that this paper described, and also can comprise material that is selected from aluminum oxide, carbon and their mixture and the preferred reversible alkali that described in detail as this paper.Containing in the sulfone mixture preferred sulfone component is tetramethylene sulfone.

The amount that contains contained ASO component in the sulfone mixture can not be higher than about 20% weight of sulfone component.ASO concentration is lower than the about 15% better of sulfone component, preferably exists to be lower than 10% concentration.When comprising the hydrogen halide composition in containing the sulfone mixture, its concentration will be lower than 10% of mixture weight.This weight percent multiply by 100 resulting percentage by the ratio of the weight sum of the weight of hydrogen halide and hydrogen halide and sulfone and draws.But in general, the concentration range of hydrogen halide in containing the sulfone mixture can be about 0.1-10%(weight).But, this concentration range is better between about 0.1-7.5%, preferably between 0.1-5.0%.

An importance of the present invention (is critical aspects even do not say it) is: contain sulfone mixture and contacting of contact material and cause and removed this at least and contain a part of hydrogen halide component in the sulfone mixture, thereby obtain treated reduced hydrogen halide concentration contain the sulfone mixture.But preferably can have a large amount of hydrogen halide components to separate, thereby make its concentration in this mixture be lower than 1.0%(weight from containing the sulfone mixture of handling), but its concentration is lower than about 0.2%(weight) then better, preferably be lower than about 0.1%.

Treatedly containing that contained ASO concentration also can reduce in the sulfone mixture, generally is to be lower than about 5% of this mixture weight.In containing in the sulfone mixture of having handled, it is 2% relatively good that ASO concentration is lower than, and preferably is lower than 1%.

Another embodiment of the inventive method is to imagine by removing the ASO of the contained at least a portion of mixture, solves the problem relevant with the regeneration that contains the sulfone alkylation catalyst mixture, and this mixture contains sulfone component, hydrogen halide component and ASO.When alkylation process was reused its catalyzer continuously, the accumulation of ASO in containing the sulfone alkylation catalyst just taken place.In the successive alkylation process, ASO reaction by product constantly increases in catalyzer, if will not get rid of, it can rise to unacceptable concentration, thereby catalyst performance is had a negative impact, and finally influences the quality of alkylation products itself.In general, the concentration that keeps containing ASO in the sulfone alkylation catalyst is not higher than 20% of catalyst weight and has just meeted the requirements.Here, the weight percent of ASO is based on the gross weight of the catalyst mixture that do not comprise the ASO component.In containing the sulfone alkylation catalyst, it is about 15% better that the concentration of ASO is lower than, and preferably is lower than 10%.

Help keeping the low concentration that contains ASO in the sulfone catalyst mixture although have some technologies, it is believed that, ASO concentration surpasses 10% of catalyst weight, will have a negative impact to catalyst performance.Therefore, in order to guarantee to contain the catalytic activity of sulfone alkylation catalyst mixture.Have at least a part of catalyzer necessary processed, to remove the ASO of wherein contained at least a portion.For reaching this purpose, need to contain sulfone alkylation catalyst mixture elder generation and a kind of contact material, contact with a kind of sorbing material again, so that from contain the sulfone alkylation catalyst mixture, remove at least a portion (preferably most of's) ASO component.

Yet, it should be noted that, before making containing the sulfone mixture and contact material contacting of obtaining, generally need from the alkylation catalyst mixture that contains tetramethylene sulfone, remove at least a portion (preferably most of's) hydrogen halide component, thereby remove at least a portion ASO component or remove at least a portion hydrogen halide component, or both all can be removed to small part.Therefore contain the sulfone mixture and will be removed at least a portion (preferably most of) hydrogen halide component contain the sulfone alkylation catalyst mixture.Any suitable method all can be used to separating hydrogen halides component from contain the sulfone alkylation catalyst mixture, as flash separation, distillation, extraction, stripping and other separation method that is suitable for.Preferred method is, and to be steam stripping agent with the steam state Trimethylmethane be divided into overhead streams and tower bottom flow two portions by gas stripping process containing the sulfone alkylation catalyst mixture, and overhead streams contains the hydrogen halide of major portion in the sulfone alkylation catalyst, and tower bottom flow is then for containing the sulfone mixture.

Usually, contain hydrogen halide component concentrations in the sulfone mixture and be lower than the about 10% of mixture weight, this weight percent multiply by 100 percentages that produce by the ratio of the weight sum of the weight of hydrogen halide and hydrogen halide and sulfone recently to be determined.But owing to be difficult to remove whole hydrogen halide from mixture, from commercial practical viewpoint, the lower bound of hydrogen halide concentration can approach about 0.1(weight), but be lower than 0.1% better.Therefore, the concentration range that contains hydrogen halide in the sulfone mixture is approximately 0.1%-10%(weight).But concentration range is about 0.1%-7.5%(weight) better, be preferably between the 0.1%-5.0%.

As previously mentioned, the sulfone mixture of handling that contains can being suitable for removing under the condition of contained at least a portion ASO, further contact with a kind of sorbent material second contact procedure, this sorbent material is chosen in aluminum oxide and their mixture preferably from carbon.Yet that had handled contains the sulfone mixture, preferably removes its contained most ASO by contacting with sorbent material, thus obtain ASO content very little contain the sulfone mixture, ASO concentration can be lower than 2% of this mixture weight usually.ASO concentration is lower than 1%(weight) better, preferably be lower than 0.1%.

In general, the contact material of the contemplated use of the present invention and sorbing material all can place in the container that defines the zone of action, contain the sulfone fluid and both can also can contact with sorbing material with contact material in this district.But the present invention does not limit and uses the standard container define the zone of action, can use in the technology any known suitable method to make to contain sulfone liquid to contact with contact material or sorbing material.

Be used for from the sorbing material of handling that the sulfone mixture is removed ASO that contains, can be any can be suitably or remove the sorbing material of at least a portion ASO composition that contains in this mixture effectively.This sorbing material preferably is selected from aluminum oxide, carbon and their mixture.

