Sulfonated styrene divinyl benzene resin and preparation method thereof, etherification catalyst and application thereof, and method for removing isobutene

Abstract

The invention relates to the technical field of petrochemical engineering, in particular to sulfonated styrene divinyl benzene resin and a preparation method thereof, an etherification catalyst and application thereof and a method for removing isobutene, and discloses a preparation method of sulfonated styrene divinyl benzene resin. The preparation method comprises the following steps: carrying out suspension polymerization on an oil phase containing styrene, divinyl benzene, a pore-foaming agent and an initiator and a water phase containing water, a dispersing agent, a dispersing aid, electrolyte and a water-phase polymerization inhibitor, curing, removing the pore-foaming agent, and sulfonating; wherein the water phase polymerization inhibitor is phenol. The prepared catalyst especially as an etherification catalyst has the advantages of appropriate particle size and high exchange equivalent, and can reduce the content of isobutene in etherified C4 when being used for a deep etherification reaction of methanol and isobutene after etherification.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical industry, and in particular to a sulfonated styrene divinyl benzene resin and a preparation method thereof, an etherification catalyst and an application thereof, and a method for removing isobutylene. Background Art

[0002] Mixed C4 separation is the main process route for producing 1-butene. There are many refineries, catalytic cracking units, ethylene cracking units, and coal-to-methanol-to-olefins units in China, which can provide abundant mixed C4 raw materials. Since the relative volatility of the components of mixed C4 is similar, it is difficult to separate them by ordinary distillation methods. From the perspective of saving energy consumption and reducing process complexity, it is necessary to remove butadiene, isobutylene and other components in mixed C4 in advance to make butene-1 easy to separate and purify. The common practice is to separate or convert butadiene through butadiene extraction, selective hydrogenation and other technologies on the basis of mixed C4 separation process technology, and then optimize the conversion and separation of isobutylene through etherification, and finally produce butene-1 through precision distillation. The source of raw materials for this process is limited. As the consumption of butene-1 increases, it is necessary to expand the source of butene-1 raw materials. There are many catalytic cracking units and coal-to-olefin units. Previously, such materials could not be used to produce butene-1 due to the inability to deeply etherify and remove isobutylene. Therefore, it is necessary to develop a suitable deep etherification resin catalyst for removing isobutylene in etherified carbon four, so that the material is suitable as a raw material for butene-1 production, thereby achieving the purpose of expanding the source of butene-1 raw materials.

[0003] CN1151334A discloses a method for preparing a macroporous strongly acidic cation exchange resin catalyst. The method of the present invention uses C3-C4 low-carbon alcohol compounds as porogens, and uses a high molecular compound compatible therewith as a dispersant and a dispersant to make styrene and polyvinyl monomers suspended copolymerized to prepare copolymer white balls with reasonable pore structure and uniform particle size. The white balls are then dynamically treated with high-temperature deionized water, and the treated white balls do not need to be expanded by organic solvents and directly undergo sulfonation reaction, which can improve production efficiency, reduce production costs, and reduce environmental pollution. It can be widely used in organic catalytic reactions such as etherification. However, the catalyst has a large particle size and is suitable for the reaction of etherifying high-concentration isobutylene to generate methyl tert-butyl ether. At a lower isobutylene concentration, the catalyst is not suitable for deep etherification and isobutylene removal reactions. Summary of the invention

[0004] The purpose of the present invention is to provide a sulfonated styrene divinyl benzene resin, which is particularly suitable for low-concentration etherification reaction, thereby overcoming the problems in the prior art that if isobutylene cannot be effectively removed, the boiling point difference between isobutylene and butene-1 is small, and qualified butene-1 products cannot be obtained through distillation, so the isobutylene concentration in C4 needs to be controlled, the existing etherification catalyst and process technology can only be suitable for the removal of relatively high-concentration isobutylene, and the existing catalyst cannot meet the process conditions for deep removal, and the like. Provided are a sulfonated styrene divinyl benzene resin and a preparation method thereof, an etherification catalyst and application thereof. The etherification catalyst has a suitable particle size and a high exchange equivalent, is used for methanol and isobutylene to carry out a deep etherification reaction of C4 after etherification, can reduce the content of isobutylene in C4 after etherification, and has a good promotion and application prospect in expanding the application field of butene-1 raw material sources.

