JPH06190288A - Method of removing acid soluble oil from sulfone containing mixture - Google Patents

Abstract

PURPOSE: To remove acid-soluble oil accumulated in an alkylation catalyst contg. a sulfone compd. and a hydrogen halide by bringing the alkylation catalyst into contact with a reversible base such as polyvinylpyridine under conditions suitable for removing at least one part of acid-soluble oil. CONSTITUTION: Acid-soluble oil formed as a by-product in an alkylation catalyst contg. a sulfone compd. and a hydrogen halide which are used for alkylation of olefinic hydrocarbons by means of isoparaffinic hydrocarbons is removed. For it, the above-mentioned catalyst is brought into contact with a reversible (reusable) base which being polyvinylpyridine, amine-substd. styrene divinylbenzene copolymer or mixtures thereof under conditions suitable for removing at least one part of acid-soluble oil from the above-mentioned catalyst in a first contacting vessel 38. Further, the above-mentioned base can be regenerated separately and reused.

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 consisting of a sulfone compound used in the alkylation of an olefinic hydrocarbon with an isoparaffinic hydrocarbon and a hydrogen halide.

[0002]

2. Description of the Related Art As disclosed in our application Japanese Patent Application No. 5-104546 filed 5.4.30 and our application Japanese Patent Application No. 5-104547 filed hei.
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, or alkylates. Alkylation reaction products generally contain 7 or more carbon atoms and are highly desirable gasoline blend components due to their high octane number as an automotive fuel.

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

[0004]

Contrary to the process of using the above-mentioned novel catalysts consisting of a sulfone component and hydrogen halide, the conventional alkylation process using hydrogen fluoride (HF) as a catalyst is a continuous alkylation process. There are certain known methods used to remove ASO from the HF catalyst used in the oxidization process. In particular, a sufficient amount of HF catalyst used in the alkylation step is treated or regenerated so that the amount of ASO can be removed at about 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 HF is stripped from ASO with a vaporized hydrocarbon such as isobutane,
It is passed as part of the vapor phase overhead from the stripping vessel and the ASO is conducted by passing it as a bottom stream to the stripping vessel for further processing.

The conventional alkylation catalyst regeneration method is the conventional H
Although well used in the regeneration of F catalysts, conventional means cannot be used to regenerate alkylation catalysts containing sulfone components. This is because the boiling range of ASO overlaps with that 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,
It is necessary to separate ASO from the sulfone in order to recover the sulfone for reuse as a catalyst in the alkylation process.

[0006]

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. A sulfone-containing mixture comprising sulfone and ASO is reversible base (rev) under conditions suitable to remove at least some of the ASO components from the sulfone-containing mixture.
The treated sulfone-containing mixture is produced by contacting with ersible base).

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

The acid-soluble oil of the present invention comprises an alkyl comprising the step of contacting a hydrocarbon mixture of an olefin and isoparaffin with an alkylation catalyst which comprises, or consists essentially of, a hydrogen halide component and a sulfone component. It is produced as a reaction by-product in the chemical conversion method. The term “acid-soluble oil” or “ASO” as used herein and in the appended claims refers to a bound polymer that is a highly olefinic oil produced by the acid-catalyzed reaction of a hydrocarbon. Is the meaning. For an extensive description and characterization of certain bound polymeric oils, see M.
iron and Lee by Journal of
Chemical and Engineering
Data Volume 8. No. 150 to 1 of 1
Page 60, "Molecular Structure
of Conjunct Polymers ". This document serves as a reference for this specification. A
The physical properties of SO depend on the particular hydrocarbons being treated, the catalyst used in the process, feed contaminants such as hydrogen sulfide, butadiene, oxygenates and other compounds, and alkylation process reaction conditions. To do. Thus, in a more narrow definition of this term, ASO comprises a by-product in the catalytic reaction of mono-olefins with isoparaffins using a catalyst mixture consisting of, or consisting essentially of, a sulfone component and a hydrogen halide component. It may be a combined polymer produced as. Preferred monoolefins suitable for use in catalysis are those having 3 to 5 carbon atoms and preferred isoparaffins are 4 to 6
It has one carbon atom. The preferred sulfone component is sulfolane and the preferred hydrogen halide component is hydrogen fluoride.

The ASO by-product derived from the hydrocarbon reaction catalyzed by a sulfone-containing alkylation catalyst is generally about 0. 0, using water at 15.6 ° C (60 ° F) as a reference. 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 within the range of.