Carbon adsorbing material can be that any being suitable for resembles the contemplated use of the present invention and be suitable for the gac that contains at least a portion ASO composition that comprises in the sulfone mixture that selective clearing was being handled.These charcoal absorption materials are characterised in that: very big specific surface area is arranged, its scope is that about 300 meters squared per gram are to 2500 meters squared per gram, this is the standard method of test D3663-84 with American Society for testing and materials (ASTM), and promptly " standard method of test of catalyst surface area " by name measured.This paper is for reference at this standard method of test D3663-84 that quotes ASTM.The further feature of charcoal absorption material is that also its pore diameter range is from about 10 microns to 50 microns.This also is to use ASTM standard method of test D4284-88, and the method for " mercury is invaded porosimeter and measured the standard method of test that catalyst pore volume distributes " promptly by name described mercury intrusion porosimeter is measured.The standard method of test D4284-88 of ASTM is incorporated herein for reference.In general, use commercially available gac to meet the requirements.For example the product by the commodity of Calgon Carbon company production and selling Calgon Filtrasorb 400 by name is exactly a kind of suitable gac.

The alumina adsorption material, can be the contemplated use of any the present invention of being suitable for and be suitable for selectivity remove partially disposed at least contain the contained ASO component of sulfone mixture, or be suitable for use as a kind of aluminum oxide that contains the neutralizing agent of at least a portion hydrogen halide component in the sulfone fluid of removing.For example, this suitable aluminum oxide comprises various commercially available activated alumina and calcination aluminum oxide.The surface area of alumina material is generally 150 meters squared per gram to 500 meters squared per gram, and this measures by ASTM D3663-84 method.The pore diameter range of alumina material is measured by the method for ASTM D4284-88 between the 25-125 micron equally.Using commercial alumina, generally is satisfactory.A kind of suitable commercial alumina that for example Alcoa company produces and the product of the commodity HF-200 by name of sale comes to this.Be used for the present invention most preferably aluminum oxide be exercise aluminum oxide (also claiming gama-alumina) with gamma (γ) crystalline structure, and other aluminum oxide is as the x-aluminum oxide of surface-area greater than about 50 meters squared per gram.

Any processing condition of handling that the sulfone mixture contacts with adsorbent composition that contain that make, if it for remove handled to contain in the sulfone mixture at least a portion ASO suitable or effective, all practicable.Generally do not think that the elimination efficiency of sorbing material depends on contact pressure to a great extent, because adsorption phenomena is regarded the liquid-solid results of interaction as.Yet operation pressure should surpass about 0.5 normal atmosphere (absolute pressure), and can rise to about 30 normal atmosphere (absolute pressure) or higher.Working pressure commonly used generally is pressed onto about 200psig from atmosphere.

As for the contact temperature, can use any suitable temperature condition to remove at least a portion ASO in the sulfone mixture that contains that handled effectively.In general, the bound of temperature is by the physical property decision of contained ASO in the physical property of processed mixture and this mixture.With regard to the lower limit of temperature, the fusing point of pure tetramethylene sulfone is 81.3-82.0 °F, but when tetramethylene sulfone and water and hydrogen fluoride formation mixture, fusing point has just significantly reduced.Therefore, the lower bound of contact temperature is about 0 °F.As for upper temperature limit, it begins this class factor of pyrolysated temperature by the sulfone component in first boil temperature and the mixture of ASO and is determined.Like this, the contact upper temperature limit just is about 400 °F.Therefore, the contact temperature range is generally between 0 °F to about 400 °F.This scope be 50-350 °F better, preferably between 60-325 °F.

After measured, in containing of will handling, the sulfone mixture contacted with the method for removing ASO wherein with sorbing material, the hydrogen halide of lower concentration (especially hydrogen fluoride) is present in the mixture even have very, also can reduce the charcoal absorption material is optionally removed ASO from mixture ability.Illustrated as the data among Fig. 2.In containing in the sulfone fluid of contacting with activated carbon material, the consequence that the hydrogen fluoride of lower concentration also can cause the effect that makes charcoal absorption ASO to lose efficacy substantially.Therefore, of the present invention one important and be actually very crucial aspect and be, make the sulfone mixture that contains that is polluted by ASO go up substantially and do not contain hydrogen halide, perhaps more generally, contained the sulfone mixture with before activated carbon material contacts or be neutralized in the contact by what ASO polluted.Any suitable method as long as it can remove at least a portion (preferably most of) hydrogen halide from containing of being polluted by ASO sulfone mixture or the composition, can adopt.Alternative other method is, can use any suitable neutralizing agent, contains at least a portion hydrogen halide contained in the sulfone mixture as long as it can be removed by what ASO polluted.The example of the neutralizing agent that these are suitable includes, but is not limited to: alkaline hydrated oxide, and as the oxyhydroxide of those basic metal and alkaline-earth metal, as potassium hydroxide, calcium hydroxide and sodium hydroxide; Basic oxide are as zinc oxide and stannic oxide; Intermediate oxide is as aluminum oxide; With reversible alkali.Preferred neutralizing agent can comprise all kinds of aluminum oxide, oxyhydroxide and reversible alkali, best in and material then be gama-alumina or reversible alkali.

Term used herein " reversible alkali " is meant a kind of aromatic compound, one or more nitrogen-atoms are arranged on its aromatic nucleus, perhaps also refer to a kind of polymkeric substance that has the aromatic compound side group, one or more nitrogen-atoms are arranged on this aromatic nucleus, wherein nitrogen-atoms has to a certain degree sterically hindered, so that the salt that is formed by the nitrogen-atoms in the aromatic compound and strong emprotid dissociates into aromatic compound and protonic acid being lower than under the decomposition temperature of aromatic compound.

Preferred reversible alkali is the compound that conforms to one of following general formula:

Or has a unitary superpolymer that conforms to one of following general formula

In the formula:

Each R ¹Represent respectively: C _2-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl or C _3-20Cycloalkyl.Wherein, C _2-20Alkyl, C _6-20Aryl, C _7-20Aralkyl, C _7-20Alkaryl or C _3-20Cycloalkyl both can be unsubstituted, also can be by halogen, and nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces; Each R ²And R ³Represent respectively: C _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C _3-20Cycloalkyl, nitro, cyano group, halogeno-group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy, wherein, C _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl, C _7-20Aralkoxy or C _3-20Cycloalkyl is unsubstituted, also can be by halogeno-group, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces;

Each a is respectively the integer of 0-4;

Each b is respectively the integer of 0-3;

Each c is respectively integer 0 or 1; With

Each d is respectively the integer of 0-2.