[0005] In order to achieve the above-mentioned purpose, the present invention provides a method for preparing a sulfonated styrene divinylbenzene resin on the one hand, which comprises: subjecting an oil phase containing styrene, divinylbenzene, a porogen, and an initiator to suspension polymerization with an aqueous phase containing water, a dispersant, a dispersant aid, an electrolyte, and an aqueous phase inhibitor, solidifying, then removing the porogen, and sulfonating; wherein the aqueous phase inhibitor is phenol.

[0006] The second aspect of the present invention provides a method for preparing the sulfonated styrene divinyl benzene resin according to the first aspect of the present invention to prepare the resin.

[0007] The third aspect of the present invention provides a catalyst prepared by the method for preparing the sulfonated styrene divinyl benzene resin according to the second aspect of the present invention.

[0008] The fourth aspect of the present invention provides use of the sulfonated styrene divinyl benzene resin described in the second aspect of the present invention and the catalyst described in the third aspect of the present invention in an etherification reaction.

[0009] The fifth aspect of the present invention provides a method for removing isobutylene from a C4 raw material, the method comprising: in the presence of the catalyst described in the third aspect of the present invention, methanol is contacted with the C4 raw material containing isobutylene to carry out an etherification reaction.

[0010] Through the above technical solution, the present invention has the following beneficial effects:

[0011] In the preparation of sulfonated styrene divinylbenzene resin, the present invention makes the particle size suitable when styrene and divinylbenzene are polymerized to produce polymer white balls by adding a dispersant, an electrolyte and a water phase inhibitor phenol. The addition of the dispersant glycerol makes the water phase viscous, reduces the collision probability of the oil phase after balling, and reduces the particle size of the white balls. The addition of the water phase inhibitor and the electrolyte reduces the solubility of the oil phase in the water phase and reduces the formation of fine particles, improves the particle size of the white balls, and then passes through suitable sulfonation conditions. Because the particle size of the white balls is small, the sulfonation depth can be deepened, the exchange equivalent can be increased, and a catalyst more suitable for the deep etherification of carbon four after etherification is prepared. The catalyst is used for the deep etherification reaction of carbon four after etherification with methanol and isobutylene, and the content of isobutylene in carbon four after etherification can be reduced. DETAILED DESCRIPTION

[0012] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0013] The present invention provides a method for preparing a sulfonated styrene divinyl benzene resin, the method comprising:

[0014] The oil phase containing styrene, divinylbenzene, porogen and initiator is subjected to suspension polymerization with the water phase containing water, dispersant, dispersant aid, electrolyte and water phase inhibitor, and then solidified, and then the porogen is removed and sulfonated; wherein the water phase inhibitor is phenol.

[0015] In the present invention, the water phase is made viscous by adding a dispersant, the collision probability of the oil phase after being balled is reduced, and the particle size of the white balls is reduced. The addition of phenol as a water phase inhibitor and an electrolyte reduces the solubility of the oil phase in the water phase and reduces the formation of fine particles. At the same time, a more appropriate rotation speed is used to improve the particle size of the white balls. Then, suitable sulfonation conditions are applied to deepen the sulfonation depth, increase the exchange equivalent, and obtain an etherification catalyst, which can reduce the content of isobutylene in carbon four after etherification.