The hydrogen halide component of the catalyst composition or catalyst mixture includes hydrogen fluoride (HF), hydrogen chloride (HCl),
It can be chosen from compounds consisting of hydrogen bromide (HBr) and mixtures of two or more of these. However, although the preferred hydrogen halide is hydrogen fluoride which can be used in anhydrous form in the catalyst composition, the hydrogen fluoride used generally contains a small amount of water. In the catalyst composition containing the hydrogen fluoride component and sulfolane, no more than about 30 weight percent of the total weight of the hydrogen fluoride component including water is present. Preferably, the amount of water present in 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 of the catalyst composition of the present invention, and more particularly the hydrogen fluoride component, these terms refer to the hydrogen halide component as 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 the ratio of the weight of water to the total weight of water and hydrogen halide multiplied by a factor of 100 to give the weight ratio in%.

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

[0012]

## STR1 ## 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, ethylmethyl sulfone and SO _2.
Included are cycloaliphatic sulfones in which the group is attached to the hydrocarbon ring. In such cases, R and R ′ together form a branched or unbranched divalent moiety preferably containing from 3 to 12 carbon atoms. Of the latter, tetramethylene sulphone or sulpholane, 3-methyl sulpholane and 2,4-dimethyl sulpholane are particularly preferred as they offer the advantage of being liquid under the process operating conditions relevant to the present invention. These sulfones can also have substituents, such as chloromethylethyl sulfone, in particular one or more halogen atoms. These sulfones can advantageously be used in the form of mixtures.

The alkylation catalyst used in the alkylation step in which the ASO reaction by-product is produced 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 a hydrocarbon mixture is contacted with an alkylation catalyst having sulfolane as the sulfone component and hydrogen fluoride as its hydrogen halide component. Good alkylation when the alkylation catalyst consists of sulfolane and hydrogen fluoride 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 3: 1 to
The range is 9: 1.

In order to improve the selectivity of the alkylation reaction of the present invention towards producing the desired highly branched hydrocarbons having 7 or more carbon atoms, the stoichiometry is substantially within the reaction zone. The presence of more than the stoichiometric amount of isoparaffin is desirable. A molar ratio of isoparaffin hydrocarbons to olefinic hydrocarbons of 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 8-15. However, while the ranges quoted above with respect to the isoparaffin to olefin molar ratio are commercially practicable ranges, in general, the higher the isoparaffin to olefin molar ratio in the alkylation reaction, the higher the corresponding ratio obtained. The quality of alkylate is good.

Alkylation reaction temperatures within the ranges contemplated by the present invention range from about -17.8 ° to about 65.6 ° C (about 0 ° to
In the range of 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. 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 with commercially attractive reaction rates. But,
Most preferably, the alkylation temperature is 10.0 ° -4
It is in the range of 8.9 ° C (50 ° to 120 ° F).

The reaction pressure contemplated by the present invention is in the range of pressures sufficient to maintain the reactants in the liquid phase up to about 15 atmospheres. Since the reactant hydrocarbons will normally be gaseous at the alkylation reaction temperature, 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 the reactants are in the liquid phase, the increased pressure has no significant effect on the alkylation reaction.

The contact time of the hydrocarbon reactants 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 sufficient to be given. Preferably, the contact time is in the range of 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 comprises about 40-90% by volume catalytic phase and about 60-10% by volume.
In the alkylation step of the present invention comprising about 1 to about 200 volumes of olefin / hour / volume catalyst in the alkylation step of the present invention, wherein the good contact between 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 isoparaffins and olefins used, the particular composition of the alkylation catalyst and the alkylation reaction conditions. Therefore, the preferred contact time is to provide an olefin space velocity within the range of about 0.1-200 (v / v / hr) and to obtain essentially complete conversion of the olefin reactant within the alkylation zone. Enough time to be taken.

The alkylation step can be carried out either batchwise or continuously, but for economic reasons the continuous step is preferred. It has been demonstrated that the tighter the contact between the feedstock and the catalyst in the alkylation step, the better the quality of the alkylate product obtained.
Keeping this in mind, when carrying out the invention in a batch operation, vigorous mechanical agitation or shaking of the reactants and catalyst is a feature of the invention.

In continuous operation, the pressures and temperatures are maintained sufficient to maintain the reactants substantially in the liquid phase, which are then passed through the forced dispersion device into the reaction zone. The dispersion device may be a jet, a nozzle, a porous thimble, or the like. The reactants are subsequently mixed with the catalyst by conventional mixing means such as mechanical stirrers or turbulent flow systems. After sufficient time, the product is continuously separated from the catalyst and withdrawn from the reaction system at the same time,
The partially spent 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 containing a sulfone component and ASO is treated by contacting it with a contact material suitable for removing at least a portion of the ASO component of the sulfone-containing mixture. Removing the ASO from the sulfone-containing mixture, which comprises the step of forming a sulfone-containing mixture. The sulfone-containing mixture of the process according to the invention can also consist of a sulfone component, a hydrogen halide component and ASO. The contact substance is
May be any of the materials described herein, and alumina, carbon,
And substances selected from the group consisting of and mixtures thereof as well as 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, this ASO concentration will be less than about 15% by weight of the sulfone component, most preferably 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, this weight% being the weight fraction of hydrogen halide to the total weight of sulfone and hydrogen halide. Is multiplied by a factor of 100 to obtain the%. However, in general, the concentration range of hydrogen halide in the sulfone-containing mixture is about 0.1 to about 10% by weight.
Is the range. However, preferably, the concentration is about 0.1
In the range of about 7.5 weights, most preferably 0.1 to
It is in the range of 5.0% by weight.