The example of preferred reversible alkali comprises: 2,4,6-tri-tert pyridine, 2,6-di-t-butyl-4-picoline, 2,6-di-tert-butyl pyridine, 2-tert .-butylpyridine, 2-benzyl-pyridine, 2,6-phenylbenzene pyridine, 2-phenylpyridine, 2, the 6-dimethoxy-pyridine, 2-phenoxypyridines, 2,6-hexichol oxygen yl pyridines, 2-toluquinoline, 6-toluquinoline, 7,8-benzoquinoline or the like.Better reversible alkali comprises 2,4,6-tri-tert pyridine, 2,6-di-t-butyl-4-picoline, 2,6-di-tert-butyl pyridine, 2-tert .-butylpyridine, 2-benzyl-pyridine, 2,6-phenylbenzene pyridine, 2-phenylpyridine, 2-phenoxypyridines, 2,6-hexichol oxygen yl pyridines and 2,6-dimethoxy-pyridine.

The polyvinylpyridine resin that is very useful in the present invention comprises homopolymer and vinylpyridine compound and 1 of vinylpyridine compound, the multipolymer of 2-alefinically unsaturated compounds.Wherein, the vinylpyridine acridine compound has certain sterically hindered, and 1, the example of 2-alefinically unsaturated compounds has vinylbenzene, Vinylstyrene, ethene, vinylchlorid or the like.In addition, vinylpyridine can with 2 or a plurality of this 1, the polymerization of 2-alefinically unsaturated compounds.This class polymerization technique is well-known technically.Example is seen the United States Patent (USP) 2,623,013 of D ' Aelio; Kirk-O thmer Encyclopedia of Chemical Technology the 3rd edition, the 21st volume, the 816th page and following pages and the 19th volume 475-476 page or leaf, this paper are incorporated in that this is for reference.

In chemical formula listed above, R ¹Be preferably C _3-10Alkyl, C _6-10Aryl, C _7-10Alkaryl, C _7-10Aralkyl, C _5-10Cycloalkyl, C _6-10Aryloxy and C _7-10Aryloxy alkyl.More preferably R ¹Be C _3-10Alkyl, C _7-10Aryloxy alkyl, C _6-10Aryloxy or C _6-10Aryl, R ¹Sec.-propyl preferably, isobutyl-, the tertiary butyl, phenoxy group or phenyl.R ²Be preferably halogeno-group or C _1-10Alkyl, R ²Be C _1-3Alkyl is then better.R ³C preferably _2-10, C _6-10, C _6-10Aryloxy or C _7-10Aryloxy alkyl, R ³Be C _3-10Alkyl, phenoxy group or phenyl are better, R ³Preferably then be sec.-propyl, isobutyl-, the tertiary butyl, phenoxy group or phenyl.A is that the integer of 0-2 is better, is preferably 0-1.B is integer 0 or 1 preferably.D is integer 0 or 1 preferably.

The reversible alkali that the present invention most preferably uses is that above-mentioned a, b are 0 polymkeric substance.Wherein, most preferred reversible alkali polymkeric substance is selected from poly--(2-vinyl pyridine), poly--(4-vinylpridine) and their mixture.

The reversible alkali that the present invention uses requires purity to be higher than 90% weight percent, be higher than 95% better, preferably more than 99%.Their boiling point preferably should be higher than at least 20 ℃ of heat decomposition temperatures under the decomposition condition.

The related problems that use all kinds of neutralizing agents are the aregeneratory problems of neutralizing agent.Many neutralizing agents are used for from liquid phase medium, especially contain when removing the hydrogen halide composition in the medium that contains the sulfone mixture of sulfone and ASO, and self finally also loses usefulness, needs to change, and cost is higher.Owing to have many on record disadvantages with material during use is aregeneratory, just wish to use a kind of material that can regenerate and use repeatedly.Therefore reversible alkali described herein provide a kind of more satisfactory in and material or contact substance; With from being contained the sulfone mixture by ASO is polluted, promptly contain and remove hydrogen halide containing in the sulfone mixture of sulfone component and ASO.

Importance that should invention described herein comprises the favourable condition of the physical properties of utilizing reversible alkali, make its as in a kind of and material remove the hydrogen halide that contains in the sulfone mixture described herein.Have been found that these reversible alkali also have certain absorption property.So when the liquid medium that contains ASO (containing the sulfone mixture as what polluted by ASO) and a kind of reversible alkali (as polyvinylpyridine) when contacting, at least a portion ASO composition is adsorbed on the reversible alkali and is able to get rid of from contain the sulfone mixture.After for some time, from containing hydrogen halide of getting rid of in the sulfone mixture and the acting in conjunction of adsorbing ASO reversible alkali was lost efficacy, thereby need regeneration.

A kind of ordinary method of reversible alkali of the inefficacy that always contacts with the liquid medium that contains strong protonic acid before this of becoming known for regenerating is to make the salt of generation be subjected to the heat energy effect to cause the decomposition of salt and discharge protonic acid.Yet, when reversible alkali is that traditional renovation process is just inapplicable when being exposed under the effect that contains the sulfone mixture that contains some ASO.It is believed that, with the reversible alkali that contains the contacted inefficacy of sulfone mixture that contains ASO one of can not abundant hot regenerated reason, may be the characterization of adsorption of aforementioned reversible alkali, when reversible alkali as a kind of reagent be used for getting rid of by ASO pollute contain the halocarbon of sulfone mixture the time, this contains and has at least a part of ASO to be adsorbed in reversible alkali in the sulfone mixture, thereby polluted reversible alkali, greatly reduced it as the reagent of removing the hydrogen halide in the liquid medium or the effectiveness of neutralizing agent.

In fact the ASO that has been found that reversible alkali absorption can't all remove by heating.Therefore, need to use other measure to remove it.Wherein a kind of method is to make the reversible alkali of inefficacy be subjected to a kind of solvent action under certain conditions, so that remove the ASO of this reversible alkali absorption of at least a portion.Adsorb ASO on it by making reversible alkali remove major part under solvent action, this is a kind of preferable methods.

Can use any solvent action in the reversible alkali that lost efficacy or be in contact with it, as long as it is suitable for removing the ASO of at least a portion or most absorption.These suitable solvents can be that those ASO are the solvent of solubility therein, and it comprises the organic solvent that is selected from alcohol, aliphatic hydrocarbon, alkyl halide, amine, aromatic hydrocarbon, ester, glycol, glycol ethers, aromatic halides and the group that the mixture of two or more compounds is formed in them.