[0016] In the present invention, the weight parts of the oil phase can be conventionally selected in the art. According to a preferred embodiment of the present invention, the oil phase contains: 100 parts of styrene; 55-75 parts of divinylbenzene; 40-60 parts of porogen; 0.8-2 parts of initiator. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0017] In the present invention, the weight percentage of the aqueous phase can be a conventional choice in the art, and according to a preferred embodiment of the present invention, the aqueous phase contains: 400-600 parts of water; 2-6 parts of dispersant; 0.1-0.5 parts of co-dispersant; 15-18 parts of electrolyte; 3-6 parts of aqueous phase inhibitor. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0018] In the present invention, the dispersant can be a conventional choice in the art. According to a preferred embodiment of the present invention, the dispersant is glycerol. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0019] In the present invention, the electrolyte can be a conventional choice in the art. According to a preferred embodiment of the present invention, the electrolyte is sodium sulfate. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0020] In the present invention, the porogen can be a conventional choice in the art. According to a preferred embodiment of the present invention, the porogen is 100# solvent oil. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0021] In the present invention, the initiator can be a conventional choice in the art. According to a preferred embodiment of the present invention, the initiator is benzoyl peroxide. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0022] In the present invention, the dispersant can be a conventional choice in the art. According to a preferred embodiment of the present invention, the dispersant is gelatin. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0023] In the present invention, the temperature of the water phase can be a conventional choice in the art. According to a preferred embodiment of the present invention, the temperature of the water phase is 50-60° C. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0024] In the present invention, the conditions for the suspension polymerization may be conventionally selected in the art.

[0025] According to a preferred embodiment of the present invention, the heating rate of the suspension polymerization is 5-20°C / 20min.

[0026] According to a preferred embodiment of the present invention, the temperature of the suspension polymerization is 80-90°C.

[0027] According to a preferred embodiment of the present invention, the suspension polymerization time is 10-20 hours.

[0028] According to a preferred embodiment of the present invention, the stirring speed of the suspension polymerization is 180-200 r / min.

[0029] By adopting the above-mentioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0030] In the present invention, the curing conditions may be conventionally selected in the art.

[0031] According to a preferred embodiment of the present invention, the curing temperature is 80-90°C.

[0032] According to a preferred embodiment of the present invention, the curing time is 5-10 hours.

[0033] By adopting the above-mentioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0034] In the present invention, the method for removing the porogen can be a conventional choice in the art. According to a preferred embodiment of the present invention, the method for removing the porogen includes: adding the solidified solid material to an aromatic hydrocarbon solvent, extracting the porogen, and washing the solid material with an organic solvent.

[0035] By adopting the above-mentioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0036] In the present invention, the aromatic hydrocarbon solvent can be a conventional choice in the art. According to a preferred embodiment of the present invention, the aromatic hydrocarbon solvent includes toluene. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0037] In the present invention, the organic solvent may be a conventional choice in the art.

[0038] According to a preferred embodiment of the present invention, the organic solvent includes acetone and / or ethanol.

[0039] According to a preferred embodiment of the present invention, the organic solvent is a mixture of acetone and ethanol.

[0040] By adopting the above-mentioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0041] In the present invention, the weight ratio of the solid material to the aromatic hydrocarbon solvent can be a conventional choice in the art. According to a preferred embodiment of the present invention, the weight ratio of the solid material to the aromatic hydrocarbon solvent is 1:10-20. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0042] In the present invention, the sulfonation method can be a conventional choice in the art. According to a preferred embodiment of the present invention, the sulfonation method comprises: the solid material obtained after removing the porogen is contacted with a sulfonation reagent for sulfonation reaction, followed by acid washing and water washing. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0043] In the present invention, the mass ratio of the solid material to the sulfonating agent can be a conventional choice in the art. According to a preferred embodiment of the present invention, the mass ratio of the solid material to the sulfonating agent is 1:6-10. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0044] In the present invention, the sulfonating agent can be a conventional choice in the art. According to a preferred embodiment of the present invention, the sulfonating agent is selected from oleum. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0045] In the present invention, the conditions of the sulfonation reaction can be conventionally selected in the art. According to a preferred embodiment of the present invention, the conditions of the sulfonation reaction include: when the temperature is programmed to 30-50°C and kept for 1-3h, 0.1-1h is heated to 50-70°C and kept for 1-3h, 0.1-3h is heated to 70-90°C and kept for 1-3h, 0.1-1h is heated to 100°C-120°C and reacted for 6-10h. In a preferred embodiment, the following steps are followed: when the temperature is programmed to 40°C and kept for 2h, 0.5h is heated to 60°C and kept for 2h, 0.5h is heated to 80°C and kept for 2h, 0.5h is heated to 100°C-120°C and reacted for 6-10h. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification carbon four deep etherification can be obtained.

