JP3172338B2 - Method for removing acid-soluble oil from sulfone-containing mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates to the regeneration of catalyst compositions used in hydrocarbon conversion processes. More particularly, the present invention relates to the regeneration of a catalyst mixture comprising a sulfone compound and a hydrogen halide used in the alkylation of an olefinic hydrocarbon with an isoparaffinic hydrocarbon.

[0002]

2. Description of the Related Art As disclosed in our Japanese Patent Application No. 5-104546 filed on 5.4.30 and our Japanese Patent Application No. 5-104547 filed on 5.4.30,
Mixtures of sulfone compounds and hydrogen halides are effective catalysts for use in the alkylation of olefinic hydrocarbons with isoparaffinic hydrocarbons to produce alkylation reaction products, ie, alkylates. The alkylation reaction product is generally a highly desirable gasoline blend containing seven or more carbon atoms and because of its high octane number as a motor fuel.

[0003] Processes utilizing catalyst compositions containing a sulfone component and a hydrogen halide component produce very high quality alkylation products, but have side reactions due to the use of such processes in the production of alkylates. One is the formation of certain polymer reaction by-products called acid-soluble oils or ASO. These polymer reaction by-products are soluble in the catalysts utilized in the alkylation step, and thus the alkylate product resulting from contacting the hydrocarbon mixture with the alkylation catalyst is converted from the alkylation catalyst. It is called an acid-soluble oil because it remains in the catalyst phase when separated. In the alkylation step where the catalyst phase is continuously separated from the alkylation reaction product and reused in the reaction zone of the process, ASO is accumulated in the catalyst. If not removed, the concentration of ASO will reach an unacceptable concentration over time. It is believed that low levels of ASO in the alkylation catalyst consisting of the sulfone component and the hydrogen halide have a beneficial effect on the alkylation step or its products. However, relatively high concentrations of ASO in the alkylation catalyst adversely affect the catalyst activity and the final alkylated end product. The ASO concentration in the alkylation catalyst that exceeds a certain allowable limit is
The octane number of the alkylate end product is reduced by the gradual decrease of alkylate octane with increasing concentration.

[0004]

In contrast to the above-mentioned process using the novel catalyst comprising a sulfone component and a hydrogen halide, the conventional alkylation process using hydrogen fluoride (HF) as catalyst comprises a continuous alkylation process. There are certain known methods used to remove ASO from the HF catalyst used in the conversion step. In particular, a sufficient amount of the HF catalyst used in the alkylation step is treated or regenerated so that the amount of ASO can be removed at approximately the same rate as the rate of accumulation of ASO in the alkylation catalyst. This involves passing a portion of the HF catalyst through a stripping vessel where the HF is stripped from the ASO with a vaporous hydrocarbon such as isobutane,
Passing as part of the gas phase overhead from the stripping vessel, the ASO is performed by passing it as a bottom stream of the stripping vessel for further processing.

[0005] Conventional alkylation catalyst regeneration processes use conventional H
It can be used satisfactorily in the regeneration of the F catalyst, but conventional means cannot be used in the regeneration of alkylation catalysts containing the sulfone component. This is because the boiling range of ASO overlaps the boiling range of certain sulfones, such as sulfolane. Therefore, simple distillation methods such as those used to separate HF from ASO cannot be used to effectively regenerate sulfone-containing alkylation catalysts. In addition to this,
In order to recover the sulfone for reuse as a catalyst in the alkylation step, it is necessary to separate ASO from the sulfone.

[0006]

SUMMARY OF THE INVENTION The process of the present invention relates to the alkylation of olefinic hydrocarbons with paraffinic hydrocarbons by utilizing a catalyst mixture containing a sulfone component. The sulfone-containing mixture comprising sulfone and ASO is converted to a reversible base (rev) under conditions suitable to remove at least a portion of the ASO component from the sulfone-containing mixture.
A treated sulfone-containing mixture is formed by contacting the mixture with an oxidizable base.

[0007] Other objects and advantages of the present invention will be apparent from the foregoing detailed description of the invention and the appended claims.

[0008] The acid-soluble oil of the present invention comprises an alkylation catalyst comprising the step of contacting a hydrocarbon mixture comprising an olefin and an isoparaffin with an alkylation catalyst comprising, or consisting essentially of, a hydrogen halide component and a sulfone component. It is produced as a reaction by-product in the conversion process. As used herein and in the appended claims, the term "acid-soluble oil" or "ASO" refers to a linked polymer that is a highly olefinic oil produced by an acid-catalyzed reaction of a hydrocarbon. Meaning. For an extensive description and characterization of certain linked polymer oils, see
Journal of by iron and Lee
Chemical and Engineering
7. Volume of Data No. 150-1 of 1
“Molecular Structure” on page 60
of Connect Polymers ". This document is a reference of this specification. A
The physical properties of SO depend on the particular hydrocarbon being treated, the catalyst used in the process, feed contaminants such as hydrogen sulfide, butadiene, oxygenates and other compounds, and the alkylation process reaction conditions, etc. I do. Thus, in a more narrow definition of this term, ASO is a by-product in the catalytic reaction of mono-olefins with isoparaffins using a catalyst mixture comprising, or consisting essentially of, a sulfone component and a hydrogen halide component. Would be a bound polymer produced as Preferred monoolefins suitable for use in the catalysis are those having 3-5 carbon atoms, with preferred isoparaffins being 4-6
Having three carbon atoms. The preferred sulfone component is sulfolane, and the preferred hydrogen halide component is hydrogen fluoride.

[0009] The ASO by-product derived from the catalyzed hydrocarbon reaction of the sulfone-containing alkylation catalyst generally uses about 10.6 ° C. (60 ° F.) water as a standard to produce about 0. Specific gravity in the range of 8 to about 1.0, about 250 to
Average molecular weight in the range of about 350 and about 40 to about 350
Is further characterized as having a bromine number in the range of

The hydrogen halide component of the catalyst composition or catalyst mixture includes hydrogen fluoride (HF), hydrogen chloride (HCl),
It can be selected from compounds comprising hydrogen bromide (HBr) and mixtures of two or more thereof. However, the preferred hydrogen halide is hydrogen fluoride which can be used in anhydrous form in the catalyst composition, but generally the hydrogen fluoride used contains a small amount of water. There is no water present in the catalyst composition comprising the hydrogen fluoride component and the sulfolane in an amount greater than about 30% by weight of the total weight of the hydrogen fluoride component including the water. Preferably, the amount of water present in the hydrogen fluoride is less than about 10% by weight. Most preferably, the amount of water present in the hydrogen fluoride component is less than 7% by weight. As used herein, when referring to the hydrogen halide component, more particularly the hydrogen fluoride component, of the catalyst composition of the present invention, these terms refer to either an anhydrous mixture or a non-anhydrous mixture. It should be understood as meaning. The weight% of water contained in the hydrogen halide component is obtained by multiplying the ratio of the weight of water to the total weight of water and hydrogen halide by a coefficient of 100 and expressing the weight ratio in%.