The reversible alkali that lost efficacy is after being subjected to this solvent action, make it be subjected to the effect of stripping fluid more under proper condition, this condition must be suitable for removing the quite most ASO that adsorbs of not kept by solvent removal, and removes the hydrogen halide that at least a portion (preferably most of) is removed from contain the sulfone mixture.The stripping fluid can be any fluid that is suitable for realizing stripping effect as herein described, as water, and hydrocarbon and rare gas element etc., and wish in gas phase, to use this stripping fluid.Can comprise methane, ethane, propane, butane, pentane, hexane, heptane, octane and their mixture more than two or two as stripping fluidic hydrocarbon suitably.But best strip, hydrocarbons is a Trimethylmethane, and nitrogen is best inertia stripping gas.

Reversible alkali is by stripping or be subjected to the condition of stripping fluid effect, is that those can cause reversible alkali regenerated condition, and it is a thermal reaction method normally, and the reversible alkali of inefficacy is regenerated by using heat energy.Therefore the stripping temperature is preferably within 100-600 the scope.When using Trimethylmethane,, preferably make it be in supercritical state in order to obtain best regeneration condition as the stripping fluid.Stripping pressure is not an importance of the present invention, and its scope can be about 0.1-140 normal atmosphere.

Just as described earlier in this article, will generate contain the sulfone mixture and neutralizing agent such as reversible alkali etc. contact before, preferably the hydrogen halide composition that contains the sulfone alkylation catalyst mixture that is polluted by ASO can be reduced to minimum level.Specifically, when major part contains when containing hydrogen halide in the sulfone alkylation catalyst mixture, for example: when the weight ratio of hydrogen halide and tetramethylene sulfone 1: 1-40: in the time of in 1 the scope, preferably most of hydrogen halide can be got rid of from catalyst mixture, to obtain containing sulfone mixture or restorative catalyst mixture.This contains the sulfone mixture or the restorative catalyst mixture can contain, and composition is or forms is sulfone component, hydrogen halide component and ASO substantially.In general, the hydrogen halide component concentrations will be lower than the about 10% of catalyst mixture weight in the restorative catalyst mixture, and this weight percent multiply by 100 percentage that obtain by the ratio of the weight of hydrogen halide and the gross weight of hydrogen halide and sulfone to be determined.Because be difficult to remove fully the whole hydrogen halide in the catalyst mixture, so the lower bound of hydrogen halide concentration can reach about 0.1%(weight), still, it preferably can be lower than 0.1%.Therefore, the concentration range of hydrogen halide can be in 0.1-10%(weight in the restorative catalyst mixture) between.Yet concentration range is that 0.1-7.5% is better, preferably 0.1-5.0%.

As for the use of neutralizing agent or neutralization materials, the restorative catalyst mixture that contains hydrogen halide contacts with neutralization materials, remove most hydrogen halide composition therefrom from the restorative catalyst mixture, and what obtained neutralizing contains the sulfone mixture.The sulfone mixture that contains that has neutralized is gone up substantially and is not contained hydrogen halide, and its hydrogen halide concentration generally is lower than 1.0%(weight), reasonablely should be lower than 0.2%, best should be lower than 0.1%.

At the restorative catalyst mixture or after containing the sulfone mixture and being neutralized, the sulfone mixture that contains of the processing that contains sulfone mixture or generation that has neutralized just can be for further processing or process, removing at least a portion ASO component of not removing in the neutralization procedure.Most of ASO component in the catalyzer that has neutralized is removed by it is contacted with the sorbing material that is suitable for removing its contained most of ASO component, thus obtain the regenerated catalyst mixture or handled contain the sulfone mixture.In most of the cases, the regenerated catalyst mixture or handled contain ASO component in the sulfone mixture, exist with about 2% the concentration that is lower than sulfone component gross weight.Be present in the weight percent of handling that contains the ASO in the sulfone mixture and be lower than about 1.0% better, best, ASO is lower than 0.1%.Regenerated catalyst mixture or the sulfone mixture of handling that contains can be used as a part that contains the sulfone alkylation catalyst mixture and reuse, and this mixture contains, and composition is or forms is sulfone and hydrogen halide substantially.

Referring now to Fig. 1.It is the synoptic diagram of alkylation process 10.The hydrocarbon material mixture that contains alkene and isoparaffin is introduced riser reactor 12 by conduit 14, riser reactor 12 defines a reaction zone, hydrocarbon mixture contacts therein with hydrofluoric catalyst mixture or mixes with containing tetramethylene sulfone, with formation reaction product and by product.Usually contain the alkene that one or more have 3-5 carbon atom in the hydrocarbon material mixture, and the isoparaffin in this mixture generally contains 4-6 carbon atom.Catalyst mixture is introduced riser reactor 12 via conduit 16, again with the mixture of hydrocarbon material mixture and catalyst mixture reaction zone by limiting by riser reactor 12, here, alkene in the hydrocarbon material mixture and isoparaffin reaction, generate alkylation reaction product, byproduct of reaction ASO also forms at this reaction zone.Reaction effluent enters settling vessel 18 from riser reactor 12, this negative area defines a disengaging zone, from catalyst mixture, to isolate alkylation reaction product, and the reaction product 20 that obtained separating and the catalyst mixture 22 that has separated.The catalyst mixture 22 that has separated will contain quite a large amount of alkylated reaction by product ASO.The reaction product 20 of having separated enters downstream process via conduit 21.The catalyst mixture 22 that has separated can be recycled in the riser reactor 12 through conduit 24 and 16, reuses as alkylation catalyst mixture.Inserted catalyst cooler 26 in conduit 24, it defines a heat transfer zone, gives heat-transfer fluid such as water etc. with the thermal exchange of the catalyst mixture 22 that separated.

The catalyst mixture 22(that has at least a part to separate is referred to as slip-stream or drag flow sometimes) enter stripping tower 30 by conduit 28.Stripping tower defines a disengaging zone, and the slip-stream separated into two parts of the catalyst mixture 22 that has separated, a part is an overhead streams, contain the most of hydrogen fluoride in the slip-stream; A part is a tower bottom flow, contains the most of tetramethylene sulfone component in the slip-stream.Tower bottom flow also contains the most of byproduct of reaction ASO in the slip-stream.The material of introducing stripping tower 30 by conduit 32 is to be used for the hydrofluoric steam state Trimethylmethane of stripping from slip-stream.Overhead streams introduces settling vessels 18 by conduit 34, hydrogen fluoride this with the catalyst mixture 22 that has separated once again in conjunction with reusing, the Trimethylmethane that stripping goes out is then incorporated the reaction product 20 of having separated into.