[0046] In the present invention, after the curing step and before the removal of the porogen, steps such as cooling, discharging, washing, and separation to obtain polymer white balls are required. Washing generally uses alternating cold and hot water, which is well known in the art and will not be described in detail in the present invention.

[0047] In the present invention, after the porogen removal step and before the sulfonation step, a drying and sieving step is required, which can be performed according to the prior art. According to a preferred embodiment of the present invention, the drying and sieving step is: the solid material after the porogen removal is naturally dried to a water content of 0.5-1wt%, sieved, and a solid material with a particle size of 0.3-0.6mm is taken.

[0048] The present invention also includes cooling after sulfonation, acid washing, water washing to finally obtain a water-containing resin, and the water-containing resin can be directly used as a catalyst, for example, as an etherification catalyst.

[0049] In the present invention, pickling is generally performed by washing with sulfuric acid. According to a preferred embodiment of the present invention, the pickling is firstly washed with sulfuric acid with a concentration of 60 wt %, and then washed with sulfuric acid with a concentration of 20 wt %.

[0050] By adopting the above-mentioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0051] The present invention provides a preparation method for preparing sulfonated styrene divinyl benzene resin.

[0052] In the present invention, the resin particle size can be a conventional choice in the art. According to a preferred embodiment of the present invention, the resin particle size is 0.3-0.9 mm. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be obtained.

[0053] In the present invention, the exchange equivalent of the resin can be a conventional choice in the art. According to a preferred embodiment of the present invention, the exchange equivalent of the resin is 5.2-5.4 mmolH+ / g dry agent. By adopting the aforementioned preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be increased, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0054] The invention provides an etherification catalyst, which is prepared from the sulfonated styrene divinyl benzene resin of the invention.

[0055] The present invention provides an application of a catalyst in an etherification reaction, preferably an application of a catalyst in an etherification reaction of an alcohol and an olefin.

[0056] The invention provides a method for removing isobutylene from a C4 raw material. The method comprises: in the presence of the catalyst of the invention, methanol is contacted with the C4 raw material containing isobutylene to carry out an etherification reaction.

[0057] In the present invention, there is no special requirement for the molar ratio of methanol to isobutylene. According to a preferred embodiment of the present invention, the molar ratio of methanol to isobutylene is 2-5: 1. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0058] In the present invention, there is no special requirement for the isobutylene content in the C4 raw material containing isobutylene. According to a preferred embodiment of the present invention, the isobutylene content in the C4 raw material containing isobutylene is 0.1-0.5wt%. By adopting the above preferred embodiment, the sulfonation depth can be further deepened, the exchange equivalent can be improved, and a catalyst more suitable for post-etherification C4 deep etherification can be prepared.

[0059] In the present invention, the conditions for the etherification reaction can be conventionally selected in the art.

[0060] According to a preferred embodiment of the present invention, the pressure of the etherification reaction is 0.8-2.0 MPa.

[0061] According to a preferred embodiment of the present invention, the space velocity of the etherification reaction is 1.0-6.0h-1.

[0062] According to a preferred embodiment of the present invention, the temperature of the etherification reaction is 60-90°C.

[0063] The present invention will be described in detail below through examples.

[0064] In the present invention, 50 ml of the catalyst for deep etherification of post-etherified C4 is loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm, and a deep etherification reaction of post-etherified C4 is carried out according to a molar ratio of methanol to isobutylene of 2-5:1, a reaction pressure of 0.8-2.0 MPa, a space velocity of 1.0-6.0 h-1, and a reaction temperature of 60-90°C.

[0065] The catalyst for deep etherification of post-etherified C4 prepared by the invention can reduce the content of isobutylene in post-etherified C4 from 0.1%-0.4% to below 400ppm under fixed bed reaction conditions.