Sulfones suitable for use in the present invention have the general formula:

[0012]

[Formula 1] R-SO ₂ -R '

Wherein each of R and R 'is a monovalent hydrocarbon alkyl or aryl substituent having 1 to 8 carbon atoms.

Is a sulfone. Examples of such substituents include dimethyl sulfone, di-n-propyl sulfone, diphenyl sulfone, ethyl methyl sulfone and SO ₂
Cycloaliphatic sulfones in which the group is attached to a hydrocarbon ring are included. In such a case, R and R 'together form a branched or unbranched divalent moiety containing preferably 3 to 12 carbon atoms. Of the latter, tetramethylene sulfone or sulfolane, 3-methylsulfolane and 2,4-dimethylsulfolane are particularly preferred because of the advantage of being liquid under the process operating conditions relevant to the present invention. These sulfones can also have substituents, for example chloromethylethylsulfone, in particular one or more halogen atoms. These sulfones can be used advantageously in the form of a mixture.

[0015] The alkylation catalyst used in the alkylation step in which the ASO reaction by-product is formed comprises, consists of, or consists essentially of a hydrogen halide component and a sulfone component as described herein. be able to. Preferably, the ASO by-product will be produced in an alkylation step in which the hydrocarbon mixture is contacted with an alkylation catalyst having sulfolane as the sulfone component and hydrogen fluoride as its hydrogen halide component. When the alkylation catalyst comprises sulfolane and hydrogen fluoride, good alkylation is achieved when the weight ratio of hydrogen fluoride to sulfolane in the alkylation catalyst is in the range of about 1: 1 to about 40: 1. The result can be obtained. The preferred weight ratio of hydrogen fluoride to sulfolane is about 2.3: 1.
To about 19: 1, more preferably from 3: 1 to about 1: 1.
The range is 9: 1.

In order to improve the selectivity of the alkylation reaction of the present invention to produce the desired highly branched hydrocarbons having seven or more carbon atoms, a substantially stoichiometric The presence of more than stoichiometric isoparaffins is desirable. A molar ratio of isoparaffinic hydrocarbon to olefinic hydrocarbon of from about 2: 1 to about 25: 1 is contemplated by the present invention. Preferably, the molar ratio of isoparaffin to olefin will be from about 5 to about 20, most preferably in the range of 8 to 15. However, the ranges recited above for the molar ratio of isoparaffins to olefins are commercially practicable, but are generally obtained accordingly as the molar ratio of isoparaffins to olefins in the alkylation reaction increases. The alkylate quality will be good.

The alkylation reaction temperature within the range expected in the present invention is from about -17.8 ° to about 65.6 ° C (about 0 ° to
About 150 ° F). Relatively low temperatures favor the alkylation reaction of isoparaffins with olefins over competing olefin side reactions such as polymerization. However, the overall reaction rate decreases with decreasing temperature. A temperature within a range, preferably from about -11.1 ° to about 54.
Within the range of 4 ° C (about 30 ° to about 130 ° F), good selectivity for alkylation of isoparaffins with olefins is obtained at commercially attractive reaction rates. But,
Most preferably, the alkylation temperature is between 10.0 ° and 4 °
8.9 ° C. (50 ° to 120 ° F.).

The reaction pressure contemplated in the present invention ranges from a pressure sufficient to maintain the reactants in the liquid phase to a pressure of about 15 atmospheres. The hydrocarbons of the reactants will normally be gaseous at the alkylation reaction temperature, so from about 2.8 to about 11.
Reaction pressures in the range of ² kg / cm ² gauge (about 40 to about 160 psig) are preferred. If all reactants are in the liquid phase, the increased pressure has no significant effect on the alkylation reaction.

The contact time of the hydrocarbon reactant in the alkylation reaction zone in the presence of the alkylation catalyst of the present invention generally results in essentially complete conversion of the olefin reactant in the alkylation zone. Must be enough to be Preferably, the contact time is in a range from about 0.05 to about 60 minutes. Using an isoparaffin to olefin molar ratio of about 2: 1 to about 25: 1, the alkylation reaction mixture is about 40-90% by volume catalyst phase and about 60-10% by volume.
In the alkylation process of the present invention, comprising from about 0.1 to about 200 volumes of olefin / hour / volume catalyst, wherein the hydrocarbon phase comprises at least one hydrocarbon phase and good contact between the olefin and isoparaffin is maintained in the reaction zone. At space velocity (v / v / h) essentially complete conversion of the olefin is obtained. The optimum space velocity depends on the type of isoparaffin and olefin used, the particular composition of the alkylation catalyst and the alkylation reaction conditions. Thus, preferred contact times provide an olefin space velocity in the range of about 0.1 to 200 (v / v / hr) and provide essentially complete conversion of the olefin reactants in the alkylation zone. It is enough time to be done.

The alkylation step can be carried out in either a batch or continuous mode of operation, but for economic reasons a continuous step is preferred. It has been demonstrated that closer contact between the feed and the catalyst in the alkylation step results in better quality alkylate products.
With this in mind, when performing the present invention in a batch operation, vigorous mechanical stirring or shaking of the reactants and catalyst is a feature of the present invention.

In continuous operation, the reactants are maintained at a pressure and temperature sufficient to maintain substantially the liquid phase, and then are passed through a forced dispersion device to the reaction zone. The dispersive device may be a jet, a nozzle, a porous thimble, or the like. Subsequently, the reactants are mixed with the catalyst by conventional mixing means such as a mechanical stirrer or turbulent flow system. After a sufficient time, the product is continuously separated from the catalyst and withdrawn from the reaction system,
The partially used catalyst is recycled to the reactor. A portion of the catalyst is continuously regenerated or reactivated and returned to the alkylation reactor as described herein or by any suitable treatment.

In one aspect of the invention, a sulfone-containing mixture comprising a sulfone component and ASO is contacted with a contact material suitable for removing at least a portion of the ASO component of the sulfone-containing mixture. Removing ASO from the sulfone-containing mixture comprising the step of producing a prepared sulfone-containing mixture. The sulfone-containing mixture of the process of the present invention can also consist of a sulfone component, a hydrogen halide component and ASO. The contact material is
Any of the materials described herein, and alumina, carbon,
And mixtures thereof, as well as the preferred reversible bases as defined herein. The preferred sulfone component of the sulfone-containing mixture is sulfolane.