The tower bottom flow that comes out from stripping tower 30 feeds first contactor 38 via conduit 36, contains a kind of contact material here, and this contact material is preferably reversible alkali, preferably the polyvinylpyridine compound.First contactor 38 defines a disengaging zone, with by absorption and/or neutral method, remove contained most of hydrogen fluoride in the tower bottom flow, produces the tower bottom flow that has neutralized, and that promptly handled contains the sulfone mixture.Have at least ASO contained in a part of tower bottom flow also to be touched material absorption and removed.

Then, the tower bottom flow that has neutralized feeds second contactor 42 by conduit 40, and this contactor contains a kind of sorbing material.It defines contained most of ASO in the tower bottom flow that a disengaging zone neutralized with removing, and produces and do not have ASO and hydrofluoric regenerated catalyst substantially, or tetramethylene sulfone liquid stream.Tetramethylene sulfone liquid stream imports settling vessels 18 by conduit 44, in order to use as the tetramethylene sulfone component in the alkylation catalyst mixture again, with tetramethylene sulfone liquid stream at this and catalyst mixture 22 remix that separated.Tetramethylene sulfone liquid is flowed through lead to downstream process by conduit 45.

For the contained contact material of first contactor 38 of regenerating, the conduit 46 that has switch-valve 50 and 52 respectively and 48 usefulness for the periodic regeneration of failed contact material are installed.Contact material in the contactor 38 periodically is subjected to enter from conduit 46 effect of the solvent of first contactor 38, thereby contact material is under such environment, promptly has at least a part to be removed by solvent by the ASO that contact material adsorbs.The solvent that contains the ASO that removes from contact material leaves contactor 38 via conduit 48 and enters downstream process.Contact material be suitable for removing after the solvent of contained at least a portion ASO contacts on the contact material, processed contact material is subjected to the effect of stripping fluid again.The stripping fluid enters first contactor 38 by conduit 46, and the contact material with is wherein contacted.The stripping fluid is flowed out from first contactor 38 by conduit 48.

The following example has proved advantage of the present invention.These embodiment for illustrative purposes only, not as restriction of the present invention to stating in the claims.

Embodiment 1

Obtain by product ASO by the catalytic hydrocarbon reaction of the catalyst mixture that contains tetramethylene sulfone and HF, and measured some physical properties of ASO.HF is about 1.5 to the weight ratio of tetramethylene sulfone in the catalyst mixture that this hydrocarbon reaction uses, and the alkane charging comprises Trimethylmethane and 2-butylene (60% is trans, the 40%th, cis-isomeride), and the molar ratio of Trimethylmethane and 2-butylene is about 11.About 90 of temperature of reaction, the about 90psig of reaction pressure.Table 1 has been listed the resultant ASO(that derives from hydrocarbon reaction and has been comprised its distillment) some physical propertiess:

Table 1

Derive from tetramethylene sulfone/ASO fraction of the catalytic hydrocarbon reaction of HF catalyst mixture and the physical properties of ASO

Each fraction bromine number of the volume percent of temperature sample

70-200 19 51

200-210 8 45

210-225 18 56

225-250 15 58

>250 40 59

The bromine number of ASO: 32

Api gravity (60): 37.1

Proportion (60): 0.8391

Embodiment 2

Example 2 big volume descriptions be used to obtain relevant carbon, in absorption property of aluminum oxide and composition thereof and the aluminum oxide and the experimental technique of properties data.

From the process of forming by tetramethylene sulfone and ASO that contains recovery ASO in the tetramethylene sulfone mixture, for testing carbon in this process or/and the application of alumina material, general experimentation comprises about 1 inch of use diameter, the Glass tubing of long 12-24 inch, the pipe end, can put glass fiber or granulated glass sphere is that active material provides support thing.Glass fiber or granulated glass sphere also can be put in the active material top, and to assist to contain the uniform distribution of tetramethylene sulfone mixture on active material top, the method for available heating glass pipe guides the mixture flow that contains tetramethylene sulfone to cross active material bed layer in case of necessity.Contain in the mixture of tetramethylene sulfone, the weight ratio of tetramethylene sulfone and ASO is about 9: 1.When the adsorptive power of active material exhausted, the filtrate color of resultant can be made indication, but the so just degree finished of monitoring reaction.

Embodiment 3

Example 3 has been set forth activated carbon beyond thought funtcional relationship between the hydrogen fluoride concentration from the ability that contains absorption ASO the tetramethylene sulfone mixture be made up of tetramethylene sulfone and ASO and this mixture.

The experimental technique that is used for acquisition table 2 data is similar to example 2 described methods substantially, and before will containing the tetramethylene sulfone mixture and absorbent charcoal material contacts, hydrofluoric various concentration after measured in this mixture.The data that obtain are listed in table 2, and it shows that unexpectedly in containing the mixture of tetramethylene sulfone, the content of acid concentration has considerable influence to the ability of charcoal absorption ASO.These data also are shown in Fig. 2

Table 2

The absorption of adding property charcoal contains the ability of ASO in the tetramethylene sulfone mixture and the funtcional relationship of HF concentration.In this mixture, the mol ratio of tetramethylene sulfone and ASO is about 9: 1.

The adsorptive power that contains tetramethylene sulfone mixture charcoal

The weight percent % of ASO on the concentration gac of middle HF

HF weight percent %

0.02 50

0.10 19

0.50 4

1.00 do not have

Embodiment 4

Example 4 explanations, commercially available various aluminum oxide all are applicable to the HF that removes in tetramethylene sulfone and the ASO mixture by absorption or neutralization.This example also illustrates, can also adsorb in the time of aluminum oxide performance neutralizing effect and contain contained a part of ASO in the tetramethylene sulfone mixture.

The experimental technique that is used for obtaining table 3 column data is similar to the method for example 2 substantially, just needs the pH value of effluent in the monitoring pipe, with the time of the neutralising capacity of determining to reach aluminum oxide.The tetramethylene sulfone mixture that contains in the example has 5%(weight) HF of concentration.Table 3 data show that before containing the tetramethylene sulfone mixture and absorbent charcoal material contacting, various commercial alumina are applicable to that all neutralization contains the tetramethylene sulfone mixture in absorption ASO.

Table 3

Various aluminum oxide are 9: 1 containing neutralization the tetramethylene sulfone mixture and removing the ability of ASO from tetramethylene sulfone and ASO weight ratio

Aluminum oxide type neutralising capacity ASO adsorptive power

meq ^*HF/g (mg/g)

LaRoche Alumina A-202 1.8 50

Alcoa Alumina HF-200 5.0 150

Engelhard Activated Bauxite 1.3 35

"Sure cat"

LaRoche SAS Alumina 4.1 120

^*Meg represents milligramequivalent

Embodiment 5

Example 5 shows that polyvinylpyridines reversibly adsorb with desorption and contains HF in tetramethylene sulfone and the ASO mixture.This example shows that also polyvinylpyridine when playing neutralizing effect, can also adsorb and contain a part of ASO contained in the sulfone mixture.