An embodiment of the invention wherein the sulfone-containing mixture is contacted with a contact material to remove at least a portion of the hydrogen halide of the sulfone-containing mixture to obtain a treated sulfone-containing mixture having a reduced concentration of hydrogen halide is an essential condition. But not 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 wt%, preferably less than about 0.2 wt%, and most preferably Is less than 0.1% by weight.

The treated sulfone-containing mixture also typically has less than about 5% by weight of the treated sulfone-containing mixture of ASO.
Has 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 ASO is present in an amount less than 1% by weight.

In another embodiment of the process of the present invention, a mixture of sulfone-containing alkylation catalysts containing a sulfone component, a hydrogen halide component and ASO is included in the mixture A.
It contemplates solving the problems associated with regeneration of the catalyst mixture by removing at least a portion of SO. Accumulation of ASO in a sulfone-containing alkylation catalyst occurs when the catalyst is continuously reused in the alkylation process. In a continuous alkylation process, the ASO reaction by-products, if not removed, will accumulate in the catalyst to unacceptable concentrations which negatively impact 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 wt% 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 above about 10% by weight of catalyst are believed to adversely affect catalyst performance. ing. Therefore, 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 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 contacting substance, whereby ASO
At least a portion, preferably a substantial portion, of the sulfone-containing alkylation catalyst mixture prior to removing at least a portion of the components or at least a portion of the hydrogen halides or both. It should be mentioned that it is preferable to remove. Thus, the sulfone-containing mixture is a sulfone-containing alkylation catalyst mixture from 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, such as evaporative separation, distillation, extraction, stripping or other suitable separation method.
One preferred method is to separate 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 consisting of the sulfone-containing mixture using isobutane vapor as a stripping agent. This is a method using stripping means.

The concentration of the hydrogen halide component in the sulfone-containing mixture is the weight percent of the mixture determined by multiplying the fraction of hydrogen halide to the total weight of hydrogen halide and sulfone by a factor of 100 to obtain%. It will be less than about 10% by weight. However, since it is very difficult to remove the entire amount of hydrogen halide in the mixture, the lower limit of hydrogen halide from a commercially viable point of view is about 0.
It is to approach 1% by weight, and preferably the concentration is 0.1.
It is to be less than 1% by weight. Therefore, the concentration of hydrogen halide in the sulfone-containing mixture is about 0.1 to about 10
It is in the range of% by weight. However, preferably the 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 the specification, the treated sulfone-containing mixture is preferably admixed with an adsorbent selected from the group consisting of carbon, alumina and mixtures thereof in the second contacting step with the ASO contained therein. Are further contacted under conditions suitable to remove at least a portion of
However, removing a substantial portion of the ASO therein by contacting the treated sulfone-containing mixture with an adsorbent material to generally provide a mixture having an ASO concentration of less than about 2% by weight of the substantially ASO-free sulfone-containing mixture. Is preferred. Preferred ASO concentrations are less than about 1% by weight, most preferably ASO is present in an amount less than 0.1% by weight.

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

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

The carbon adsorbent material is any activated carbon material suitable for selective removal of at least a portion of the ASO components contained in the use and treated sulfone-containing mixture as contemplated by the present invention. . Activated carbon adsorbent is
"Standard TestMethod for
Surface Area of Catalyst
Approximately 300-measured by American Society for Testing and Materials (ASTM) standard test method D3663-84 entitled "s".
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 is incorporated herein by reference and is part of the reference. Furthermore, the activated carbon adsorbent is "Standard Te
st Method for Determining
Pore Volume Distribution
of Catalysts by Measure Int
AS under the heading "Russion Porometry"
It can also be characterized by its pore diameter in the range of about 10 to about 50 μm as measured by the mercury indentation porosimetry described in TM Standard Test D4284-88. Standard Test Method D4284-88 is hereby incorporated by reference and is part of the reference. The use of commercially available activated carbon is generally desirable. One such suitable commercially available activated carbon is, for example, Calgon Car.
Calgon Filtersorb 400 manufactured and sold by bon Corporation
It is a known product under the brand name of.