[0066] Example 1

[0067] The etherification catalyst provided in this embodiment comprises the sulfonated styrene divinyl benzene resin described in this application and / or the resin prepared by the preparation method described in this application, and the specific method is as follows:

[0068] Polymerization: 100 parts of styrene, 55 parts of divinylbenzene, 40 parts of 100# solvent oil, and 0.8 parts of benzoyl peroxide were mixed evenly by weight to obtain an oil phase; 400 parts of water, 2 parts of gelatin, 0.1 parts of glycerol, 15 parts of sodium sulfate, and 3 parts of phenol were added to the polymerization kettle, stirred and heated to 50°C to make it completely dissolved, and then the oil phase was added, the stirring speed was 180 rpm, and then the temperature was raised to 80°C at 10°C / 20min. After reacting for 10 hours, the stirring was stopped, the heat was kept for curing for 5 hours, cooled, discharged, and the polymer was washed three times with hot water and cold water respectively, and the polymer white ball was separated.

[0069] Removing the porogen: Add polymer white balls into toluene, with the mass ratio of white balls to toluene being 1:10, extract the porogen, and then wash the white balls with acetone and ethanol respectively.

[0070] Drying and sieving: Place the polymer white balls after removing the porogen in a ventilated place to evaporate the residual water, dry the white balls to a moisture content of 0.5wt%, sieve, and take the white balls with a particle size between 0.3-0.6mm as qualified white balls as the sulfonation matrix.

[0071] Sulfonation: immerse the sulfonated matrix in fuming sulfuric acid, wherein the mass ratio of the sulfonated matrix to fuming sulfuric acid is 1:6, stir to fully mix the sulfonated matrix and fuming sulfuric acid, start to keep the temperature at 40℃ for 2h, then heat it to 60℃ for 0.5h and keep it for 2h, heat it to 80℃ for 0.5h and keep it for 2h, heat it to 100℃ for 0.5h and react for 6h, end the reaction, and cool. Move the resin product to a water washing column, first rinse it with 60% sulfuric acid, the volume ratio of white ball and 60% sulfuric acid is 1:5, then rinse it with 20% sulfuric acid, the volume ratio of white ball to 20% sulfuric acid is 1:5, finally rinse it with a large amount of deionized water until it is neutral, separate the resin with a water content of about 50wt%, which is the catalyst for post-etherification C4 deep etherification.

[0072] 50 ml of the catalyst for deep etherification of post-ether C4 was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm. The reaction pressure was 0.8 MPa and the space velocity was 1.0 h -1 The reaction temperature is 60°C, and the deep etherification reaction of the etherified C4 is carried out. The content of isobutylene in the etherified C4 can be reduced from 0.1wt% to 71ppm.

[0073] Example 2

[0074] Polymerization: 100 parts of styrene, 75 parts of divinylbenzene, 60 parts of 100# solvent oil, and 2 parts of benzoyl peroxide were mixed evenly by weight to obtain an oil phase; 600 parts of water, 6 parts of gelatin, 0.5 parts of glycerol, 18 parts of sodium sulfate, and 6 parts of phenol were added to the polymerization kettle, stirred and heated to 60°C to completely dissolve, and then the oil phase was added, the stirring speed was 200 rpm, and then the temperature was raised to 90°C at 10°C / 20min. After reacting for 20 hours, the stirring was stopped, the heat was kept for curing for 10 hours, cooled, discharged, and the polymer was washed three times with hot water and cold water respectively, and the polymer white ball was separated.

[0075] Removal of porogen: Add polymer white balls into toluene, with the mass ratio of white balls to toluene being 1:20, extract the porogen, and then wash the white balls with acetone and ethanol respectively.

[0076] Drying and sieving: Place the polymer white balls after removing the porogen in a ventilated place to evaporate the residual water, dry the white balls to a moisture content of 0.8wt%, sieve, and take the white balls with a particle size between 0.3-0.6mm as qualified white balls as the sulfonation matrix.