The experimental technique that this example is used is similar substantially with example 2 and example 4, and just the needing of exception born pressure until 600psig with metallic reactors replacement Glass tubing.In addition, reacting fluid and regenerative fluid need to take out adsorption bed with pump, can not lean on gravity to flow out naturally.

Tetramethylene sulfone/ASO is that the mixture of 90: 10 volume ratio+5%HF is pumped to and remains on 100 and environmental stress 50 milliliters of Reillex are housed ^TMOn the bed of 425 polyvinylpyridines, mixture is pumped on this polymkeric substance with 20 milliliters/hour speed, reduces to before 4.0 in the pH of effluent liquid value, collects about 108 milliliters of liquid.After interrupting the charging of mixture, improve bed temperature to about 300 °F, pressure rises to 550psig.Trimethylmethane passes through the polymkeric substance bed with 30 milliliters/hour speed under these conditions.The initial color of isobutane stream fluid is very dark, and acidity is very strong.Continue the pumping Trimethylmethane, up to effluent liquid pH value greater than 6.0.At this moment, temperature and pressure has been reduced to initial condition, and tetramethylene sulfone/ASO/HF mixture quilt pumping once more passes through polymkeric substance.When the polyvinyl pyridine bed contacts for the second time with mixture, be brought down below before 4.0, collect 100 milliliters of effluent liquid in the pH value.This shows that the regeneration of Trimethylmethane is quite effective.

The calculation result of HF that obtains with regeneration period that removes from the polyvinylpyridine bed and the amount of ASO shows, the adsorbable about 5 mmole HF of every gram polymkeric substance, and 80% ASO is aggregated thing absorption in the initial sample mixture, and this is the result to whole adsorption process cumulative measurement in the circulation.

Although explained this invention according to present preferred examples, the technician who is good at technology can make rational variation and modification to this.These variations and revising all within this and the claims scope of having stated.

Claims (57)

1, a kind of method, it comprises that contain sulfone mixture and a kind of reversible alkali that will contain sulfone component and ASO contact being suitable for containing under the condition of removing at least a portion ASO composition the sulfone mixture from this, what obtain handling contains the sulfone mixture.

2, according to the method described in the claim 1, wherein above-mentioned reversible alkali is a kind of compound that conforms to one of following chemical formula

Or contain the unitary polymkeric substance that conforms to one of following chemical formula

In the formula:

R ¹Represent C respectively at every turn _2-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl or C _3-20Cycloalkyl, wherein C _2-20Alkyl, C _6-20Aryl, C _7-20Aralkyl, C _7-20Alkaryl or C _3-20Cycloalkyl can be unsubstituted, also can be by halogen, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces, R ²And R ³Represent C respectively at every turn _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C _3-20Cycloalkyl, nitro, cyano group, halogen, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy, wherein C _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl, C _7-20Aralkoxy or C _3-20Cycloalkyl is unsubstituted or by halogen, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces;

The each appearance of a is respectively the integer of a 0-4;

The each appearance of b is respectively the integer of a 0-3;

The each appearance of c be respectively integer 0 or 1 and

The each appearance of d is respectively the integer of a 0-2.

3, method according to claim 2, in this technology, above-mentioned reversible alkali is that above-mentioned a, b are 0 polymkeric substance.

4, method according to claim 3, wherein, above-mentioned reversible alkali is selected from poly--(2-vinyl pyridine), poly--(4-vinylpridine) and their mixture.

5, method according to claim 4, the wherein above-mentioned sulfone component that contains in the sulfone mixture is a tetramethylene sulfone.

6, method according to claim 5 wherein is not higher than the 20%(weight of sulfone component at the above-mentioned content that contains ASO in the sulfone mixture).

7, according to the described method of claim 6, wherein contact pressure arrives in the scope of about 30 normal atmosphere (absolute pressure) about 0.5, and the contact temperature is between 0-400 °F.

8, method according to claim 7, wherein above-mentioned processing contain the sulfone mixture comprise be lower than 2%(weight) ASO of concentration.

9, a kind of method, it comprise with contain sulfone component, hydrogen halide component and ASO contain sulfone mixture and a kind of reversible alkali be suitable for removing contact under this condition that contains at least a portion ASO composition in the sulfone mixture with obtain a kind of handled contain the sulfone mixture.

10, method according to claim 9, wherein above-mentioned reversible alkali are compounds that conforms to one of following chemical formula

Or one contain the unitary polymkeric substance that conforms to one of following chemical formula

In the formula:

R ¹Represent C respectively at every turn _2-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl or C _3-20Cycloalkyl, wherein C _2-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl or C _3-20Cycloalkyl can be unsubstituted, also can be by halogen, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces; R ²And R ³When occurring, represent C respectively at every turn _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C _3-20Cycloalkyl, nitro, cyano group, halogen, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy, wherein C _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C ₇-C ₂₀Aralkyl, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl, C _7-20Aralkoxy or C _3-20Cycloalkyl is unsubstituted, or by halogen, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces;

The each appearance of a is respectively the integer of a 0-4;

The each appearance of b is respectively the integer of a 0-3;

The each appearance of c is respectively integer 0 or 1; With

The each appearance of d is respectively the integer of 1 0-2.

11, method according to claim 10, wherein this reversible alkali is that above-mentioned a, b value are 0 polymkeric substance.

12, method according to claim 11, wherein this reversible alkali is selected from by poly--(2-vinyl pyridine), poly--(4-vinylpridine), and the group formed of their mixture.

13, method according to claim 12, the wherein said sulfone component that contains the sulfone mixture is a tetramethylene sulfone, this hydrogen halide composition that contains in the sulfone mixture is a hydrogen fluoride.

14, method according to claim 13 wherein contains described that contained hydrogen halide composition is lower than 10% of hydrogen halide and sulfone component gross weight in the sulfone mixture, contains that the ASO amount then is not higher than 20% of hydrogen halide and sulfone component gross weight in the sulfone mixture.

15, according to the described method of claim 14, wherein, that handled contains in the sulfone mixture, and the concentration of hydrogen halide is lower than 0.2%(weight).

