Catalyst for synthesizing mtbe and its preparation method and application

Abstract

The application belongs to the technical field of MTBE synthesis catalysts, and particularly relates to an MTBE synthesis catalyst, a preparation method and application thereof. The preparation method of the MTBE synthesis catalyst comprises the following steps: an oil phase composed of styrene, methyl methacrylate, divinylbenzene, a pore former and an initiator, and an aqueous phase composed of water, a dispersing agent and a co-dispersing agent are subjected to suspension copolymerization, and then the MTBE synthesis catalyst is prepared through solidification, pore former removal, drying and screening of a sulfonated matrix prepared through the above steps, and then through sulfonation, acid washing and water washing. The MTBE synthesis catalyst has suitable particle size, suitable pore structure and high exchange equivalent, and the hydrophobic groups on the white balls can timely remove the generated water from the reaction system, so that the MTBE synthesis catalyst has a good application prospect in the application field of synthesizing methyl tert-butyl ether from tert-butyl alcohol and methanol.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of MTBE synthesis catalysts, and particularly relates to an MTBE synthesis catalyst and a preparation method and application thereof. BACKGROUND

[0002] Most of the current processes for producing methyl tert-butyl ether are based on the liquid phase reaction of isobutylene and methanol catalyzed by cation exchange resin. Due to the sharp expansion of the demand for methyl tert-butyl ether, the isobutylene raw material cannot meet the demand. In recent years, due to the continuous expansion of propylene oxide production, the amount of by-product tert-butyl alcohol is increasing, so the process route of preparing methyl tert-butyl ether from methanol and tert-butyl alcohol is also extremely valuable.

[0003] At present, there are a large number of reports on catalysts for the reaction of methanol and tert-butyl alcohol to prepare methyl tert-butyl ether. The proton acid catalytic mechanism of the current reaction has reached a consensus. Zeolite molecular sieves such as HY, HZSM-5 and HM can be applied to the reaction. However, zeolite catalysis has problems such as high reaction temperature, many side reactions, long separation process and the like, and it is difficult to be applied in industrialization. Traditional macroporous cation resin catalysts can also be applied to the reaction of methanol and tert-butyl alcohol to generate methyl tert-butyl ether. Since water is generated in the reaction, and water will cause the loss of sulfonate, if the exchange equivalent of the current macroporous cation resin catalyst is not improved, the service time of the resin catalyst will be greatly reduced due to the loss of sulfonate. Therefore, it is necessary to prepare a macroporous cation resin catalyst by using a suitable process, so as to improve the exchange equivalent of the macroporous cation resin catalyst and improve the diffusion speed of the material to achieve the purpose of improving the conversion rate of tert-butyl alcohol. Since the improvement of the exchange equivalent will improve the conversion rate, and since the improvement of the exchange equivalent will reduce the speed of the sulfonate in the same reaction system, the service time of the resin catalyst will be prolonged.

[0004] Patent CN1389297 discloses a preparation method of a macroporous cation exchange resin catalyst with high exchange capacity. C10-C40 saturated alkane pore-forming agent is used, and a high molecular compound suitable therefor is used as a dispersing aid to make the copolymer white ball with reasonable pore structure and uniform particle size by suspension copolymerization of styrene and a polyvinyl monomer. Then, a low-boiling-point solvent that can be mutually soluble with the pore-forming agent is used to purify the pore structure of the white ball, so as to obtain a resin catalyst with an exchange equivalent greater than 5.0 mmol / g for use in light hydrocarbon etherification and organic catalytic reaction. The deficiency of the present application is that the resin particles are not uniform, the range of the resin particles is 0.3-1.2 mm, the range is relatively wide, the size of the particles is different, the strength of the resin is not uniform, the larger particles in the reactor are easy to break, which causes the problem of the increase of the pressure drop of the reactor, and then the formation of a bias flow in the reactor, which is not conducive to the diffusion of the material for the reaction of tert-butyl alcohol and methanol, and the reaction conversion rate is low.

