CN105817262B - A method of handling polystyrene sulfonic acid resin catalyst using sulfoxide solvent - Google Patents

Abstract

A kind of method utilizing sulfone solvent to process polystyrene sulfonic acid resin catalyst, relate to a kind of method of processing resin catalyst, described method comprises the following process: polystyrene sulfonic acid resin catalyst is added in the container that sulfone solvent is housed, Introduce gas at a pressure of 1.0-20.0 MPa, control the treatment temperature at 100-150°C, and process for 0.5-20.0 h. The polar organic sulfone solvent is also used as a water-carrying agent, a pore-enlarging agent and a structural modifier of the sulfonic acid resin. Function; Catalyst is the resinous catalyst that contains sulfonic acid functional group, and the present invention adopts polar organic sulfone solvent heat treatment polystyrene sulfonic acid resin catalyst, and after processing, sulfonic acid resin catalyst is used for methylal carbonylation reaction, and does not pass through Compared with sulfone-treated sulfonic acid resin catalysts, it exhibits excellent reactivity, stability and selectivity to methyl methoxyacetate.

Description

A kind of method utilizing sulfone solvent to process polystyrene sulfonic acid resin catalyst

technical field

The invention relates to a method for treating a resin catalyst, in particular to a method for treating a polystyrene sulfonic acid resin catalyst with a sulfone solvent.

Background technique

Methyl methoxyacetate (MMAc) is an important organic chemical raw material, which can be used for the kinetic resolution of chiral amine compounds, the synthesis of vitamin B6 and sulfa-5-pyrimidine, and the catalyst for polymerization reactions; Petroleum route (use cheap and easy-to-obtain methylal as the reaction raw material, synthesize high value-added MMAc through carbonylation reaction) produce the upstream product of ethylene glycol, a bulk chemical raw material, from MMAc (generate ethylene glycol monomethyl ether through hydrogenation reaction , and then generate ethylene glycol through hydrolysis reaction), ethylene glycol is mainly used in polyester fiber, antifreeze, unsaturated polyester resin, lubricant, plasticizer, non-ionic surfactant and explosives, coatings, inks, etc. Production and demand are constantly increasing. At the same time, the product methyl methoxyacetate can be hydrogenated to produce ethylene glycol monomethyl ether and the downstream product ethylene glycol dimethyl ether can be obtained through methyl etherification.

At present, there are very few synthetic methods of methyl methoxyacetate reported in literature and patents, mainly including the following 4 methods:

(1) Synthesis of chloroacetic acid and sodium methoxide: chloroacetic acid and sodium methoxide are used as raw materials to first synthesize methoxyacetic acid, which is then reacted with methanol to synthesize methyl methoxyacetate. The reaction equation is as follows:

CH ₂ ClCOOH + CH ₃ ONa → CH ₃ OCH ₂ COOH +NaCl.......................... .................................(1)

CH ₃ OCH ₂ COOH + CH ₃ OH → CH ₃ OCH ₂ COOCH ₃ +H ₂ O................... ...............................(2)

Although the reaction of chloroacetic acid and sodium methylate is relatively easy to carry out, chloroacetic acid is prepared by a substitution reaction between acetic acid and chlorine gas. The reaction process is complicated, and the corrosion is serious and pollutes the environment, so it is not suitable for large-scale production. Moreover, the yield of methyl methoxyacetate produced by the esterification reaction of methoxyacetic acid and methanol is relatively low, only about 60%, and it is difficult to obtain a high yield.

(2) Ethylene glycol monomethyl ether oxidation method

Using ethylene glycol monomethyl ether as raw material, methoxyacetic acid is synthesized through oxidation reaction, and then esterified with methanol to form methoxyacetic acid methyl ester. The reaction equation is as follows:

3HO(CH ₂ ) ₂ COCH ₃ + 3O ₂ → 4CH ₃ OCH ₂ COOH + 4CH ₃ OH → 4CH ₃ OCH ₂ COOCH ₃ ...................(3)

However, this method produces a large amount of waste water and waste gas, serious environmental pollution, and large investment in equipment. Therefore, this method not only has a complicated synthesis route, but also has limited sources of raw material ethylene glycol monomethyl ether, an immature oxidation process, and low esterification efficiency.