The ASO component of the sulfone-containing mixture can be present in an amount up to about 20% by weight of the sulfone component. Preferably, the ASO concentration will be less than about 15% by weight of the sulfone component, and most preferably will be present at a concentration of less than 10% by weight. If a hydrogen halide component is present in the sulfone-containing mixture, its concentration will be less than about 10% by weight of the mixture, where the weight percentage is the weight fraction of hydrogen halide to total weight of sulfone and hydrogen halide. Is multiplied by a coefficient 100 to obtain%. However, in general, the concentration range of hydrogen halide in the sulfone-containing mixture is from about 0.1 to about 10% by weight.
Range. However, preferably, the concentration is between about 0.1 and
In the range of about 7.5 weight percent, most preferably 0.1 to
It is in the range of 5.0% by weight.

An embodiment of the present invention which comprises contacting the sulfone-containing mixture with a contact material to remove at least a portion of the hydrogen halide in the sulfone-containing mixture to obtain a treated sulfone-containing mixture having a reduced hydrogen halide concentration is an essential condition. Not important but important. However, a significant portion of the hydrogen halide is removed from the treated sulfone-containing mixture to reduce the concentration of hydrogen halide in the treated sulfone-containing mixture to less than about 1.0% by weight, preferably less than about 0.2% by weight, and most preferably Has a concentration of less than 0.1% by weight.

The treated sulfone-containing mixture also has an ASO content generally less than about 5% by weight of the treated sulfone-containing mixture.
With a reduced concentration of The preferred concentration of ASO in the treated sulfone-containing mixture is less than about 2% by weight, and most preferably the ASO is present in an amount less than 1% by weight.

In another embodiment of the process of the present invention, a mixture of a sulfone-containing alkylation catalyst comprising a sulfone component, a hydrogen halide component and ASO is used to form the A contained in the mixture.
It is intended to address the problems associated with regenerating the catalyst mixture by removing at least a portion of the SO. ASO accumulation in the sulfone-containing alkylation catalyst occurs when the catalyst is continuously reused in the alkylation step. In the continuous alkylation step, if the ASO reaction by-products are not removed, they accumulate in the catalyst to an unacceptable level, which negatively affects the catalyst performance and, ultimately, the quality of the alkylation product itself. It is generally desirable to maintain the ASO concentration in the sulfone-containing alkylation catalyst below about 20% by weight, based on the total weight of the catalyst mixture excluding the ASO component. Preferably, less than about 15% by weight of the sulfone-containing alkylation catalyst, most preferably ASO
Is less than 10% by weight.

While maintaining a low concentration of ASO in the sulfone-containing catalyst mixture has certain process advantages, ASO concentrations greater than about 10% by weight of the catalyst are believed to adversely affect catalyst performance. ing. Thus, in order to maintain the catalytic activity of the sulfone-containing alkylation catalyst mixture, at least a portion of the catalyst must be treated to remove at least a portion of the ASO contained in such a catalyst. To this end, at least a portion, preferably a substantial portion, of the ASO component of the sulfone-containing alkylation catalyst mixture is removed by contacting the sulfone-containing alkylation catalyst mixture with a contact material and then with an adsorbent material.

However, the resulting sulfone-containing alkylation catalyst mixture is contacted with a contact material, thereby producing an ASO
Prior to removing at least a portion of the components and / or removing at least a portion of the hydrogen halide, at least a portion, preferably a substantial portion, of the hydrogen halide component of the sulfone-containing alkylation catalyst mixture. It should be noted that it is preferable to remove. Accordingly, the sulfone-containing mixture is a sulfone-containing alkylation catalyst mixture in which at least a portion, preferably a substantial portion, of the hydrogen halide component has been removed. Any suitable method can be used to separate the hydrogen halide from the sulfone-containing alkylation catalyst mixture, for example, evaporative separation, distillation, extraction, stripping or other suitable separation methods.
One preferred method involves separating the sulfone-containing mixture into an overhead stream containing the major portion of the hydrogen halide component of the sulfone-containing alkylation catalyst and a bottom stream comprising the sulfone-containing mixture using isobutane vapor as the stripping agent. This is a method using stripping means.

The concentration of the hydrogen halide component in the sulfone-containing mixture is determined by multiplying the fraction of hydrogen halide with respect to the total weight of hydrogen halide and sulfone by a factor of 100 to obtain% by weight of the mixture. Will be less than about 10% by weight. However, since it is very difficult to remove all of the hydrogen halide in the mixture, the lower limit of hydrogen halide from a commercially feasible point of view is about 0.1.
1% by weight, and preferably the concentration is 0.1%.
It is to be less than 1% by weight. Thus, the concentration of hydrogen halide in the sulfone-containing mixture is between about 0.1 and about 10
% By weight. However, preferably, this concentration is in the range of about 0.1 to about 7.5% by weight, most preferably in the range of 0.1 to 5.0% by weight.

As mentioned earlier in this specification, the treated sulfone-containing mixture is preferably treated with an adsorbent selected from the group consisting of carbon, alumina and mixtures thereof in the second contacting step with the ASO contained therein. Further under suitable conditions to remove at least a portion of
However, a mixture having an ASO concentration of less than about 2% by weight of a substantially ASO-free sulfone-containing mixture by removing a substantial portion of the ASO therein by contacting the treated sulfone-containing mixture with an adsorbent material Is preferable. Preferred ASO concentrations are less than about 1% by weight, and most preferably ASO is present in an amount less than 0.1% by weight.

Generally, both the contact and adsorbent materials contemplated for use according to the present invention are in the form of solid particulate matter and are contained as a bed in a vessel defining a contact zone, Within the zone, the sulfone-containing fluid can be contacted with either a contact or adsorbent. However, the present invention is not limited to the use of standard vessels that define a contact zone, but uses any suitable means known in the art for contacting a sulfone-containing fluid with either a contact or adsorbent material. be able to.

The adsorbent material used to remove ASO from the treated sulfone-containing mixture is any that is capable of suitably or effectively removing at least a portion of the ASO component contained in such a mixture. Adsorbent. Preferably, the adsorbent is selected from the group consisting of alumina, carbon and mixtures thereof.

The carbon sorbent material is any activated carbon material that is suitable for selective removal of at least a portion of the ASO component contained in the use and treated sulfone-containing mixture as contemplated by the present invention. . Activated carbon adsorbent
"Standard TestMethod for
Surface Area of Catalyst
s "as measured by the American Society for Testing and Materials (ASTM) standard test method D3663-84.
It can be characterized by its large specific surface area, which is in the range of about 2500 m ² / g. Standard ASTM test D
3663-84 are incorporated herein by reference. Furthermore, the activated carbon adsorbent is "Standard Te
st Method for Determining
PoreVolume Distribution
of Catalysts byMetricy Int
rusion Porosimetry ”
It can also be characterized by its pore diameter ranging from about 10 to about 50 μm as measured by the mercury intrusion porosimetry described in TM Standard Test D4284-88. Standard test method D4284-88 is incorporated herein by reference. The use of commercially available activated carbon is generally desirable. One such suitable commercially available activated carbon is, for example, Calgon Car
Calgon Filtrasorb 400 manufactured and sold by Bon Corporation
It is a product known by the trademark name.