[0005] Patent CN111957346A discloses an etherification catalyst for preparing methyl tert-butyl ether from methanol and tert-butyl alcohol and a preparation method thereof, liquid paraffin is used as a pore former, and the copolymer white ball is obtained by suspension copolymerization of an oil phase and a dispersion phase, extraction, drying and screening, and then the copolymer white ball is prepared by sulfonation and washing. The compatible high molecular compound in the aqueous phase is a dispersion aid, which enables the suspension copolymerization of styrene and a multi-vinyl monomer, and the copolymer white ball with reasonable pore structure and uniform particle size is prepared. The pore structure of the white ball is purified by using a low-boiling-point solvent that is miscible with the pore former, and the resin catalyst with an exchange equivalent greater than 5.0 mmol / g is used for the reaction of tert-butyl alcohol and methanol. The patent has the following disadvantages: the crosslinking degree is too large, which leads to insufficient introduction of sulfonate groups, low catalyst activity, and the addition of polyvinyl alcohol in the aqueous phase leads to small catalyst particles, and the water content in the product causes the pressure drop in the reactor to increase, and the catalyst is broken. SUMMARY

[0006] The technical problem to be solved by the present application is to provide an MTBE synthesis catalyst with suitable particle size, suitable pore structure, high exchange equivalent, and hydrophobic groups on the white ball that can remove the generated water from the reaction system in time, which has good popularization and application prospect in the application field of synthesizing methyl tert-butyl ether from tert-butyl alcohol and methanol. The present application also provides a preparation method and application thereof.

[0007] The preparation method of the MTBE synthesis catalyst comprises the following steps: suspension copolymerization of an oil phase composed of styrene, methyl methacrylate, divinylbenzene, a pore former and an initiator, and an aqueous phase composed of water, a dispersant and a dispersant aid, solidification, pore former removal, drying and screening to obtain a sulfonated matrix, and then sulfonation, acid washing and water washing to obtain the MTBE synthesis catalyst.

[0008] In the present application, the oil phase is composed of the following raw materials in parts by weight:

[0009]

[0010] In the present application, the aqueous phase is composed of the following raw materials in parts by weight:

[0011] Water 400 parts,

[0012] Dispersant 4-10 parts,

[0013] Dispersant aid 0.05-0.1 parts.

[0014] In the present application, the pore former is tert-amyl alcohol.

[0015] In the present application, the initiator is benzoyl peroxide.

[0016] In the present application, the dispersant is gelatin.

[0017] In the present application, the dispersant aid is sodium chloride.

[0018] Specifically comprising the following steps:

[0019] (1) Polymerization: uniformly mix styrene, methyl methacrylate, divinylbenzene, porogen, initiator to obtain an oil phase; mix water, dispersant, dispersant aid, and heat to 50-60°C to obtain an aqueous phase; add the oil phase to the aqueous phase, stir, and heat to 70-80°C to perform suspension copolymerization reaction, after 8-18h of reaction, stop stirring, incubate for 5-10h, then cool, discharge, and wash with water to separate the polymer white balls;

[0020] (2) Porogen removal: add the polymer white balls to water, heat to boiling and maintain the boiling state, when 60-80wt% of the water evaporates, add an equal amount of water, and continue boiling until no porogen is detected in the residual water;

[0021] (3) Drying and sieving: naturally dry the polymer white balls after porogen removal to a water content of 0.5-1wt%, sieve, and take the polymer white balls with a particle size of 0.5-0.8mm as the sulfonation matrix;

[0022] (4) Sulfonation: immerse the sulfonation matrix in fuming sulfuric acid, stir to mix the sulfonation matrix and fuming sulfuric acid thoroughly, program the temperature to 100-120°C for 6-10h of reaction, then cool, wash with acid, and wash with water to obtain the MTBE synthesis catalyst.

[0023] In one embodiment, in step (1), after adding the oil phase to the aqueous phase, maintain the stirring speed at 140-150rpm, and heat to 70-80°C at a heating rate of 10°C / 20min to perform suspension copolymerization reaction.

[0024] In one embodiment, in step (1), when washing with water, wash the polymer with hot water and cold water for 3 times respectively to separate the polymer white balls.

[0025] In step (2), the weight ratio of the polymer white balls to water is 1:10-20. Preferably, distilled water is used, and the porogen tert-amyl alcohol is removed completely using the azeotrope of water and tert-amyl alcohol.

[0026] In step (4), the mass ratio of the sulfonation matrix to fuming sulfuric acid is 1:6-10.

[0027] In one embodiment, in step (4), when programming the temperature, incubate at 40°C for 2h, heat to 60°C for 2h at a heating rate of 0.5h, heat to 80°C for 2h at a heating rate of 0.5h, heat to 100-120°C for 6-10h at a heating rate of 0.5h, and end the reaction.

[0028] In one embodiment, in step (4), the acid washing is first washed with 60wt% sulfuric acid, and then washed with 20wt% sulfuric acid.

[0029] In step (4), the water washing is until the water washing liquid is neutral, and then the resin with a water content of about 50wt% is separated, which is the MTBE synthesis catalyst.