16, method according to claim 15, wherein, contact pressure is from about 0.5 to about 30 normal atmosphere (absolute pressure), and the contact temperature is from about 0 °F to about 400 °F.

17, a kind of method of removing the ASO of contained contamination level the sulfone mixture that contains from forming by tetramethylene sulfone, ASO and HF, comprise: will contain sulfone mixture and a kind of reversible alkali and contact being suitable for containing under ASO that removes the described contamination level of at least a portion the sulfone mixture and the condition of removing at least a portion HF from this, contain the sulfone mixture with what obtain handling, this processing contain the HF that the sulfone mixture contains the lingering section of above-mentioned contamination level ASO and reduced concentration.

18, method according to claim 17, wherein above-mentioned reversible alkali are a kind of compounds that conforms to one of following chemical formula:

Or a kind of unitary polymkeric substance that conforms to one of following chemical formula that contains:

In the formula:

R ¹C is represented in each appearance respectively _2-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl or C _3-20Cycloalkyl, wherein C _2-20Alkyl, C _6-20Aryl, C _7-20Aralkyl, C _7-20Alkaryl or C _3-20Cycloalkyl is unsubstituted or by halogen, nitro, cyano group, C _1-20, alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces; R ²And R ³Each appearance is respectively C _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C _3-20Cycloalkyl, nitro, cyano group, halogen, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy, wherein, C _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C ₁-C ₂₀Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl, C _7-20Aralkoxy or C _3-20Cycloalkyl is unsubstituted, or by halogen, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces;

The each appearance of a is respectively a 0-4 integer;

The each appearance of b is respectively the integer of a 0-3;

The each appearance of c is respectively integer 0 or 1; With

The each appearance of d is respectively from 0 to 2 integer.

19, method according to claim 18, wherein said reversible alkali are that a, b are 0 polymkeric substance.

20, method according to claim 19, wherein said reversible alkali are selected from the group of being made up of poly--(2-vinyl pyridine), poly--(4-vinylpridine) and their mixture.

21, method according to claim 20 wherein also comprises: the sulfone mixture that contains of described processing is contacted with carbon, and with the lingering section of the ASO that removes most of above-mentioned contamination level, what obtain not containing substantially ASO contains the sulfone mixture.

22, method according to claim 21 wherein, contains in the sulfone mixture described, and the HF composition is lower than 10% of HF and tetramethylene sulfone gross weight, and the ASO that contains contamination level described in the sulfone mixture is not higher than 20% of HF and tetramethylene sulfone gross weight.

23, method according to claim 22, wherein said processing contain the sulfone mixture contain be lower than 0.2%(weight) the HF that has reduced concentration.

24, method according to claim 23, wherein, the above-mentioned concentration that contains ASO in the sulfone mixture that does not contain ASO substantially is lower than 2%(weight).

25, a kind of method, comprise that the restorative catalyst mixture that will contain tetramethylene sulfone, ASO and HF contacts with a kind of reversible alkali, thereby remove quite most HF component in this restorative catalyst mixture, to produce a kind of catalyst mixture that has neutralized.

26, method according to claim 25, wherein said reversible alkali is the compound that one of following chemical formula conforms to:

Or a kind of unitary polymkeric substance that conforms to one of following chemical formula that contains:

In the formula:

R ¹C is represented in each appearance respectively _2-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl or C _3-20Cycloalkyl, wherein C _2-20Alkyl, C _6-20Aryl, C _7-20Aralkyl, C _7-20Alkaryl or C _3-20Cycloalkyl is unsubstituted or by halogen, nitro, cyano group, C _1-20, alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces; R ²And R ³C is represented in each appearance respectively _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C _3-20Cycloalkyl, halogen, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy, wherein, C _1-20Alkyl, C _6-20Aryl, C _7-20Alkaryl, C _7-20Aralkyl, C ₁-C ₂₀Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl, C _7-20Aralkoxy or C _3-20Cycloalkyl is unsubstituted, or by halogen, nitro, cyano group, C _1-20Alkoxyl group, C _6-20Aryloxy, C _7-20Aryloxy alkyl or C _7-20Aralkoxy replaces;

The each appearance of a is respectively the integer of a 0-4;

The each appearance of b is respectively the integer of a 0-3;

The each appearance of c is respectively integer 0 or 1; With

The each appearance of d is respectively from 0 to 2 integer.

27, method according to claim 26, wherein said reversible alkali are that a, b are 0 polymkeric substance.

28, method according to claim 27, wherein said reversible alkali are selected from by poly--(2-vinyl pyridine), poly--(4-vinylpridine), and the group formed of their mixture.

29, method according to claim 28 wherein also comprises: the above-mentioned catalyst mixture that has neutralized contacted with charcoal, thereby remove quite most ASO composition in the above-mentioned catalyst mixture that has neutralized, obtain a kind of regenerated catalyst mixture.

30, method according to claim 29, comprising:

Use above-mentioned regenerated catalyst mixture to contain the catalyst mixture of sulfone and HF as at least a portion, and the hydrocarbon mixture that will contain alkene and isoparaffin contacts in reaction zone with this catalyst mixture, thereby obtains an alkylation reaction mixture that contains alkylate and ASO.

31, method according to claim 30 wherein also comprises:

In the disengaging zone, from above-mentioned catalyst mixture, isolate alkylate, obtain a catalyst mixture that has separated, this mixture contains in a large number the ASO that the contact procedure by claim 30 produces; With

Use this catalyst mixture that has separated at least as a part of above-mentioned catalyst mixture.

32, method according to claim 31 wherein also comprises: at least the part of the above-mentioned catalyst mixture that has separated is divided into liquid stream that contains above-mentioned restorative catalyst mixture and the hydrogen fluoride liquid stream that contains HF.

33, method according to claim 32 wherein also comprises: use above-mentioned hydrogen fluoride liquid stream as the part in the above-mentioned at least catalyst mixture.

34, a kind of method, comprise and to contact from above-mentioned containing under the condition of removing the contained hydrogen halide composition of this mixture of a part the sulfone mixture at least being suitable for by contain sulfone mixture and the reversible alkali that sulfone component, halocarbon composition and ASO form that what obtained neutralizing contains the sulfone mixture.

35, method according to claim 34 wherein also comprises: make above-mentioned reversible alkali use a kind of solvent treatment under certain condition, so that the ASO that this reversible alkali adsorbs during the contact procedure of claim 34 has at least a part to be removed by this solvent.