(3) Methyl chloroacetate and sodium methoxide substitution method

Using methyl chloroacetate and sodium methoxide as raw materials, methyl methoxyacetate was synthesized by substitution reaction. The reaction equation is as follows:

ClCH ₂ COOCH ₃ + CH ₃ ONa → CH ₃ OCH ₂ COOCH ₃ +NaCl…………………………………(4)

However, the two raw materials of this method, methyl chloroacetate and sodium methoxide, are difficult to prepare and are not suitable for large-scale production.

(4) Methylal carbonylation method

Using simple and easy-to-obtain methylal as a raw material, methyl methoxyacetate is synthesized through carbonylation reaction, and the reaction equation is as follows:

CH ₃ OCH ₂ OCH ₃ + CO → CH ₃ OCH ₂ COOCH ₃ (main reaction)……………………… ..............(5)

2CH ₃ OCH ₂ OCH ₃ → 2CH ₃ OCH ₃ + HCOOCH ₃ (side reaction) …………………………………(6)

A.T. Bell uses methylal (DMM) as a raw material to synthesize methyl methoxyacetate through carbonylation, and the selectivity of methyl methoxyacetate is 79%. The advantage of this synthesis method is that the reaction process is simple and there are few by-products; the reaction raw material methylal has a wide range of sources and is easy to synthesize (by the condensation reaction of methanol and formaldehyde), which is suitable for large-scale industrial production. Shi Lei of Dalian Institute of Physical Chemistry used Nafion-H and modified Nafion-H as catalysts for the carbonylation of DMM, and the selectivity of MMAc reached 90%.

At present, the modification methods of sulfonic acid resin reported in the literature are as follows: the sulfonic acid resin is grafted onto silica, aluminum oxide or activated carbon with a large specific surface to improve the dispersion of the acid center of the sulfonic acid resin ; The hydrogen in the sulfonic acid resin is replaced by fluorine to prepare perfluorinated sulfonic acid resin. Because the C-F bond of the perfluorosulfonic acid resin has a high bond energy, it has stronger acidity and high service temperature; the metal ion part is used Proton-substituted modified perfluorosulfonic acid resin, etc.

For the DMM carbonylation reaction, the water content in the reaction process has a great influence on the reaction, as shown in equation (7-9), the reaction raw material DMM can react with a small amount of water to generate DMM ₂ and methanol, and at the same time due to the water In the presence of DMM, formaldehyde can be released, formaldehyde can form methyl glycolate with CO and methanol, methanol can dehydrate itself to form dimethyl ether, and release water at the same time, so the water content in this reaction should be avoided as much as possible.

2CH ₃ OCH ₂ OCH _{3 +} H ₂ O → CH ₃ OCH ₂ OCH ₂ OCH ₃ + 2CH ₃ OH……………………………………………………………………………………. (7) HCHO + CO + CH ₃ OH → HOCH ₂ COOCH ₃ (MG)…………………………………(8) 2CH ₃ OH → CH ₃ OCH ₃ +H ₂ O……………………… …………………………………………… (9) However, due to the particularity of the structure of sulfonic acid resin, it cannot be dried under high temperature for a long time, so there is always a small amount of DMM carbonylation reaction Water is introduced.

Contents of the invention

The object of the present invention is to provide a kind of method that utilizes sulfone solvent to process polystyrene sulfonic acid resin catalyst, the inventive method adopts polar organic sulfone solvent to heat process polystyrene sulfonic acid resin catalyst, after the treatment, sulfonic acid resin catalyst is used for formaldehyde The acetal carbonylation reaction, compared with the untreated sulfonic acid resin catalyst, showed excellent reactivity, stability and product selectivity to methyl methoxyacetate.

The purpose of the present invention is achieved through the following technical solutions:

A kind of method utilizing sulfone solvent to process polystyrene sulfonic acid resin catalyst, described method comprises the following process: polystyrene sulfonic acid resin catalyst is added in the container that sulfone solvent is housed, feeds the gas of 1.0-20.0 MPa pressure , control the treatment temperature at 100-150°C, and the treatment time at 0.5-20.0 h. The polar organic sulfone solvent acts as a water-carrying agent, a pore-enlarging agent and a structural modifier of the sulfonic acid resin at the same time; the catalyst is a sulfonic acid functional group The resin catalyst is a mixture of one or more of D-009B, DA-330, NKC-9, D-006, Amberlyst-15, D-072, etc.; the sulfone solvent contains two oxygen-sulfur double bond functional groups The organic matter is a mixture of one or more of dimethyl sulfone, methyl vinyl sulfone, sulfolene, sulfolane, diethyl sulfone, and allyl sulfone; the gas is one of CO and _N2 gases or a mix of both.