The alumina adsorbent material is included in the used and treated sulfone-containing mixture contemplated by the present invention.
It may be any alumina suitable for use as a neutralizing agent for the selective removal of at least a portion of the SO component or the removal of at least a portion of the hydrogen halide of a sulfone-containing fluid. Such suitable aluminas include, for example, a number of commercially available activated aluminas and calcined aluminas. Generally, the alumina material is ASTM D366.
It has a surface area in the range of about 150 to about 500 m ² / g, measured at 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
Another alumina such as (Chi) -alumina.

The process conditions for contacting the treated sulfone-containing mixture with the adsorbent composition are:
Any condition suitable or effective to remove at least a portion of the concentration of SO may be used. The removal efficiency of the adsorbent substance is considered not to be highly dependent on the contact pressure because the adsorption phenomenon is considered to be the result of liquid-solid interaction, but the process pressure is about 0.5 atm. (Absolute pressure) should be exceeded, in the range of about 30 atmospheres (absolute pressure) or higher. More common working pressures typically range from about atmospheric pressure to about 14.1 kg / cm ² gauge (200 psi).
It will be in the range of g).

With respect to the contact temperature, any suitable temperature can be used which allows effective removal of at least a portion of the ASO from the treated sulfone-containing mixture. 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 mixture. Considering the lower limit temperature, pure sulfolane is about 27.4 ° to 27.8 ° C (about 81.3 to 82.
A melting point of 0 ° F.), but when the sulfolane is a mixture of water and hydrogen fluoride, this melting point is much lower.
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 ASO and the temperature at which the sulfone component of the mixture begins to pyrolyze. That is, the upper limit of contact temperature is about 204.4 ° C (about 400 ° F).
Therefore, the contact temperature is generally 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
0 ° to about 350 ° F), most preferably 1
The range is from 5.6 ° to 162.8 ° C (60 ° to 325 ° F).

In the step of removing ASO by contacting the treated sulfone-containing mixture with an adsorbent, activated carbon that selectively removes ASO from the mixture when low concentrations of hydrogen halide compounds, especially hydrogen fluoride, are also present in the mixture. It has been determined to have the effect of reducing the capacity of the adsorbent. As illustrated in the data shown in FIG. 2, even low concentrations of hydrogen fluoride in a sulfone-containing fluid contacted with activated carbon material have the effect of essentially abolishing ASO removal of carbon. Accordingly, one of the important and potentially significant aspects of the present invention is that the sulfone-containing mixture contaminated with ASO is substantially free of hydrogen fluoride concentration, or more generally ASO contaminated sulfone. Neutralizing the containing mixture prior to contacting with the carbonaceous material or prior to cocurrent contact with 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 neutralizing agent suitable for removing at least a portion of the hydrogen halide contained in the ASO contaminated sulfone-containing mixture can be used. Examples of such suitable neutralizing agents include, but are not limited to, KO
Alkaline and alkaline earth metal basic hydroxides such as H, Ca (OH) ₂ and NaOH; basic oxides such as zinc oxide and tin oxide; amphoteric oxides such as aluminum oxide; and reversible. Includes a base. Preferred neutralizing agents include various types of alumina, hydroxides and reversible bases, with the most preferred neutralizing agent being γ
-Alumina or a reversible base.

As used herein, a "reversible base"
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 a strong protic base is the decomposition temperature of the nitrogen compound. The nitrogen atom is sterically hindered so that it is dissociated into a nitrogen compound and a protic acid at a lower temperature.

Suitable reversible bases are:

[Chemical 2]

A compound corresponding to one of the following; or the following formula:

[0041]

[Chemical 3]

A polymer-containing unit corresponding to one of the above.

(In the formula, R¹Is in each case separately C_2-20
Alkyl, C_6-20Aryl, C_7-20Alkaryl, C
_7-20Aralkyl or C_3-20Cycloalkyl
At the time of 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;
R²And R³Is in each case separately C_1-20Alkyl,
C_6-20Aryl, C_{7- 20}Alkaryl, C_7-20Aralchi
Le, C_3-20Cycloalkyl, nitro, cyano, halo, C
_1-20Alkoxy, C_6-20Aryloxy, C_7-20Arca
Reel Oxy or C_7-20This is Aralkoxy
When C_1-20Alkyl, C_6-20Aryl, C _7-20alkali
C_7-20Arakil, C_1-20Alkoxy, C_6-20Ants
Roxy, C_7-20Alkaryloxy, C_7-20Aral
Coxy or C_3-20Cycloalkyl groups are halo and nit
B, cyano, C_1-20Alkoxy, C_6-20Aryl Oki
Shi, C_{7- 20}Alkaryloxy or C_7-20Araloki
Unsubstituted or substituted by Si; a is
, Each is independently an integer from 0 to 4; b is in each case separately
Is an integer from 0 to 3; c is in each case separately 0 or
Is 1; and d is in each case separately an integer from 0 to 2
Is. )

Examples of preferred reversible bases are 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 are 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.