[0077] Sulfonation: immerse the sulfonated matrix in fuming sulfuric acid, wherein the mass ratio of the sulfonated matrix to the fuming sulfuric acid is 1:10, stir to fully mix the sulfonated matrix and the fuming sulfuric acid, start to keep the temperature at 40°C for 2h, then heat it to 60°C for 0.5h and keep it for 2h, heat it to 80°C for 0.5h and keep it for 2h, heat it to 100°C for 0.5h and react for 6h, end the reaction, and cool. Move the resin product to a water washing column, first rinse it with 60% sulfuric acid, the volume ratio of white ball and 60% sulfuric acid is 1:10, then rinse it with 20% sulfuric acid, the volume ratio of white ball to 20% sulfuric acid is 1:10, and finally rinse it with a large amount of deionized water until it is neutral, and separate the resin with a water content of about 50wt%, which is the catalyst for post-etherification C4 deep etherification.

[0078] 50 ml of the catalyst for deep etherification of post-etherification C4 was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm. The reaction pressure was 2.0 MPa and the space velocity was 6.0 h -1 The reaction temperature is 90°C, and a deep etherification reaction of the etherified C4 is carried out. The content of isobutylene in the etherified C4 can be reduced from 0.4wt% to 286ppm.

[0079] Example 3

[0080] Polymerization: 100 parts of styrene, 65 parts of divinylbenzene, 55 parts of 100# solvent oil, and 1 part of benzoyl peroxide were mixed evenly by weight to obtain an oil phase; 500 parts of water, 4 parts of gelatin, 0.3 parts of glycerol, 16 parts of sodium sulfate, and 5 parts of phenol were added to the polymerization kettle, stirred and heated to 55°C to completely dissolve, and then the oil phase was added, the stirring speed was 190 rpm, and then the temperature was raised to 85°C at 10°C / 20min. After reacting for 15 hours, the stirring was stopped, the temperature was kept and cured for 8 hours, cooled, discharged, and the polymer was washed three times with hot water and cold water respectively, and the polymer white ball was separated.

[0081] Removal of porogen: Add polymer white balls into toluene, with the mass ratio of white balls to toluene being 1:15, extract the porogen, and then wash the white balls with acetone and ethanol respectively.

[0082] Drying and sieving: Place the polymer white balls after removing the porogen in a ventilated place to evaporate the residual water, dry the white balls to a moisture content of 1.0wt%, sieve, and take the white balls with a particle size between 0.3-0.6mm as qualified white balls as the sulfonation matrix.

[0083] Sulfonation: immerse the sulfonated matrix in fuming sulfuric acid, wherein the mass ratio of the sulfonated matrix to fuming sulfuric acid is 1:9, stir to fully mix the sulfonated matrix and fuming sulfuric acid, start to keep the temperature at 40℃ for 2h, then heat it to 60℃ for 0.5h and keep it for 2h, heat it to 80℃ for 0.5h and keep it for 2h, heat it to 105℃ for 0.5h and react for 7h, end the reaction, and cool. Move the resin product to a water washing column, first rinse it with 60% sulfuric acid, the volume ratio of white ball and 60% sulfuric acid is 1:8, then rinse it with 20% sulfuric acid, the volume ratio of white ball to 20% sulfuric acid is 1:8, finally rinse it with a large amount of deionized water until it is neutral, separate the resin with a water content of about 50wt%, which is the catalyst for post-etherification C4 deep etherification.

[0084] 50 ml of the catalyst for deep etherification of post-etherification C4 was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm. The reaction pressure was 1.0 MPa and the space velocity was 4.0 h -1 The reaction temperature is 70°C, and the deep etherification reaction of the etherified C4 is carried out. The content of isobutylene in the etherified C4 can be reduced from 0.2wt% to 135ppm.

[0085] Comparative Example 1

[0086] The resin catalyst was prepared using the preparation scheme in Example 1 disclosed in CN1151334A.