In the method for treating polystyrene sulfonic acid resin catalyst with sulfone solvent, the preferred treatment temperature is 150° C.; the preferred treatment pressure is 3.5 MPa, and the preferred treatment time is 6 h.

In the method for treating a polystyrene sulfonic acid resin catalyst with a sulfone solvent, diethyl sulfone solvent has the best effect among the sulfone solvents, and the optimal treatment atmosphere is a CO gas atmosphere.

Advantage and effect of the present invention are:

The invention provides a simple and practical modification method for sulfonic acid resin catalysts, using polar organic sulfone solvents to heat treat polystyrene sulfonic acid resin catalysts, and the polar organic sulfone solvents are simultaneously used as water-carrying agents and pore-enlarging agents Works together with structural modifiers for sulfonic acid resins. The treated sulfonic acid resin catalyst is used in the carbonylation reaction of methylal. Compared with the untreated sulfonic acid resin catalyst, it shows excellent reactivity, stability and selectivity of the product methyl methoxyacetate.

Description of drawings

Fig. 1 is the figure of influence of catalyst pretreatment time on DMM conversion rate and product MMAc selectivity.

Detailed ways

The present invention will be described in detail below in conjunction with examples.

The product of the present invention is detected and determined through gas chromatography and mass spectrometry analysis. Through gas-mass spectrometry analysis and detection, the products after the reaction are determined, including dimethyl ether, methyl formate, dimerized methylal, methanol, methyl methoxyacetate, methyl glycolate and the like. The conventional treatment conditions for resin catalysts are as follows: in an oven at 120°C for 6 h. The conditions for resin catalyst sulfone treatment are to put a certain mass of catalyst into a reaction kettle containing a solvent that does not tolerate sulfone, and treat it for different times under certain temperature and pressure and different filling atmospheres. After the treated catalyst was filtered, it was dried in an oven at 120 °C for 6 h. The evaluation conditions of the catalyst are as follows: Weigh 30 mL of DMM, 30 mL of 1,4-dioxane solvent, and 1 g of the modified sulfonic acid resin catalyst, respectively add them to the reaction kettle, and use N ₂ under the condition of 1.0 MPa The air in the kettle was replaced three times to make the remaining air content in the kettle less than 0.1%, and 3.0 MPa CO was introduced and left to stand for 30 minutes, which was used for leak detection of the reactor, and the gas in the kettle was emptied after ensuring that the device was not leaking. The stirring speed of the reactor was 500 rpm, 3.0 MPa CO was introduced, the reaction temperature was controlled at 110 °C, and the reaction was carried out for 6 hours. Cool down to room temperature after the reaction, filter the product after adding 2 g of ethanol as an internal standard, analyze the peak area of the mixture methylal and methyl methoxyacetate with gas chromatography, and then calculate the conversion rate of methylal and methoxyacetic acid Methyl ester selectivity.

Example 1

Put 10 grams of D-006 sulfonic acid resin catalyst into 100 mL of insoluble sulfone solvent (dimethyl sulfone, methyl vinyl sulfone, sulfolene, sulfolane, diethyl sulfone, allyl sulfone, etc.) In the reactor, treat the sulfonic acid resin catalyst in the temperature range of 100-150 °C for 2-6 h. After the treated catalyst was filtered, it was dried in an oven at 120 °C for 6 h. The evaluation conditions of the catalyst are as follows: Weigh 30 mL of DMM, 30 mL of 1,4-dioxane solvent, and 1 g of the modified sulfonic acid resin catalyst, respectively add them to the reaction kettle, and use N ₂ under the condition of 1.0 MPa The air in the kettle was replaced three times to make the remaining air content in the kettle less than 0.1%, and 3.0 MPa CO was introduced and left to stand for 30 minutes, which was used for leak detection of the reactor, and the gas in the kettle was emptied after ensuring that the device was not leaking. The stirring speed of the reactor was 500 rpm, 3.0 MPa CO was introduced, the reaction temperature was controlled at 110 °C, and the reaction was carried out for 6 hours. DMM conversion rate and product MMAc selectivity are shown in Table 1.

Table 1. Effects of different sulfone solvents on the conversion of raw material DMM and the selectivity of product MMAc.