Polyvinyl pyridine resins useful in the present invention include homopolymers of vinyl pyridine compounds with suitable steric hindrance, vinyl pyridine compounds and 1,2-, such as styrene, divinyl benzene, ethylene, vinyl chloride and the like. Copolymers with ethylenically unsaturated compounds are included. Additionally, vinyl pyridine can be polymerized with two or more such 1,2-ethylenically unsaturated compounds. Such polymerization methods are well known in the art. For example, the D. Aelio U. S. P.
2, 623, 013; Kirk-Othmer Enc.
ycropedia of Chemical Tec
hology . 3rd Ed. Vol 21.81
See pages 6-817 and Vol 19.475-476. These publications are incorporated herein by reference.

In the formulas shown above, 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- Ten}
Aryloxy and C _7-10 alkaryloxy. More preferably, R ¹ is C _3-10 alkyl, C _7-10
Alkaryloxy, C _6-10 aryloxy or C _6-
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 may be suitably used as part of the processes described herein are:

[0048]

[Chemical 4]

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

Is equivalent to one of

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

Thus, the polyvinylpyridine materials or resins and amine-substituted styrene divinylbenzene copolymer materials or resins useful as the reversible bases of the present invention generally have styrene having nitrogen-containing groups attached during or after polymerization. / Divinylbenzene copolymer is included. The basic functional group is attached to the polymer backbone either by a carbon-carbon bond such as divinylpyridine or a carbon-nitrogen bond such as 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 particle form at normal conditions and are selected from the group consisting of polyvinylpyridine, amine substituted styrenedivinylbenzene 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%, preferably at least 95%, and most preferably at least 99% by weight. The boiling points 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-reproducibility. Ultimately used when many neutralizing agents are used to remove hydrogen halides from liquid media, especially sulfone-containing mixtures containing sulfone components and ASO; Will be required. Regeneration is possible due to a number of known disadvantages associated with the use of non-renewable neutralizer materials,
In addition, it is desirable to use a material that can be reused repeatedly. Thus, the reversible bases described herein are preferred neutralizing agents or contact materials for the removal of hydrogen halide from ASO contaminated sulfone-containing mixtures or sulfone-containing mixtures containing ASO and sulfone components.

Important aspects of the invention described herein include:
The use of the advantages of the physical properties of reversible bases is also included, such as utilizing the reversible base as a neutralizing agent material for the removal of hydrogen halide from 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 transferred onto the reversible base. It is removed from the sulfone-containing mixture by adsorption. Hydrogen halide and AS removed from the sulfone-containing mixture over time
The combination of O adsorption makes the reversible base used up and thus requires its regeneration.

One of the traditional methods known for the regeneration of used reversible bases, which has been previously exposed to a liquid medium containing a strong protic acid, is to apply heat energy to the salt obtained, whereby This is a method of causing dissociation of a salt to release a protic acid. This traditional means for regenerating spent reversible bases, however, is unsuitable only after the reversible bases have already been exposed to a sulfone-containing mixture containing a concentration of ASO. One of the reasons why the thermal regeneration of the spent reversible base already contacted with the sulfone-containing mixture containing a certain concentration of ASO is inadequate is believed to be due to the adsorption properties of the reversible base as described above. There is. AS
When used as an agent for the removal of hydrogen halide from an O-contaminated sulfone-containing mixture, at least a portion of the ASO concentration of the sulfone-containing mixture is adsorbed by the reversible base, thus contaminating the reversible base and removing It has reduced efficacy as an agent for the removal of hydrogen halides from liquid media or as a neutralizing agent.

It has been found that it is virtually impossible to remove ASO adsorbed by reversible bases only by thermal means, and other means are required to remove adsorbed ASO. One such means is to expose the spent reversible base to a solvent under conditions that remove at least a portion of the ASO adsorbed by the reversible base. It is preferred that 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 are A
SO is a solvent in which SO 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 thereof. An organic solvent of choice is included.