36, method according to claim 35, wherein above-mentioned solvent is a kind of organic solvent, is selected from the group of being made up of two kinds of alcohol, aliphatic hydrocarbon, haloalkane, amine, aromatic hydrocarbon, ester, glycol, glycol ethers, aromatic halide and they or multiple mixture.

37, method according to claim 36 wherein also comprises: with above-mentioned reversible alkali under the stripping condition with a kind of stripping fluid handling so that regeneration this reversible alkali.

38, according to the described method of claim 37, wherein, the stripping condition of the treatment process of claim 37 comprises that the stripping temperature is about 100-600 °F, and stripping pressure is about the 0.1-140 normal atmosphere.

39, according to the described method of claim 38, wherein, above-mentioned stripping fluid is selected from the group of being made up of rare gas element, steam and steam state hydrocarbon.

40, a kind of alkylation comprises following operation:

The hydrocarbon mixture that will contain alkene and isoparaffin contacts at reaction zone with the catalyst mixture that contains tetramethylene sulfone and HF, thereby obtains a kind of reaction product and a kind of byproduct of reaction;

In first disengaging zone, from above-mentioned catalyst mixture, isolate this reaction product, thereby obtain a kind of reaction product of having separated and a kind of catalyst mixture that has separated, contain a large amount of byproducts of reaction in this mixture;

Use the above-mentioned catalyst mixture that has separated at least as the part of above-mentioned catalyst mixture;

Make the above-mentioned catalyst mixture that has separated have a part at least by second disengaging zone, thereby the isolating catalyst mixture of this at least a portion is separated into the overhead streams and the tower bottom flow in this district, overhead streams comprises the most of HF composition in above-mentioned at least a portion separating catalyst mixture, and tower bottom flow then contains most of tetramethylene sulfone component and the most of byproduct of reaction in this catalyst mixture;

Use the HF composition of the overhead streams of above-mentioned second disengaging zone as the aforementioned catalyst mixture of at least a portion;

With the tower bottom flow of above-mentioned second disengaging zone be selected from by poly--(2-vinyl pyridine), poly--(4-vinylpridine), and the reversible alkali of the group formed of their mixture contact, removing contained a large amount of HF in this second disengaging zone tower bottom flow, the second disengaging zone tower bottom flow that has obtained neutralizing;

This second disengaging zone tower bottom flow that has neutralized is contacted with charcoal to remove a large amount of above-mentioned most of byproducts of reaction, obtain not containing substantially the tetramethylene sulfone liquid stream of above-mentioned byproduct of reaction and HF;

Use this tetramethylene sulfone liquid stream as the tetramethylene sulfone component in the above-mentioned catalyst mixture of at least a portion.

41, according to the described alkylation of claim 40, wherein also comprise: above-mentioned reversible alkali is periodically used a kind of solvent treatment under appropriate condition, during the contact operation of claim 40 so that at least a portion ASO that is adsorbed on the reversible alkali is removed by this solvent.

42, according to the described method of claim 41, wherein above-mentioned solvent is a kind of organic solvent, and it is selected from the group of being made up of alcohol, aliphatic hydrocarbon, haloalkane, amine, aromatic hydrocarbon, ester, glycol, glycol ethers, aromatic halide and they two kinds or multiple mixture.

43, according to the described method of claim 42, wherein also comprise, under the stripping condition with above-mentioned reversible alkali with a kind of stripping fluid handling, so that this reversible alkali of regeneration.

44, according to the described method of claim 43, wherein, the stripping condition of the treatment process in the claim 43 comprises that the stripping temperature is in about 100-600 scope, and stripping pressure is between about 0.1-140 normal atmosphere.

45, according to the described method of claim 44, wherein, above-mentioned stripping fluid is selected from the group of being made up of rare gas element, steam and steam state hydrocarbon.

46, method according to claim 1, wherein also comprise, under appropriate condition with a kind of solvent treatment of above-mentioned reversible alkali, so that removed by this solvent at least a portion ASO that is adsorbed on this reversible alkali during the contact operation described in the claim 1.

47, method according to claim 36, wherein, above-mentioned solvent is a kind of organic solvent, is selected from the group of being made up of two kinds of alcohol, aliphatic hydrocarbon, haloalkane, amine, aromatic hydrocarbon, ester, glycol, glycol ethers, aromatic halide and they or multiple mixture.

48, method according to claim 9 wherein also comprises, above-mentioned reversible alkali is used a kind of solvent treatment under appropriate condition, so that this reversible alkali adsorbed ASO during the contact operation of claim 9 has at least a part to be removed by this solvent.

49, according to the described method of claim 48, wherein, above-mentioned solvent is a kind of organic solvent, and it is selected from by alcohol, aliphatic hydrocarbon, haloalkane, amine, aromatic hydrocarbon, ester, glycol, glycol ethers, aromatic halide and two or more mixture is formed in them group.

50, according to the described method of claim 49, wherein also comprise, with above-mentioned reversible alkali under the stripping condition with a kind of stripping fluid handling so that regeneration this reversible alkali.

51, according to the described method of claim 50, wherein, the stripping condition of the described treatment process of claim 50 comprises that the stripping temperature is from about 100 °F to about 600 °F, and stripping pressure is pressed onto about 140 normal atmosphere from about 0.1 atmosphere.

52, according to the described method of claim 51, wherein above-mentioned stripping fluid is selected from by rare gas element, the group that water vapor and steam state hydrocarbon are formed.

53, method according to claim 17, wherein also comprise, under proper condition with a kind of solvent treatment of above-mentioned reversible alkali, so that at least a portion ASO that is adsorbed by this reversible alkali during the described contact operation of claim 17 can remove by this solvent.

54, method according to claim 36, wherein, above-mentioned solvent is a kind of organic solvent, is selected from by alcohol, aliphatic hydrocarbon, haloalkane, amine, aromatic hydrocarbon, ester, glycol, glycol ethers, aromatic halide and the mixture more than two or two is formed in them group.

55, according to the described method of claim 37, wherein also comprise, under the stripping condition with above-mentioned reversible alkali with a kind of stripping fluid handling, so that make reversible alkali regeneration.

56, according to the described method of claim 55, wherein, the stripping condition of the described treatment process of claim 55 comprises: the stripping temperature is in being about 100-600 scope, and stripping pressure is in the 0.1-140 barometric pressure range.

57, according to the described method of claim 39, wherein, above-mentioned stripping fluid is selected from by rare gas element, the group that water vapor and steam state hydrocarbon are formed.

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