As can be seen from the reaction data in Table 1, using D-006 polystyrene sulfonic acid resin as a catalyst, when the catalyst is not modified by sulfone solvent, the conversion rate of DMM is only 30%, and the selectivity of MMAc is only 28%, but when the catalyst The conversion rate of DMM and the selectivity of MMAc both increased after modified with sulfone solvent. When diethylsulfone was used as solvent and D-0064 h was treated at 130℃, the conversion of DMM was 88%, and the selectivity of MMAc was 65%.

Example 2

Put 10 grams of different types of polystyrene sulfonic acid resin catalysts (D-009B, DA-330, D-006, D-072, Amberlyst-15, NKC-9) into a 100mL reaction kettle containing diethylsulfone solvent , at 100-150°C, 5.0 MPa, and CO atmosphere for 6 h. After the treated catalyst was filtered, it was dried in an oven at 120 °C for 6 h. The evaluation conditions of the catalyst are as follows: Weigh 30 mL of DMM, 30 mL of 1,4-dioxane solvent, and 1 g of the modified sulfonic acid resin catalyst, respectively add them to the reaction kettle, and use N ₂ under the condition of 1.0 MPa The air in the kettle was replaced three times to make the remaining air content in the kettle less than 0.1%, and 3.0 MPa CO was introduced and left to stand for 30 minutes, which was used for leak detection of the reactor, and the gas in the kettle was emptied after ensuring that the device was not leaking. The stirring speed of the reactor was 500 rpm, 3.0 MPa CO was introduced, the reaction temperature was controlled at 110 °C, and the reaction was carried out for 6 hours. Cool down to room temperature after the reaction, filter the product after adding 2 g of ethanol as an internal standard, analyze the peak area of the mixture methylal and methyl methoxyacetate with gas chromatography, and then calculate the conversion rate of methylal and methoxyacetic acid The selectivity of methyl ester, DMM conversion rate and product MMAc selectivity are shown in table 2.

Table 2. The influence of different resin catalysts on the conversion rate of raw material DMM and the selectivity of product MMAc.

catalyst Sulfone solvent Processing temperature (°C) DMM conversion rate (%) MMAc selectivity (%) DA-330 Diethylsulfone 100 68 57 D-072 Diethylsulfone 110 72 60 D-006 Diethylsulfone 120 84 64 D-009B Diethylsulfone 110 86 67 Amberlyst-15 Diethylsulfone 130 89 72 NKC-9 Diethylsulfone 150 92 88

As can be seen from Table 2, when different types of polystyrene sulfonic acid resin catalyst catalysts (D-009B, DA-330, D-006, D-072, Amberlyst-15, NKC-9) in the same sulfone solvent, in After modification under the same conditions, there are still significant differences in the conversion rate of DMM and the selectivity of MMAc. Among them, NKC-9 catalyst was treated in diethyl sulfone at 150 °C for 6 h, and then used for DMM carbonylation reaction after conventional drying procedures. As a result, the conversion rate of DMM reached 92%, and the selectivity of MMAc was 88%. The effect is better.

Example 3

Put 10 grams of NKC-9 catalyst into a 100 mL reaction kettle containing diethyl sulfone solvent, and treat it at 150 °C, 5.0 MPa, and CO atmosphere for 0.5-20 h. After the treated catalyst was filtered, it was dried in an oven at 120 °C for 6 h. The evaluation conditions of the catalyst are as follows: Weigh 30 mL of DMM, 30 mL of 1,4-dioxane solvent, and 1 g of the modified sulfonic acid resin catalyst, respectively add them to the reaction kettle, and use N ₂ under the condition of 1.0 MPa The air in the kettle was replaced three times to make the remaining air content in the kettle less than 0.1%, and 3.0 MPa CO was introduced and left to stand for 30 minutes, which was used for leak detection of the reactor, and the gas in the kettle was emptied after ensuring that the device was not leaking. The stirring speed of the reactor was 500 rpm, 3.0 MPa CO was introduced, the reaction temperature was controlled at 110 °C, and the reaction was carried out for 6 hours. Cool down to room temperature after the reaction, filter the product after adding 2 g of ethanol as an internal standard, analyze the peak area of the mixture methylal and methyl methoxyacetate with gas chromatography, and then calculate the conversion rate of methylal and methoxyacetic acid The selectivity of methyl ester, DMM conversion rate and product MMAc selectivity are shown in table 3.

Table 3. Effects of different catalyst treatment times on the conversion rate of raw material DMM and the selectivity of product MMAc.