The spent reversible base after exposure to the solvent is
Then the residual adsorbed ASO not removed by the solvent
Is exposed to a stripping fluid under conditions suitable to remove a substantial portion of, and at least a portion of, preferably a substantial portion of, the hydrogen halide removed from the sulfone-containing mixture. The stripping fluid can be any fluid that suitably performs the stripping function described herein, including water, hydrocarbons and inert gases. Stripping fluids are preferably used in the gas phase. Hydrocarbons suitable for use as the stripping fluid 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 the reversible base is regenerated, and the spent reversible base is generally regenerated by the use of thermal energy. It is a thermal method. Therefore, the stripping temperature is preferably about 3
7.8 ° to about 315.6 ° C (about 100 ° to about 600 °
It is within the range of F). When isobutane is used as the stripping fluid, in order to obtain the best regeneration results, the supercritical state or higher is required.
Use in a state) is preferred. Stripping pressure is not a critical element of the invention and may range from about 0.1 to about 140 atmospheres.

As previously mentioned herein, it is desirable to minimize hydrogen halide in the ASO contaminated sulfone-containing alkylation catalyst prior to contacting the resulting sulfone-containing mixture with a reversible base. Especially 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, especially halogenation. It is preferred to remove a major portion of hydrogen from the catalyst mixture to obtain a sulfone-containing mixture or a recovered catalyst mixture. The sulfone-containing mixture or recovered catalyst mixture comprises, consists of, or consists essentially 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 fraction of hydrogen halide with respect to the total weight of hydrogen halide and sulfone by a factor of 100 to yield%. Would be less than. Although it is very difficult to remove all hydrogen halide from the catalyst mixture,
The lower limit concentration of hydrogen halide can approach approximately 0.1% by weight, preferably the lower limit concentration of hydrogen halide can be less than 0.1% by weight. Thus, the concentration range of hydrogen halide in the recovered catalyst mixture is in the range of 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 0.
It is in the range of 1 to 5.0% by weight.

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

AS that was 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 could be further processed to remove the O component. A significant portion of the ASO component of the neutralization catalyst is removed by contacting the neutralization catalyst with an adsorbent material suitable for removing a significant portion of the ASO component contained therein to regenerate the regenerated catalyst mixture or treated sulfone. A containing 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 less than about 1.0 and most preferably less than 0.1 weight percent.
The regenerated catalyst mixture or the treated sulfone-containing mixture can be reused as part of a sulfone-containing alkylation catalyst mixture that comprises, consists of, or consists essentially of sulfone and hydrogen halide.

Referring to FIG. 1, the alkylation step 10 is shown in schematic form. A hydrocarbon feed mixture consisting of olefins and isoparaffins is introduced into reactor-upcomer 12 by conduit 14. Reactor-rise tube 12
Defines a reaction zone in which a hydrocarbon mixture is contacted or mixed with a catalyst mixture consisting of 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 tube 12 via conduit 16. The mixture of the hydrocarbon feed mixture and the catalyst mixture is defined by the reactor-rise tube 12 in which the reaction of the olefin of the hydrocarbon feed mixture with the isoparaffin of the hydrocarbon feed mixture is carried out to produce the alkylate reaction product. Enter the reaction zone. The reaction by-product ASO is also formed in the reaction zone. The reaction effluent from the reactor-rise pipe 12 enters the reactor-rise pipe 12 into a settling vessel 18, which separates the alkylate reaction product from the catalyst mixture and separates the reaction product 20 and the separated product. The separation zone for producing the catalyzed catalyst mixture 22 is defined. 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-upcomer 12 via conduits 24 and 16 for reuse as the alkylation catalyst mixture. Inserted in 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 heat transfer medium such as water.

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

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

The neutralized bottoms stream then contains adsorbed material by conduit 40 and removes a major portion of the ASO contained in the neutralized bottoms stream to substantially contain ASO and hydrogen fluoride. There is no regenerated catalyst or second contact vessel 42 that produces a sulfolane stream that is substantially free of ASO and hydrogen fluoride. This stream of sulfolane enters settling 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 optionally sent downstream for reprocessing through conduit 45.

To regenerate the contact material contained within 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 spent contact material. It is prepared. The contact material in the contact container 38 is periodically exposed to the solvent introduced by the conduit 46 into the first contact container 38, thereby removing at least a portion of the ASO absorbed by the contact material by the solvent. Expose the contact substance under such conditions. The ASO-containing solvent removed from the contact material exits the first contact vessel 38 for downstream processing by conduit 48. Contact material, AS contained on the contact material
Exposure to a solvent suitable for removal of at least a portion of O 2 is followed by exposing the previously exposed contact material to the strip fluid. The stripping fluid is introduced into the first contact vessel by conduit 46 and exposed to the contact material contained therein under conditions such that the contact material is regenerated. The stripping fluid is discharged from the first contact vessel 38 by conduit 48.

Examples The following examples illustrate the advantages of the present invention. These examples are for illustrative purposes only and are not intended to limit the invention as set forth in the appended claims.