[0087] In a 10-liter stainless steel stirred kettle with a reflux condenser, add 4500g water, 28.3g gelatin, 21g ammonium polystyrene-maleic anhydride (Mw=400,000), 240g sodium chloride and 0.4g methylene blue, heat and stir to completely dissolve the additives in the kettle and heat to 70°C, then add an organic phase mixture consisting of 770g styrene (styrene content>99%), 430g divinylbenzene (divinylbenzene content 50%), 780g sec-butyl alcohol and 12g benzoyl peroxide, stir and heat to 86°C, and react for 10 hours. Filter the reaction product, and the obtained polymer white ball is placed in 90°C deionized water, boiled under reduced pressure at 0.07MPa for 6 hours, washed twice with deionized water, and dried at room temperature to obtain 1180g white balls. 92% of the particles have a particle size range of 0.28mm-1.00mm. In a 10-liter enameled stirred kettle, add 700 g of dry polymer white balls, add 4200 g of 20% fuming sulfuric acid dropwise under stirring, control the temperature in the kettle below 70°C, then heat to 90°C and react for 2 hours; heat to 105°C and react for 4 hours; heat to 115°C and react for 4 hours, cool, and dilute the product in the kettle according to the following steps:

[0088] ① Under stirring and at a temperature below 40°C, add 5000 g of 50% dilute sulfuric acid into the kettle. After the addition is complete, suck out the dilute sulfuric acid in the kettle until the liquid level just covers the top of the resin.

[0089] ② Under stirring and at a temperature below 40°C, add 5000 g of 30% dilute sulfuric acid into the kettle. After the addition is complete, suck out the dilute sulfuric acid in the kettle.

[0090] ③Follow the steps in ② and slowly add 5000g of 30% dilute sulfuric acid.

[0091] ④ Under stirring and at a temperature below 40°C, add deionized water dropwise into the kettle and simultaneously suck out the liquid from the kettle at a certain speed until the liquid becomes neutral.

[0092] The product in the kettle is centrifuged and filtered to obtain the hydrogen-type ion exchange resin, and the white balls with a particle size between 0.3-0.6 mm are selected as qualified white balls as the sulfonation matrix.

[0093] The same evaluation process conditions as in Example 1 were adopted:

[0094] The isobutylene content in the etherified C4 was reduced from 0.1wt% to 526ppm

[0095] Comparative Example 2

[0096] The resin catalyst was prepared using the preparation scheme in Example 2 disclosed in CN1151334A.

[0097] In the same stirred tank as in Comparative Example 1, 5400g of water, 31.2g of gelatin, 1.8g of polydimethyldiallylammonium chloride (Mw=1.2 million), 240g of sodium chloride and 0.4g of methylene blue were added, the temperature was raised to 70°C, and then an organic phase mixture consisting of 570g of styrene (styrene content>99%), 630g of divinylbenzene (divinylbenzene content 50%), 800g of sec-butyl alcohol and 12g of benzoyl peroxide was added, the temperature was raised to 86°C with stirring, and the reaction was performed for 10 hours. The reaction product was filtered, and the obtained polymer white balls were placed in 100°C deionized water, boiled at normal pressure for 4 hours, and then washed twice with 80°C deionized water, dried at room temperature, and 1160g of white balls were obtained. The white balls with a particle size between 0.3-0.6mm were qualified white balls as sulfonated matrix.

[0098] The same evaluation process conditions as in Example 2 were used:

[0099] The isobutylene content in the post-ether C4 can be reduced from 0.4wt% to 1857ppm.

[0100] Comparative Example 3

[0101] The resin catalyst was prepared using the preparation scheme in Example 3 disclosed in CN1151334A.

[0102] In the polymerization formula, except that 1.4 g of ammonium styrene-maleic anhydride was used as a dispersant and 750 g of tert-butyl alcohol was used as a porogen, the other methods were the same as those in comparative example 1. 1180 g of white balls were obtained, and white balls with a particle size of 0.3-0.6 mm were selected as qualified white balls as the sulfonation matrix.