Processing time (h) Sulfone solvent catalyst DMM conversion rate (%) MMAc selectivity (%) 0.0 -- NKC-9 36 34 0.5 Diethylsulfone NKC-9 65 59 1.0 Diethylsulfone NKC-9 67 64 3.0 Diethylsulfone NKC-9 87 82 6.0 Diethylsulfone NKC-9 92 88 10.0 Diethylsulfone NKC-9 83 78 20.0 Diethylsulfone NKC-9 74 71

It can be seen from Table 3 that when NKC-9 was treated in diethyl sulfone for 0.5 h, it was used in DMM carbonylation reaction, the conversion rate of DMM was 65%, and the selectivity of MMAc was 59%. Under the same pretreatment conditions, the catalyst treatment time was increased , both DMM conversion and MMAc selectivity were increased. When treated for 6.0 h, the conversion rate of DMM was 92%, and the selectivity of MMAc was 88%. The conversion rate of DMM and the selectivity of MMAc decreased when the catalyst treatment time continued to increase. sex dropped to 71%.

Example 4

Put 10 grams of NKC-9 catalyst into a reaction kettle containing 100 mL of diethyl sulfone solvent, and treat it at 90-150 °C, 5.0 MPa, and CO atmosphere for 6.0 h. After the treated catalyst was filtered, it was dried in an oven at 120 °C for 6 h. The evaluation conditions of the catalyst are as follows: Weigh 30 mL of DMM, 30 mL of 1,4-dioxane solvent, and 1 g of the modified sulfonic acid resin catalyst, respectively add them to the reaction kettle, and use N ₂ under the condition of 1.0 MPa The air in the kettle was replaced three times to make the remaining air content in the kettle less than 0.1%, and 3.0 MPa CO was introduced and left to stand for 30 minutes, which was used for leak detection of the reactor, and the gas in the kettle was emptied after ensuring that the device was not leaking. The stirring speed of the reactor was 500 rpm, 3.0 MPa CO was introduced, the reaction temperature was controlled at 110 °C, and the reaction was carried out for 6 hours. Cool down to room temperature after the reaction, filter the product after adding 2 g of ethanol as an internal standard, analyze the peak area of the mixture methylal and methyl methoxyacetate with gas chromatography, and then calculate the conversion rate of methylal and methoxyacetic acid The selectivity of methyl ester, DMM conversion rate and product MMAc selectivity are shown in table 4.

Table 4. Effects of different treatment temperatures of the catalyst on the conversion rate of raw material DMM and the selectivity of product MMAc.

Processing temperature (°C) Sulfone solvent catalyst DMM conversion rate (%) MMAc selectivity (%) 90 Diethylsulfone NKC-9 55 38 100 Diethylsulfone NKC-9 77 64 110 Diethylsulfone NKC-9 87 69 130 Diethylsulfone NKC-9 90 72 150 Diethylsulfone NKC-9 92 88

It can be seen from Table 4 that when the pretreatment temperature of the NKC-9 catalyst is 90°C, the DMM conversion rate is 55%, and the MMAc selectivity is 38%; when the catalyst pretreatment temperature is increased, the DMM conversion rate and the MMAc selectivity increase gradually. When the temperature is 150°C, the conversion rate of DMM is 92%, and the selectivity of MMAc is 88%;

Example 5

Put 10 grams of NKC-9 catalyst into a reaction kettle containing 100 mL diethyl sulfone solvent, and treat it at 150 °C, 5.0 MPa, and different atmospheres (CO, N ₂ ) for 6.0 h. After the treated catalyst was filtered, it was dried in an oven at 120 °C for 6 h. The evaluation conditions of the catalyst are as follows: Weigh 30 mL of DMM, 30 mL of 1,4-dioxane solvent, and 1 g of the modified sulfonic acid resin catalyst, respectively add them to the reaction kettle, and use N ₂ under the condition of 1.0 MPa The air in the kettle was replaced three times to make the remaining air content in the kettle less than 0.1%, and 3.0 MPa CO was introduced and left to stand for 30 minutes, which was used for leak detection of the reactor, and the gas in the kettle was emptied after ensuring that the device was not leaking. The stirring speed of the reactor was 500 rpm, 3.0 MPa CO was introduced, the reaction temperature was controlled at 110 °C, and the reaction was carried out for 6 hours. Cool down to room temperature after the reaction, filter the product after adding 2 g of ethanol as an internal standard, analyze the peak area of the mixture methylal and methyl methoxyacetate with gas chromatography, and then calculate the conversion rate of methylal and methoxyacetic acid The selectivity of methyl ester, DMM conversion rate and product MMAc selectivity are shown in table 5.