[0030] In the preparation process of the present application, by controlling the raw material ratio and reaction conditions, when styrene and divinylbenzene are polymerized to produce polymer white balls, the crosslinking degree is controlled to be 15%-18%, and then the polymer white balls are solidified, and the tertiary amyl alcohol non-good solvent is matched, so that the pore size of the polymer white balls is increased as much as possible under the condition of the determined crosslinking degree, and the pore structure is stabilized by resin solidification. The relatively stable microstructure is beneficial to the introduction and fixation of sulfonic acid groups, improves the exchange equivalent after sulfonation, and due to the presence of sodium chloride and high rotation speed, the particles of the resin catalyst are appropriately reduced. The relatively small particles and the white balls with large pore size not only further improve the sulfonation efficiency, but also are beneficial to the diffusion of the material, reduce the generated water covering on the active center site, and further improve the conversion rate. Especially, methyl methacrylate is added in the polymerization process. The introduction of methyl methacrylate will cause hydrophobic groups in the pore, so that the generated water is timely separated from the pore to improve the conversion rate. The above elements cooperate with each other to prepare a resin catalyst suitable for the synthesis of methyl tert-butyl ether from methanol and tert-butyl alcohol, which has suitable particle size, suitable pore structure, high exchange equivalent, and appropriate strength.

[0031] The second object of the present application is to provide an MTBE synthesis catalyst prepared by the above preparation method.

[0032] The second object of the present application is to provide an application of the MTBE synthesis catalyst for synthesizing methyl tert-butyl ether from methanol and tert-butyl alcohol.

[0033] In one embodiment, the MTBE synthesis catalyst is loaded into a fixed bed reactor with an inner diameter of 10mm and a length of 1000mm, and the molar ratio of methanol to tert-butyl alcohol is 3:1, the reaction pressure is 0.8-2.0MPa, the space velocity is 0.5-4h -1 , the reaction temperature is 60-90℃, and the etherification of methanol tert-butyl alcohol is carried out to prepare methyl tert-butyl ether.

[0034] The MTBE synthesis catalyst prepared by the present application has a tert-butyl alcohol conversion rate of >73% under the fixed bed reaction conditions.

[0035] Compared with the prior art, the present application has the following beneficial effects:

[0036] (1) The present application controls the crosslinking degree of the polymer white ball to be 15%-18%, and adds methyl methacrylate during polymerization, and then solidifies the white ball, and uses tertiary amyl alcohol as a non-good solvent, so that the resin white ball can increase the pore size as much as possible under the condition of the determined crosslinking degree, improve the exchange equivalent after sulfonation, and remove the generated water from the active center site in time, and the above elements cooperate with each other to prepare a resin catalyst for synthesizing methyl tert-butyl ether, which has a suitable particle size, a suitable pore structure, a high exchange equivalent, and a suitable strength.

[0037] (2) The catalyst prepared by the present application has a suitable particle size, a suitable pore structure, and a high exchange equivalent, and the hydrophobic group on the white ball can remove the generated water from the reaction system in time, so that the catalyst has a good application prospect in the field of synthesizing methyl tert-butyl ether from tert-butyl alcohol and methanol. DETAILED DESCRIPTION

[0038] The present application will be further described below in combination with examples, but the protection scope of the present application is not limited to this. Changes made by the person skilled in the art to the technical solutions of the present application shall be within the protection scope of the present application.

[0039] In the examples, the raw materials used, unless otherwise specified, are all conventional commercially available raw materials; and the process methods used in the examples, unless otherwise specified, are all conventional methods in the art.

[0040] Example 1

[0041] (1) Polymerization: 100 parts of styrene, 5 parts of methyl methacrylate, 30 parts of divinylbenzene, 30 parts of tertiary amyl alcohol, and 1 part of benzoyl peroxide were uniformly mixed to obtain an oil phase; 400 parts of water, 4 parts of gelatin, and 0.05 parts of sodium chloride were added to a polymerization kettle, stirred, and heated to 50°C until completely dissolved, and then the oil phase was added, the stirring speed was 140 r / min, and then the temperature was increased to 70°C at a rate of 10°C / 20 min. After 8 h of reaction, the stirring was stopped, and the temperature was maintained for 5 h for solidification, and then the polymer was washed with hot water and cold water for three times, and the polymer was separated.