[0034] The alumina adsorbent material is used in the present invention and the A contained in the treated sulfone-containing mixture.
Any alumina suitable for use as a neutralizing agent for the selective removal of at least a portion of the SO component or for the removal of at least a portion of the hydrogen halide in a sulfone-containing fluid may be used. Such suitable aluminas include, for example, a number of commercially available activated and calcined aluminas. Generally, the alumina material is ASTM D366
It has a surface area in the range of from about 150 to about 500 meters ² / g as measured in 3-84. Also, the pore diameter of the alumina material is about 2 as measured by ASTM D4284-88.
It is in the range of 5 to about 125 μm. The use of commercially available alumina is generally desirable. One such suitable commercially available alumina is the product known by its trade name HF-200 manufactured and sold by Alcoa. The most preferred alumina for use in the present invention, chi has a calcined alumina, and about 50 m ² / g or more surface area with a known γ-crystal structure as γ- alumina with a surface area of more than about 50 m ² / g
(Chi) -Other aluminas such as alumina.

The process conditions for contacting the treated sulfone-containing mixture with the adsorbent composition are as follows:
Any condition suitable or effective for removing at least a part of the concentration of SO may be used. The removal efficiency of the adsorbent material is believed to be highly independent of the contact pressure, since the adsorption phenomenon is believed to be the result of liquid-solid interaction, but the process pressure is about 0.5 atm. (Absolute pressure) and is in the range of about 30 atmospheres (absolute pressure) or higher. More common working pressures are generally from about atmospheric to about 14.1 kg / cm ² gauge (200 psi).
g).

With respect to the contact temperature, any suitable temperature that can effectively remove at least a portion of the ASO from the treated sulfone-containing mixture can be used. In general, the upper and lower temperature limits are set by the physical properties of the mixture to be treated and the physical properties of the ASO contained in such a mixture. Considering the minimum temperature, pure sulfolane is about 27.4-27.8 ° C (about 81.3-82.
Although the melting point is 0 ° F., this melting point is much lower when sulfolane is a mixture with water and hydrogen fluoride.
Therefore, the lower limit of the contact temperature is about -17.8 ° C. (about 0 °
F). The upper limit of the contact temperature is determined by such factors as the initial boiling point of the ASO and the temperature at which the sulfone component of the mixture begins to pyrolyze. That is, the upper limit of the contact temperature is about 204.4 ° C. (about 400 ° F.).
Accordingly, contact temperatures generally range from about −17.8 ° to about 20 °.
The range is 4.4 ° C (about 0 ° to about 400 ° F). Preferably, the contact temperature is from about 10.0 to about 176.7 ° C (about 5 ° C).
0 ° to about 350 ° F.), and most preferably 1 °.
The range is from 5.6 ° to 162.8 ° C (60 ° to 325 ° F).

In the step of removing ASO by bringing the treated sulfone-containing mixture into contact with an adsorbent, if a low concentration of a hydrogen halide compound, particularly hydrogen fluoride, is also present in the mixture, activated carbon that selectively removes ASO from the mixture is used. It has been determined that it has the effect of reducing the capacity of the sorbent. As illustrated in the data shown in FIG. 2, even low concentrations of hydrogen fluoride in the sulfone-containing fluid contacted with the activated carbon material have the effect of essentially nullifying ASO removal of carbon. Thus, one important and potentially important aspect of the present invention is that the sulfone-containing mixture that is contaminated with ASO has substantially no hydrogen fluoride concentration, or more generally, the ASO-contaminated sulfone. Neutralizing the contained mixture before contacting it with the carbonaceous material or before co-currently contacting the mixture. Any suitable means can be used to remove at least a portion, preferably a significant portion, of the hydrogen halide from the ASO-contaminated sulfone-containing mixture or composition. Alternatively, any suitable neutralizing agent can be used to remove at least a portion of the hydrogen halide contained in the ASO-contaminated sulfone-containing mixture. Examples of such suitable neutralizing agents include, but are not limited to, KO
Basic hydroxides of alkali and alkaline earth metals such as H, Ca (OH) ₂ and NaOH; basic oxides such as zinc oxide and tin oxide; amphoteric oxides such as aluminum oxide; Sex bases. Preferred neutralizing agents include various types of alumina, hydroxides and reversible bases, but the most preferred neutralizing material is γ
-Alumina or a reversible base.

"Reversible base" as used herein
The term "reversible base" refers to a polymer having an aromatic or pendant nitrogen atom having one or more nitrogen atoms, in which the salt formed by the nitrogen atom and the strong protic base has a decomposition temperature of the nitrogen compound. The nitrogen atom is sterically hindered at lower temperatures to dissociate into the nitrogen compound and the protic acid.

A preferred reversible base is:

Embedded image

A compound corresponding to one of the following: or

[0041]

Embedded image

This is a polymer-containing unit corresponding to one of the following.

(Where R¹Is in each case separately C_2-20
Alkyl, C_6-20Aryl, C_7-20Alkaryl, C
_7-20Aralkyl or C_3-20A cycloalkyl,
At the time, C _2-20Alkyl, C_6-20Aryl, C_7-20Aral
Kill, C_7-20Alkaryl or C_3-20Cycloalkyl
Is halo, nitro, cyano, C_1-20Alkoxy, C_6-20
Aryloxy, C_7-20Alkaryloxy or C
_7-20Unsubstituted or substituted by aralkoxy;
R^TwoAnd R^ThreeIs in each case separately_1-20Alkyl,
C_6-20Aryl, C_{7- 20}Alkaryl, C_7-20Aralki
Le, C_3-20Cycloalkyl, nitro, cyano, halo, C
_1-20Alkoxy, C_6-20Aryloxy, C_7-20Arca
Reeloxy or C_7-20Aralkoxy, this
When C_1-20Alkyl, C_6-20Aryl, C _7-20alkali
, C_7-20Arakill, C_1-20Alkoxy, C_6-20Ants
Oxy, C_7-20Alkaryloxy, C_7-20Aral
Coxy or C_3-20Cycloalkyl groups are halo, nitro
B, cyano, c_1-20Alkoxy, C_6-20Aryloxy
Si, C_{7- 20}Alkaryloxy or C_7-20Aralkoki
Unsubstituted or substituted by a;
B is independently an integer from 0 to 4; b is in each case
Is an integer from 0 to 3; c is each independently 0 or
Is 1; and d is each independently an integer from 0 to 2
It is. )

Examples of preferred reversible bases include 2,4,6
-Tri-t-butylpyridine, 2,6-di-t-butyl-4-methylpyridine, 2,6-di-t-butylpyridine, 2-t-butylpyridine, 2-benzylpyridine,
2,6-diphenylpyridine, 2-phenylpyridine,
2,6-dimethoxypyridine, 2-phenoxypyridine, 2,6-phenoxypyridine, 2-methylquinoline, 6-methylquinoline, 7,8-benzoquinoline and the like are included. More preferred reversible bases include 2,4
6-tri-t-butylpyridine, 2,6-di-t-butyl-4-methylpyridine, 2,6-di-t-butylpyridine, 2-t-butylpyridine, 2-benzylpyridine, 2,6 -Diphenylpyridine, 2-phenylpyridine, 2-phenoxypyridine, 2,6-diphenoxypyridine and 2,6-dimethoxypyridine.