[0103] The same evaluation process conditions as in Example 3 were used:

[0104] The isobutylene content in the etherified C4 was reduced from 0.2wt% to 791ppm.

[0105] Comparative Example 4

[0106] In Example 1, phenol was replaced with methylene blue, and the rest was the same as in Example 1.

[0107] The same evaluation process conditions as in Example 1 were used:

[0108] The isobutylene content in the etherified C4 was reduced from 0.1wt% to 284ppm.

[0109] Comparative Example 5

[0110] In Example 1, phenol was removed, and the rest was the same as in Example 1.

[0111] The same evaluation process conditions as in Example 1 were used:

[0112] The isobutylene content in the post-ether C4 can be reduced from 0.1wt% to 553ppm.

[0113] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a sulfonated styrene divinyl benzene resin, It is characterized in that The method includes: The oil phase containing styrene, divinylbenzene, porogen, and initiator is subjected to suspension polymerization with the aqueous phase containing water, dispersant, dispersant aid, electrolyte, and aqueous phase inhibitor, and then solidified, and then the porogen is removed and sulfonated; wherein, The water phase inhibitor is phenol.

2. The preparation method according to claim 1, in, In parts by weight, The oil phase contains: and / or The aqueous phase contains: and / or The dispersant is glycerol; and / or The electrolyte is sodium sulfate; and / or The porogen is 100# solvent oil; and / or The initiator is benzoyl peroxide; and / or The dispersant is gelatin.

3. The preparation method according to any one of claims 1 or 2, in, The temperature of the aqueous phase is 50-60°C; and / or The conditions for suspension polymerization include: Heating rate: 5-20℃ / 20min; Temperature 80-90°C; and / or The polymerization time is 10-20h; and / or Stirring speed 180-200r / min; and / or Curing conditions include: Temperature: 80-90°C; and / or Time: 5-10h.

4. The preparation method according to any one of claims 1 to 3, in, The method for removing the porogen includes: adding the solidified solid material into an aromatic hydrocarbon solvent, extracting the porogen, and washing the solid material with an organic solvent; Preferably, The aromatic hydrocarbon solvent comprises toluene; and / or The organic solvent comprises acetone and / or ethanol, preferably a mixture of acetone and ethanol; and / or The weight ratio of the solid material to the aromatic solvent is 1:10-20; and / or The sulfonation method comprises: the solid material obtained after removing the porogen is contacted with a sulfonation reagent to carry out a sulfonation reaction, followed by acid washing and water washing; Preferably, The mass ratio of the solid material to the sulfonating agent is 1:6-10; and / or The sulfonating agent is selected from oleum; and / or The conditions of the sulfonation reaction include: heating to 30-50°C and keeping for 1-3h, heating to 50-70°C for 0.1-1h and keeping for 1-3h, heating to 70-90°C for 0.1-3h and keeping for 1-3h, heating to 100-120°C for 0.1-1h and reacting for 6-10h.

5. The sulfonated styrene divinyl benzene resin prepared by the preparation method according to any one of claims 1 to 4.

6. The resin according to claim 5, in, The resin particle size is 0.3-0.9 mm; and / or The exchange equivalent of the resin is 5.2-5.4 mmol H+ / g dry agent.

7. An etherification catalyst, It is characterized in that The sulfonated styrene divinyl benzene resin according to claim 5 or 6.

8. Use of the catalyst according to claim 7 in an etherification reaction, preferably in an etherification reaction of an alcohol and an olefin.

9. A method for removing isobutylene from a C4 raw material, It is characterized in that The method includes: In the presence of the catalyst according to claim 7, methanol is contacted with a C4 raw material containing isobutylene to carry out an etherification reaction; Preferably, the molar ratio of methanol to isobutylene is 2-5:1; and / or The isobutylene content in the isobutylene-containing C4 raw material is 0.1-0.5wt%.

10. The method according to claim 9, in, The conditions for the etherification reaction include: The pressure is 0.8-2.0MPa; and / or Airspeed: 1.0-6.0h -1 ; and / or The temperature is 60-90℃.

Images