Example I An ASO by-product derived from a hydrocarbon reaction catalyzed by a catalytic mixture of sulfolane and HF was obtained to determine the physical properties of the ASO by-product. The catalyst mixture used for the hydrocarbon reaction contained an HF to sulfolane weight ratio of about 1.5 and the hydrocarbon charge contained isobutane and 2-butene (60% trans, 40% cis isomer). The molar ratio of 2-butene is 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 produced ASO obtained from the hydrocarbon reaction.

[0072]

TABLE I Distillation of ASO derived from hydrocarbon reactions catalyzed by sulfolane / HF catalyst mixtures and other physical properties of ASO Temperature ℃ (° F) Bromine number of the volume% 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 carbon, alumina and their adsorption properties and the experimental methods used to obtain the adsorption properties of alumina.

A general experimental procedure using carbon or aluminum or both materials in the recovery of ASO from a sulfolane-containing mixture of sulfolane and ASO has 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, and either glass wool or beads on the top of the active substance to place the sulfolane-containing mixture on the active substance. It was distributed in the average. The glass cylinder was optionally heated to facilitate the flow of the sulfolane-containing mixture through the bed of active material. The sulfolane-containing mixture had a sulfolane to ASO weight ratio of about 9: 1. The color of the resulting filtrate was monitored to determine when the adsorption capacity of the active substance was exhausted and therefore the experiment was completed.

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

The experimental method 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 established before contacting the mixture with activated carbon material. The data obtained are shown in Table II, which illustrates 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 Activated carbon's ability to adsorb ASO from sulfolane-containing mixtures with a sulfolane to ASO ratio of 9: 1 as a function of HF concentration HF concentration in sulfolane-containing mixtures Carbon absorption capacity HF weight % Weight of ASO on carbon 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 by either adsorption or neutralization. This example also illustrates that alumina can perform a neutralizing function while at the same time 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. The same experimental method was used for. The sulfolane-containing mixture contained HF at a concentration of 5% by weight. The data presented in Table III also illustrates 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. Has been done.

[0080]

Table III Ability of various aluminas to neutralize and remove ASO from a sulfolane-containing mixture having a sulfolane to ASO weight ratio of 9: 1. Neutralization capacity ASO adsorption capacity Alumina type (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 can perform a neutralizing function and at the same time adsorb some of the ASO from the sulfone-containing mixture.

The experimental method used in this example is as described in 42.
Substantially the same method as described in Examples II and IV was used, except that a metal reactor was used in place of the glass cylinder to withstand pressures up to 600 kg / cm ² gauge (600 psig). In addition to this, the process and regenerated fluids were pumped through the adsorption bed instead of flowing under the force of gravity.

90/10 (by volume) sulfolane / ASO
Mix + 5% HF in 50 ml Reillex maintained at 100 ° F (37.8 ° C) and ambient pressure.
^Pumped onto a ^TM 425 polyvinyl pyridine bed. The mixture was pumped over 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 was collected. Stop the mixture feed, bring the bed temperature to about 148.9 ° C (about 300 ° F) and the pressure to 3
It was set at 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 completely dark and very acidic. Pumping of isobutane 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. On the second contact of the mixture with polyvinyl pyridine, 100 ml of effluent collected before the pH of the effluent dropped below 4.0, indicating that regeneration with isobutane was very effective. There is.

The calculation of the amount of HF and ASO removed from the polyvinyl pyridine bed and obtained during the regeneration step was cumulatively measured over the entire adsorption portion of the cycle, with the polymer being about 5 mmol HF / g polymer and It shows 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 sulfolane and ASO mixture. This example also illustrates that amine-substituted styrene divinylbenzene copolymers can also perform a neutralizing function while at the same time adsorbing some of the ASO contained in the sulfone-containing mixture.

The experimental method used in this example is as described in 42.
A method substantially similar to that described in Examples II and IV was used, except that a metal reactor was used in place of the glass cylinder to withstand pressures up to 18 kg / cm ² gauge (600 psig). In addition to this, the process and regenerated fluids were pumped into the adsorption bed instead of flowing by the force of gravity.

90/10 (by volume) sulfolane / ASO
Add a mixture of + 5% HF to about 37.8 ° C (about 100 ° F)
And 80 ml Rohm maintained at ambient pressure
& Haas Amberlyst A-21, pumped over 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 pH of the effluent dropped below 4.0. The mixture feed was stopped and the resin regenerated.

The calculation of the amount of HF and ASO obtained with the resin bed removed and during the regeneration step was approximately 5 m of polymer as measured cumulatively over the entire adsorption portion of the cycle.
It was shown to adsorb about 70% of the ASO in the mole HF / g polymer and the original sample mixture. FIG. 3 shows the results of this adsorption test. The time when the leakage of hydrogen fluoride was present in the experiment was taken as the point of 100% experiment.
Shown in. The% of ASO remaining refers to the amount of ASO contained in the feed removed by the resin and not passed into the bed effluent. As illustrated by the adsorption curve, A
Adsorption of SO and neutralization of hydrogen fluoride occurred simultaneously.