The polyvinyl pyridine resin useful in the present invention includes a homopolymer of a vinyl pyridine compound having an appropriate steric hindrance, a vinyl pyridine compound and a 1,2- such as styrene, divinylbenzene, ethylene or vinyl chloride. Copolymers with ethylenically unsaturated compounds are included. Further, vinylpyridine can be polymerized with two or more such 1,2-ethylenically unsaturated compounds. Such polymerization methods are well known in the art. For example, U. of D'Aelio. S. P.
2,623,013; Kirk-Othmer Enc
ycropedia of Chemical Tec
hnology . 3rd Ed. Vol 21.81
See pages 6-817, and Vol 19.475-476. These publications are incorporated herein by reference.

In the above formula, R ¹ is preferably C _3-10 alkyl, C _6-10 aryl, C _7-10 alkaryl, C _7-10 aralkyl, C _5-10 cycloalkyl, C ₆ -alkyl. _Ten
Aryloxy and _C7-10 alkaryloxy. More preferably, R ¹ is C _3-10 alkyl, C _7-10
Alkaryloxy, C _6-10 aryloxy or C _6-
It is ₁₀ aryl; most preferably, R ¹ is isopropyl, isobutyl, t- butyl, phenoxy or phenyl. R ² is preferably halo or C _1-10 alkyl. More preferably, R ² is C _1-3 alkyl. R ³ is preferably C _2-10 , C _6-10 aryloxy or C _7-10 alkaryloxy. More preferably, R ³ is C _3-10 alkyl, phenoxy or phenyl. Most preferably, R ³ is isopropyl, isobutyl, t- butyl, phenoxy or phenyl.
Preferably, a is an integer from 0 to 2, most preferably 0 or 1. Preferably, b is an integer of 0 or 1. Preferably d is an integer of 0 or 1.

Other reversible bases that can be suitably used as part of the process described herein are:

[0048]

Embedded image

Wherein R is independently in each case hydrogen or C _1-20 alkyl, X is a halogen ion, preferably R is a methyl group and X is chlorine.

This is equivalent to one of the following.

That is, in addition to the polyvinylidene resin,
The most useful resin material in the present invention is an amine-substituted styrene divinylbenzene copolymer.

Thus, polyvinylpyridine materials or resins and amine-substituted styrene divinylbenzene copolymer materials or resins useful as reversible bases of the present invention generally include styrene having a nitrogen-containing group attached during or after polymerization. / Divinylbenzene copolymer. The basic functional group is attached to the polymer backbone by either a carbon-carbon bond, such as, for example, divinylpyridine, or a carbon-nitrogen bond, such as, for example, a dialkylamine or trialkylammonium hydrohalide resin. The basic functional group can be incorporated into the polymer by any conventional method known in the art. Preferred reversible bases suitable for use in the present invention are in solid particulate form under standard conditions and are selected from the group consisting of polyvinyl pyridine, amine-substituted styrene divinyl benzene copolymers and mixtures thereof. But,
The most preferred reversible base is selected from the group consisting of poly- (2-vinylpyridine), poly- (4-vinylpyridine) and mixtures thereof.

The reversible base used in the present invention is 90%
It is desirable to have a purity of at least 95%, most preferably at least 99% by weight. The boiling point of these bases should be at least 20 degrees above the thermal dissociation temperature, preferably under dissociation conditions.

One of the problems associated with the use of many types of neutralizing agents is their non-renewable nature. When many neutralizing agents are used to remove hydrogen halide from a liquid medium, especially a sulfone-containing mixture containing a sulfone component and ASO, it will eventually be used up; Is required. Regeneration is possible due to a number of known disadvantages associated with the use of non-renewable neutralizer materials,
It is desirable to use a substance that can be repeatedly reused. Thus, the reversible base described herein is a preferred neutralizing agent or contact material for removing hydrogen halide from an ASO-contaminated sulfone-containing mixture or a sulfone-containing mixture containing a sulfone component and ASO.

Important aspects of the invention described herein include:
It also includes the use of the reversible base's physical property advantages, such as utilizing the reversible base as a neutralizer material for removing hydrogen halide from the sulfone-containing mixtures described herein. It has been found that such reversible bases also have some adsorptive properties.

Thus, when a liquid medium containing ASO, such as an ASO-contaminated sulfone-containing mixture, is contacted with a reversible base, such as poly (vinyl pyridine), at least a portion of the ASO component is deposited on the reversible base. It is removed from the sulfone-containing mixture by adsorption. Over time, the hydrogen halide and AS removed from the sulfone-containing mixture
In the combination of O adsorption, the reversible base is used up and therefore needs to be regenerated.

One of the traditional methods known for the regeneration of spent reversible bases previously exposed to a liquid medium containing a strong protic acid is to apply thermal energy to the resulting salt, In this method, the salt is dissociated to release the protic acid. This traditional means for regenerating spent reversible bases, however, is not suitable after the reversible base has already been exposed to a sulfone-containing mixture containing a certain concentration of ASO. One of the reasons that thermal regeneration of spent reversible bases already contacted with a sulfone-containing mixture containing a certain concentration of ASO is inadequate is attributed to the aforementioned adsorption properties of reversible bases. I have. AS
When used as an agent for the removal of hydrogen halides from O-contaminated sulphone containing mixtures, at least a portion of the ASO concentration of the sulphone containing mixture is adsorbed by the reversible base, thus contaminating the reversible base and dissolving The effectiveness as an agent for removing hydrogen halide from a liquid medium or as a neutralizing agent is reduced.

It has been found that it is virtually impossible to remove ASO adsorbed by the reversible base by thermal means alone, and that other means are needed to remove adsorbed ASO. One such means is to expose the used reversible base to a solvent under conditions that remove at least a portion of the ASO adsorbed by the reversible base. Preferably, exposing the reversible base to a solvent removes a significant portion of the ASO adsorbed by the reversible base.

Any solvent can be used to expose or contact the spent reversible base, provided that the solvent is suitable for removing at least a portion of the adsorbed ASO, or a significant portion of the adsorbed ASO. Such suitable solvents include A
SO is a solvent that is soluble and is selected from the group consisting of alcohols, aliphatic hydrocarbons, alkyl halides, amines, aromatic hydrocarbons, esters, glycols, glycol ethers, aromatic halides, and mixtures of two or more of these. The organic solvent selected is included.