Table 5. Effect of catalyst pretreatment atmosphere on the conversion rate of raw material DMM and the selectivity of product MMAc.

Fill the atmosphere Sulfone solvent Processing temperature (°C) Processing time (h) DMM conversion rate (%) MMAc selectivity (%) N ₂ Diethylsulfone 150 6.0 78 53 CO Diethylsulfone 150 6.0 92 88

It can be seen from Table 5 that under the same conditions of catalyst pretreatment temperature and time, when _N2 is used as the filling atmosphere, the conversion rate of DMM is 78%, and the selectivity of MMAc is 53%; while when CO is used as the modifying atmosphere, The conversion rate of DMM was 92%, and the selectivity of MMAc was 88%, both of which have been significantly improved, indicating that the modification atmosphere is very important to the modification of the catalyst. A certain chemical reaction occurred during the modification process, making the modified catalyst more stable. It is beneficial for the carbonylation reaction of DMM to generate MMAc.

Example 6

Put 10 g of NKC-9 catalyst into a reaction kettle containing 100 mL of diethyl sulfone solvent, and treat it at 150 °C, (1.0-20) MPa, CO atmosphere for 6.0 h. After the treated catalyst was filtered, it was dried in an oven at 120 °C for 6 h. The evaluation conditions of the catalyst are as follows: Weigh 30 mL of DMM, 30 mL of 1,4-dioxane solvent, and 1 g of the modified sulfonic acid resin catalyst, respectively add them to the reaction kettle, and use N ₂ under the condition of 1.0 MPa The air in the kettle was replaced three times to make the remaining air content in the kettle less than 0.1%, and 3.0 MPa CO was introduced and left to stand for 30 minutes, which was used for leak detection of the reactor, and the gas in the kettle was emptied after ensuring that the device was not leaking. The stirring speed of the reactor was 500 rpm, 3.0 MPa CO was introduced, the reaction temperature was controlled at 110 °C, and the reaction was carried out for 6 hours. Cool down to room temperature after the reaction, filter the product after adding 2 g of ethanol as an internal standard, analyze the peak area of the mixture methylal and methyl methoxyacetate with gas chromatography, and then calculate the conversion rate of methylal and methoxyacetic acid The selectivity of methyl ester, DMM conversion rate and product MMAc selectivity are shown in table 6.

Table 6. The influence of catalyst pretreatment pressure on the conversion rate of raw material DMM and the selectivity of product MMAc.

Handling pressure (MPa) Processing temperature (°C) catalyst DMM conversion rate (%) MMAc selectivity (%) 1.0 150 NKC-9 71 40 2.5 150 NKC-9 80 58 3.5 150 NKC-9 99 92 5.0 150 NKC-9 92 88 10.0 150 NKC-9 89 79 20.0 150 NKC-9 87 73

It is known from Table 6 that when the pretreatment pressure of NKC-9 catalyst is 1.0 MPa, the DMM conversion rate is 71%, and the MMAc selectivity is 40%; increasing the CO pressure in the atmosphere during pretreatment, the DMM conversion rate and the selectivity of MMAc all increase, At 3.5 MPa, the catalytic effect of the treated catalyst is the best, its DMM conversion rate is 99%, and the MMAc selectivity is 92%; when the pressure of CO in the atmosphere continues to increase during the pretreatment, the DMM conversion rate and MMAc selectivity begin to decrease, and at 20.0 MPa , DMM conversion rate 87%, MMAc selectivity 73%.

The above are only a few embodiments of the application, and do not limit the application in any form. Although the application is disclosed as above with preferred embodiments, it is not intended to limit the application. Any skilled person familiar with this field, Without departing from the scope of the technical solution of the present application, any changes or modifications made using the technical content disclosed above are equivalent to equivalent implementation cases, and all belong to the scope of the technical solution.

Claims (1)

1. a method utilizing sulfone solvent to process polystyrene sulfonic acid resin catalyst, is characterized in that, described method comprises the following process: polystyrene sulfonic acid resin catalyst is joined in the container that sulfone solvent is housed, feeds 3.5 MPa pressure gas, controlled treatment temperature 150°C, treatment time 6 h, sulfone solvent acts as water carrier, pore expander and structural modifier of sulfonic acid resin at the same time; sulfone solvent contains two oxygen-sulfur double bonds Functional organic diethyl sulfone solvent; gas is CO.