While the present invention has been described in terms of its presently preferred embodiments, those skilled in the art will be able to make reasonable variations and modifications. Such modifications and improvements are within the scope of the described invention and the appended claims.

[Brief description of drawings]

FIG. 1 (Schematic) Schematic representation of one of the method aspects of the invention.

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

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 9/16 9280-4H // C07B 61/00 300 (72) Inventor Robert Bruce Eldridge Oklahoma, United States Bartlesville, Kingston Drive 2808

Claims (21)

[Claims] 1. A sulfone component and an acid-soluble oil (AS
A method for removing the ASO from a sulfone-containing mixture comprising O), wherein the sulfone-containing mixture is treated with polyvinyl pyridine, or an amine under conditions suitable to remove at least a portion of the ASO component from the sulfone-containing mixture. The method for removing ASO, characterized in that it is brought into contact with a reversible base which is a copolymer of substituted styrene and divinylbenzene or a granular solid of a mixture of said reversible base. 2. The method of 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. 4. The method of claim 1, wherein prior to said contacting, the ASO in said sulfone-containing mixture is present in an amount up to about 20% by weight of said sulfone-containing mixture excluding said ASO component. The method according to item 1. 5. The contacting is performed at a pressure in the range of 0.5 to about 30 absolute atmospheric pressure, and at about -17.8 ° to about 204.4.
A method according to any one of claims 1 to 4 carried out at a temperature in the range of 0 ° C (about 0 ° to about 400 ° F). 6. The treated sulfone-containing mixture comprises about 2 parts.
A method according to any one of claims 1 to 5, comprising ASO in a concentration of less than wt%. 7. A process according to any one of claims 1 to 6, wherein the sulfone-containing mixture further comprises a hydrogen halide component. 8. The method according to claim 7, wherein the hydrogen halide is hydrogen fluoride. 9. 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 hydrogen halide and sulfone components, and said sulfone. 9. A process according to claim 7 or 8 wherein the ASO in the containing mixture is present in an amount up to about 20% by weight of the total weight of hydrogen halide and sulfone components. 10. The treated sulfone-containing mixture comprises hydrogen halide in an amount less than about 0.2% by weight.
The method of any one of 1-9. 11. A step of exposing the reversible base to the solvent under conditions such that at least a portion of the ASO adsorbed by the reversible base is removed by the solvent during the contacting. 11. The method of any one of claims 1-10, further comprising. 12. The organic solvent, wherein the solvent is alcohol, aliphatic hydrocarbon, alkyl halide, amine, aromatic hydrocarbon, ester, glycol, glycol ether, aromatic halide or a mixture of two or more thereof. 12. The method of claim 11, wherein: 13. The method of claim 11 or 12 comprising exposing the reversible base to a stripping fluid under stripping conditions that regenerate the reversible base. 14. The stripping condition includes about 3
14. The method of claim 13 including a stripping temperature in the range of about 100-600 ° F (7.8 ° -315.6 ° C) and a stripping pressure in the range of about 0.1-140 atmospheres. 15. A method according to claim 13 or 14, wherein the stripping fluid is an inert gas, steam or vapor hydrocarbon. 16. The treated sulfone-containing mixture is contacted with an adsorbent material that is carbon, thereby removing an additional portion of the ASO from the treated mixture to substantially produce ASO.
16. The method of any one of claims 1-15, further comprising the step of producing a sulfone-containing mixture that is free of. 17. The sulfone-containing mixture is contacted in a reaction zone with a hydrocarbon mixture consisting of an olefin and isoparaffin with a catalyst mixture containing the hydrogen halide component and the sulfone component to form an alkylated carbon. 8. An alkylation reaction mixture comprising hydrogen and at least a portion of the ASO produced as a byproduct of the alkylation process, the mixture being used in the alkylation reaction mixture. 17. The method of any one of 16 to 16. 18. In a separation zone, the alkylated hydrocarbons are separated from the catalyst mixture to form a separated catalyst mixture containing a substantial amount of ASO produced in the alkylation step. 18. The method of claim 17, further comprising the step consisting of: 19. The method of claim 18, comprising separating at least a portion of the separated catalyst mixture into a stream containing the sulfone-containing mixture and a stream containing the hydrogen fluoride. 20. The method further comprising utilizing the hydrogen fluoride stream as at least a portion of the catalyst mixture.
The method described in. 21. A process according to any one of claims 17 to 20 comprising the use of said sulfone containing mixture as at least part of the catalyst mixture in said alkylation step.