The spent reversible base after exposure to the solvent is
Then the residual adsorbed ASO not removed by the solvent
And is exposed to a stripping fluid under conditions suitable to remove at least a portion, preferably a substantial portion, of the hydrogen halide removed from the sulfone-containing mixture. The stripping fluid may be any fluid that suitably performs the stripping function described herein, including, for example, water, hydrocarbons, and inert gases. The stripping fluid is preferably used in the gas phase. Hydrocarbons that can be suitably used as stripping fluids include methane, ethane, propane, butane, pentane, hexane, heptane, octane and mixtures of two or more thereof, with the most preferred stripping hydrocarbon being isobutane. . Nitrogen is the preferred inert stripping gas.

The conditions under which the reversible base is stripped or exposed with the stripping fluid are such that regeneration of the reversible base takes place, and generally the spent reversible base is regenerated by the use of thermal energy. Is a thermal method. Therefore, the stripping temperature is preferably about 3
7.8 ° to about 315.6 ° C (about 100 ° to about 600 °
F). When isobutane is used as a stripping fluid, a supercritical state (supercritical) is required to obtain the best regeneration result.
Use in the state) is preferred. Stripping pressure is not a critical element of the present invention and may range from about 0.1 to about 140 atmospheres.

As mentioned hereinabove, it is desirable to minimize the hydrogen halide in the ASO-contaminated sulfone-containing alkylation catalyst before contacting the resulting sulfone-containing mixture with a reversible base. Particularly when the significant portion of the sulfone-containing alkylation comprises hydrogen halide, such as when the weight ratio of hydrogen halide to sulfolane is in the range of about 1: 1 to about 40: 1, the halogenation is particularly preferred. Preferably, a major portion of the hydrogen is removed from the catalyst mixture to obtain a sulfone-containing or recovered catalyst mixture. The sulfone-containing or recovered catalyst mixture comprises, consists essentially of, or consists of a sulfone component, a hydrogen halide component, and ASO. Generally, the concentration of the hydrogen halide component in the recovered catalyst mixture is about 10% by weight, determined by multiplying the percentage of hydrogen halide to the total weight of hydrogen halide and sulfone by a factor of 100 to give%. Will be less than. It is very difficult to remove all the hydrogen halide from the catalyst mixture,
The lower concentration of hydrogen halide can be close to about 0.1% by weight, preferably the lower concentration of hydrogen halide can be less than 0.1% by weight. Thus, the concentration range of the hydrogen halide in the recovered catalyst mixture ranges from about 0.1 to about 10% by weight. However, preferably, the concentration is from about 0.1 to about 7.5% by weight, and most preferably, from about 0.1% by weight.
It is in the range of 1 to 5.0% by weight.

When a neutralizing agent or neutralizing agent is used, a significant portion of the hydrogen halide component of the recovered catalyst mixture is contacted by contacting the recovered catalyst mixture containing a concentration of hydrogen halide with the neutralizing agent. Removal produces a neutralized sulfone-containing mixture. The neutralized sulfone-containing mixture is significantly free of hydrogen halide; it will generally have a concentration of less than about 0.1% by weight. Preferably, the neutralized sulfone-containing catalyst mixture has a concentration of hydrogen halide of less than about 0.2% by weight, and most preferably 0.1% by weight.
Will be less than.

The AS not removed during the neutralization step by neutralization of the recovered catalyst mixture or the sulfone-containing mixture
The neutralized sulfone-containing mixture or the resulting treated sulfone-containing mixture would be able to be further processed to remove the O component. By contacting the neutralized catalyst with an adsorbent material suitable for removing a significant portion of the ASO component contained therein, a significant portion of the neutralized catalyst's ASO component is removed to provide a regenerated catalyst mixture or treated sulfone. A contained mixture is formed. The ASO component of the regenerated catalyst mixture or the treated sulfone-containing mixture will, in most instances, be present at a concentration of less than about 2% by weight of the total weight of the sulfone component. Preferably, the weight percent of ASO present in the treated sulfone-containing mixture will be present in an amount of about 1.0 and most preferably less than 0.1 weight percent.
The regenerated catalyst mixture or treated sulfone-containing mixture can be reused as part of a sulfone-containing alkylation catalyst mixture containing, consisting of, or consisting essentially of sulfone and hydrogen halide.

Referring to FIG. 1, an alkylation step 10 is shown schematically. A hydrocarbon feed mixture consisting of olefins and isoparaffins is introduced by conduit 14 into reactor riser 12. Reactor-riser 12
Defines a reaction zone in which the hydrocarbon mixture is contacted or mixed with a catalyst mixture comprising sulfolane and hydrogen fluoride to produce a reaction product. The olefins of the hydrocarbon feed mixture will generally consist of one or more olefins having 3 to 5 carbon atoms, and the isoparaffins of the hydrocarbon feed mixture will generally have 4 to 6 carbon atoms. . The catalyst mixture is introduced into the reactor-rise pipe 12 through a conduit 16. The mixture of hydrocarbon feed mixture and catalyst mixture is defined by a reactor riser 12 in which the reaction of the olefins of the hydrocarbon feed mixture with the isoparaffins of the hydrocarbon feed mixture produces an alkylate reaction product. Into the reaction zone. In the reaction zone, a reaction by-product ASO is also formed. The reaction effluent from the reactor riser 12 enters the settling vessel 18 from the reactor riser 12, which vessel separates the alkylate reaction product from the catalyst mixture and separates the reaction product 20 and the separation. The separation zone for producing the prepared catalyst mixture 22 is limited. The separated catalyst mixture 22 will contain a substantial amount of the alkylation reaction product, ASO.
The separated reaction product 20 passes downstream via conduit 21 for processing. The separated catalyst mixture 22 can be recycled to the reactor riser 12 via conduits 24 and 16 for reuse as the alkylation catalyst mixture. Inserted into the conduit 24 is a catalyst cooler 26, which defines a heat transfer zone for heat exchange from the separated catalyst mixture 22 to a heating medium such as water.

The separated catalyst mixture 22, sometimes referred to as a slip stream or a drag stream,
At least partially enters stripping tower 30 via conduit 28. This limits the separation zone for separating the slip stream of the separation catalyst mixture 22 into an overhead stream containing a major portion of the hydrogen fluoride contained in the slip stream and a bottom stream containing a major portion of the sulfolane component of the slip stream. I do. The bottom stream contains reaction by-products contained in the slip stream,
The main part of ASO is also included. Vaporized isobutane for stripping hydrogen fluoride from the slip stream is introduced into stripping column 30 through conduit 32. The overhead stream passes through the settling vessel 18 via conduit 34.
In this, the separated catalyst mixture 2 was used to reuse hydrogen fluoride.
2 and the isobutane for stripping is mixed with the separated reaction product 20.

The bottoms stream from the stripping column 30 enters via a conduit 36 a first contact vessel 38 containing a contact material, preferably a reversible base, most preferably a polyvinylpyridine compound. The first contact vessel 38 defines a separation zone for removing a major portion of the hydrogen fluoride contained in the bottoms stream by adsorption or neutralization or both to produce a neutralized bottoms stream or a treated sulfone-containing mixture. At least a portion of the ASO contained in the bottoms stream is also adsorbed by the contact material and thereby removed.

The neutralized bottoms stream then contains the adsorbate by conduit 40 and removes a major portion of the ASO contained in the neutralized bottoms stream to substantially contain ASO and hydrogen fluoride. Enters a second contact vessel 42 that produces a stream of regenerated catalyst or a sulfolane stream substantially free of ASO and hydrogen fluoride. This sulfolane stream enters sedimentation vessel 18 via conduit 44 where it is remixed with separated catalyst mixture 22 for reuse as the sulfolane component of the alkylation catalyst mixture. The sulfolane stream is sent downstream through conduit 45 for reprocessing, if desired.

To regenerate the contact material contained in the first contact vessel 38, conduits 46 and 48, each having valves 50 and 52, respectively, are provided to allow for periodic regeneration of the used contact material. It is prepared. The contact material in contact vessel 38 is periodically exposed to a solvent introduced into first contact vessel 38 by conduit 46, thereby removing at least a portion of the ASO absorbed by the contact material by the solvent. Exposure of contact material under such conditions. The solvent containing ASO removed from the contact material exits the first contact vessel 38 for downstream processing by conduit 48. Contacting the contact substance with the AS contained on the contact substance;
Following exposure to a solvent suitable for removing at least a portion of the O, the previously exposed contact material is exposed to a strip fluid. The stripping fluid is introduced into the first contact vessel by conduit 46 and exposes the contact material contained therein under conditions to regenerate the contact material. The stripping fluid is discharged from the first contact vessel 38 by a conduit 48.

EXAMPLE The following example illustrates the advantages of the present invention. These examples are for illustrative purposes only, and are not meant to limit the invention as set forth in the appended claims.

Example I To determine the physical properties of the ASO by-product, an ASO by-product derived from a hydrocarbon reaction catalyzed by a catalyst mixture of sulfolane and HF was obtained. The catalyst mixture used for the hydrocarbon reaction contained a weight ratio of HF to sulfolane of about 1.5 and the hydrocarbon charge contained isobutane and 2-butene (60% trans, 40% cis isomer). The molar ratio of 2-butene to about 11
Met. The reaction temperature is about 32.2 ° C. (about 90 ° F.) and the reaction pressure is about 6.33 kg / cm ² gauge (about 90 ° F.).
psig). Table I shows certain physical properties, including distillation of the resulting ASO obtained from the hydrocarbon reaction.

[0072]

TABLE 1 TABLE I sulfolane / HF catalyst mixture other physical properties Temperature ℃ distilled and ASO of ASO derived from hydrocarbon reaction catalyzed (° F) bromine number of volume percent fraction of the sample 21.1 - 93.3-(70-200) 19 51 93.3-98.9-(200-210) 8 45 98.9-107.2-(210-225) 18 56 107.2-121.1-(225-250) 15 58> 121.1 (250) 40 59 ASO Bromine number 32 API specific gravity 15.6 ° C (60 ° F) 37.1 specific gravity 15.6 ° C (60 ° F) 0.8391

EXAMPLE II This example II generally describes the carbon, alumina and their adsorption properties and the experimental method used to obtain the adsorption properties of alumina.

General experimental procedures using carbon or aluminum or both materials in the recovery of ASO from a sulfolane-containing mixture of sulfolane and ASO include a diameter of about 2.5
4 cm (1 inch) and length 30.48-60.9
The use of a 6 cm (12-24 inch) glass cylinder was included. Place either glass wool or beads on the bottom of the cylinder to support the active substance, place either glass wool or beads on the top of the active substance and place the sulfolane-containing mixture on the active substance on the active substance. The distribution was averaged. The glass cylinder was heated, if desired, to facilitate the flow of the sulfolane-containing mixture through the bed of active material. The sulfolane-containing mixture had a weight ratio of sulfolane to ASO of about 9: 1. The color of the resulting filtrate was an indicator of the spent active substance adsorption capacity and was therefore monitored to determine when the experiment was complete.

Example III In this example III, a mixture of sulfolane and ASO from a sulfolane-containing mixture of sulfolane and ASO as a function of the concentration of hydrogen fluoride in the
2 illustrates an unexpected relationship between the ability of activated carbon to adsorb SO.

The experimental procedure used to obtain the data shown in Table II was substantially the same as that shown in Example II. Various concentrations of hydrogen fluoride in the sulfolane-containing mixture were determined before contacting the mixture with activated carbon material. The data obtained are shown in Table II and illustrate that the level of acid concentration in the sulfolane-containing mixture has an unexpectedly large effect on the ASO adsorption capacity of activated carbon. These data are also plotted in FIG.

[0077]

TABLE II The ability of activated carbon to adsorb ASO from a sulfolane-containing mixture with a 9: 1 sulfolane to ASO ratio as a function of HF concentration HF concentration in the sulfolane-containing mixture Carbon absorption capacity Weight of HF % ASO on carbon% by weight 0.02 50 0.10 19 0.50 4 1.00 Nil

Example IV This example IV illustrates that various commercially available aluminas can be suitably used to remove HF from a mixture of sulfolane and ASO either by adsorption or neutralization. This example also illustrates that alumina can perform a neutralizing function while adsorbing some of the ASO contained in the sulfolane-containing mixture.

To obtain the data shown in Table III, substantially as described in Example II except that the pH of the effluent from the cylinder was monitored to determine when the neutralizing capacity of the alumina was reached. A similar experimental procedure was used. The sulfolane-containing mixture contained HF at a concentration of 5% by weight. The data presented in Table III also illustrate that various commercially available aluminas can be suitably used to neutralize sulfolane-containing mixtures with some ASO adsorption prior to contacting the neutralized mixture with activated carbon. Have been.

[0080]

TABLE III Ability of various aluminas to neutralize and remove ASO from a sulfolane-containing mixture with a 9: 1 weight ratio of sulfolane to ASO Neutralization capacity ASO adsorption capacity Type of alumina (meq ^* HF / g) (mg / g) LaRoche Alumina A-202 1.8 50 Alcoa Alumina HF-200 5.0 150 Engelhard Activated Bauxite “Sure cat” 1.3 35 LaRoche SAS Alumina 4.1 120

^* Meq represents milliequivalent.

Example V This example V illustrates that polyvinylpyridine reversibly adsorbs and desorbs HF from a mixture of sulfolane and ASO. This example also illustrates that polyvinyl pyridine performs a neutralizing function and at the same time can partially adsorb ASO from the sulfone-containing mixture.

The experimental method used in this example is as follows:
Substantially the same method as described in Examples II and IV was used, except that a metal reactor was used instead of a glass cylinder to withstand pressures up to 18 kg / cm ² gauge (600 psig). In addition, the process and regeneration fluid were pumped through the bed instead of flowing by gravity.

90/10 (volume) sulfolane / ASO
The mixture of + 5% HF was added to a 50 ml Reillex maintained at 37.8 ° C. (100 ° F.) and ambient pressure.
^Pumped onto a ^TM 425 polyvinyl pyridine bed. The mixture was pumped onto the polymer at a rate of 20 ml / hour. About 10 before the pH of the effluent drops below 4.0
8 ml of effluent were collected. The mixture feed was stopped and the bed temperature was reduced to about 300 ° F (148.9 ° C) and the pressure was reduced to 3 ° C.
8.66 kg / cm ² gauge (550 psig). Isobutane was passed over the polymer at a rate of 30 ml / hour and under the conditions described above. The isobutane effluent was initially quite dark and very acidic. Isobutane pumping was continued until the pH of the effluent was above 6.0. At this point, the temperature and pressure are reduced to their initial state and the sulfolane / ASO
The / HF mixture was pumped back onto the polymer. In the second contact of the mixture with polyvinylpyridine, 100 ml of effluent was collected before the effluent pH dropped below 4.0, indicating that regeneration with isobutane was very effective. I have.

The calculation of the amount of HF and ASO removed from the polyvinylpyridine bed and obtained during the regeneration step was determined to be about 5 mmole HF / g polymer and about 5 mmole HF / g polymer, measured cumulatively over the entire adsorption portion of the cycle. This indicates that about 80% of the ASO in the original sample mixture was adsorbed.

EXAMPLE VI This example VI illustrates that an amine-substituted styrene divinylbenzene copolymer reversibly adsorbs and desorbs HF from a mixture of sulfolane and ASO. This example also illustrates that the amine-substituted styrene divinylbenzene copolymer can also perform a neutralizing function while adsorbing some of the ASO contained in the sulfone-containing mixture.

The experimental method used in this example was as follows:
A method substantially similar to that described in Examples II and IV was used except that a metal reactor was used instead of a glass cylinder to withstand pressures up to 18 kg / cm ² gauge (600 psig). In addition, the process and regeneration fluids were pumped into the bed instead of flowing by gravity.

90/10 (volume) sulfolane / ASO
+ 5% HF mixture at about 37.8 ° C. (about 100 ° F.)
And 80 ml Rohm maintained at ambient pressure
& Haas Amberlyst A-21, pumped onto a bed of amine-substituted styrene divinylbenzene copolymer. The mixture was pumped over the polymer at a rate of 30 ml / hour. About 365 ml of effluent was collected before the effluent pH dropped below 4.0. The supply of the mixture was stopped and the resin was regenerated.

In the calculation of the amount of HF and ASO obtained when the resin bed was removed and obtained during the regeneration step, the polymer, measured cumulatively over the entire adsorption portion of the cycle, was about 5 m
It showed that about 70% of the ASO in the mole HF / g polymer and the original sample mixture had been adsorbed. FIG. 3 shows the results of the adsorption test. The time at which there was a hydrogen fluoride leak in the experiment was taken as the point of the 100% experiment in FIG.
Shown in The percentage of ASO remaining refers to the amount of ASO contained in the feed removed by the resin and not passing into the bed effluent. As illustrated in the adsorption curve, A
SO adsorption and hydrogen fluoride neutralization occurred simultaneously.

While the invention has been described in terms of the presently preferred embodiments, those skilled in the art will recognize that reasonable modifications and improvements are possible. Such variations and modifications are within the scope of the described invention and the appended claims.

[Brief description of the drawings]

FIG. 1 (diagram) is a schematic diagram of one embodiment of the method of the present invention.

FIG. 2 (Graph) H contained in the sulfone-containing mixture
3 is a plot illustrating the ability of activated carbon to adsorb ASO from the mixture as a function of the weight percent of F.

FIG. 3 (Graph) Adsorption curves of ASO by aliphatic amine-substituted polymers used for simultaneous removal of ASO and HF from sulfolane containing ASO and HF.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI / C07B 61/00 300 C07B 61/00 300 (72) Inventor Robert Bruce Eldridge Kingston Drive, Bartles Building, Oklahoma, USA 2808 (56) References JP-A-6-198200 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 21/00-38/00 B01D 15/00

Claims (9)

(57) [Claims] 1. A sulfone component and an acid-soluble oil (AS)
O) comprising removing the ASO from a sulfone-containing mixture comprising at least one of the following steps: removing the ASO component from the sulfone-containing mixture under conditions suitable for removing at least a portion of the ASO component from the sulfone-containing mixture. -The method for removing ASO as described above, wherein the ASO is brought into contact with a particulate solid of a reversible base which is a copolymer of substituted styrene and divinylbenzene, or a mixture of the reversible bases. 2. The method according to claim 1, wherein the reversible base is poly- (2-vinylpyridine), poly- (4-vinylpyridine) or a mixture thereof. 3. The method according to claim 1, wherein the sulfone component of the sulfone-containing mixture is sulfolane. Wherein said sulfone-containing mixture The method according to any one of claim 1 3, further comprising a hydrogen halide component. 5. The method of claim 1, wherein prior to said contacting, a hydrogen halide component is present in said sulfone-containing mixture in an amount of less than about 10% by weight of the total weight of said hydrogen halide and sulfone components; 5. The method of claim 4 , wherein the ASO in the containing mixture is present in an amount up to about 20% by weight of the total weight of the hydrogen halide and sulfone components. 6. A step of exposing said reversible base to said solvent under conditions such that at least a portion of the ASO adsorbed by said reversible base is removed by said solvent during said contacting. The method according to any one of claims 1 to 5 , further comprising: 7. The method of claim 6 , comprising exposing said reversible base to a stripping fluid under stripping conditions that regenerate said reversible base. 8. The treated sulfone-containing mixture is contacted with an adsorbent that is carbon, thereby removing the additional portion of the ASO from the treated mixture to produce a substantially ASO-free sulfone-containing mixture. The method according to any one of claims 1 to 7 , further comprising a step. 9. An alkylated carbonized mixture comprising contacting a hydrocarbon mixture comprising an olefin and isoparaffin with a catalyst mixture comprising the hydrogen halide component and the sulfone component in a reaction zone. 5. The process of claim 4 wherein said alkylation step comprises forming an alkylation reaction mixture comprising said catalyst mixture containing hydrogen and at least a portion of ASO formed as a by-product in the alkylation step. The method according to any one of claims 1 to 8 .