[0042] (2) Deswelling agent: the polymer white ball was added to a reaction kettle, distilled water was added, the weight ratio of the white ball to the distilled water was 1:10, the temperature was increased to boiling, the water was evaporated by 80 wt%, the temperature was decreased to supplement the evaporation amount of water, and the boiling was continued to remove the tertiary amyl alcohol, and the deswelling agent was completely removed by using the azeotropy of water and tertiary amyl alcohol, and no deswelling agent was detected in the residual water.

[0043] (3) Drying and screening: the polymer white ball after deswelling agent was placed in a ventilated place to volatilize the residual water, the white ball was dried to a water content of 0.5 wt%, and then screened, and the white ball with a particle size of 0.5-0.8 mm was taken as a qualified white ball as a sulfonation matrix.

[0044] (4) Sulfonation: The sulfonation matrix is immersed in fuming sulfuric acid, with a mass ratio of sulfonation matrix to fuming sulfuric acid of 1:6, and stirred to mix the sulfonation matrix and fuming sulfuric acid thoroughly. The temperature is kept at 40°C for 2 hours, then raised to 60°C for 2 hours, then raised to 80°C for 2 hours, then raised to 100°C for 6 hours, and then the reaction is stopped. The resin product is moved to a water washing column, first washed with 60% sulfuric acid at a volume ratio of white ball to 60% sulfuric acid of 1:5, then washed with 20% sulfuric acid at a volume ratio of white ball to 20% sulfuric acid of 1:5, and finally washed with a large amount of deionized water until neutral. The resin with a water content of about 50 wt% is separated, which is the MTBE synthesis catalyst.

[0045] The above fresh MTBE synthesis catalyst 50 ml is loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm to perform a synthesis test of methanol tert-butyl alcohol etherification to produce methyl tert-butyl ether. The chemical properties of the prepared catalyst are evaluated. The molar ratio of methanol to tert-butyl alcohol is 3:1. The reaction pressure is 0.8 MPa, the space velocity is 0.5 h -1 , and the reaction temperature is 60°C. Under the fixed bed reaction conditions, the conversion rate of tert-butyl alcohol is 77.64%.

[0046] Example 2

[0047] (1) Polymerization: 100 parts of styrene, 10 parts of methyl methacrylate, 40.5 parts of divinylbenzene, 50 parts of tert-amyl alcohol, and 2 parts of benzoyl peroxide are mixed uniformly to obtain an oil phase; 400 parts of water, 10 parts of gelatin, and 0.1 part of sodium chloride are added to a polymerization kettle, stirred, and heated to 60°C to completely dissolve, then the oil phase is added, the stirring speed is 150 revolutions / min, and then the temperature is raised to 80°C at a rate of 10°C / 20 min. After 18 hours of reaction, the stirring is stopped, the temperature is kept constant for 10 hours for solidification, and then the product is cooled, discharged, washed with hot water and cold water three times, and the polymer is separated as white balls.

[0048] (2) Deswelling agent removal: The polymer white balls are added to a reaction kettle, distilled water is added, the weight ratio of white balls to distilled water is 1:20, the temperature is raised to boiling, the boiling state is maintained, after 60 wt% of water is evaporated, the temperature is lowered and the same amount of water is added, and the boiling is continued to remove the deswelling agent completely by using the azeotrope of water and tert-amyl alcohol, until no deswelling agent is detected in the residual water.

[0049] (3) Drying and sieving: The polymer white balls after deswelling agent removal are placed in a ventilated place to volatilize the residual water, dried to a water content of 1 wt%, sieved, and the white balls with a particle size of 0.5-0.8 mm are taken as qualified white balls as the sulfonation matrix.

[0050] (4) Sulfonation: The sulfonation matrix is immersed in fuming sulfuric acid, with the mass ratio of sulfonation matrix to fuming sulfuric acid being 1:10, and the sulfonation matrix is stirred to mix with the fuming sulfuric acid. The temperature is kept at 40°C for 2 hours, then increased to 60°C for 2 hours, then increased to 80°C for 2 hours, then increased to 100°C for 6 hours, and then the reaction is stopped. The resin product is moved to a water washing column, first washed with 60% sulfuric acid at a volume ratio of white ball to 60% sulfuric acid of 1:10, then washed with 20% sulfuric acid at a volume ratio of white ball to 20% sulfuric acid of 1:10, and finally washed with a large amount of deionized water until neutral. The resin with a water content of about 50% by weight is separated, which is the MTBE synthesis catalyst.

[0051] The above fresh MTBE synthesis catalyst 50ml is loaded into a fixed bed reactor with an inner diameter of 10mm and a length of 1000mm to perform a synthesis test of methanol tert-butyl alcohol etherification to produce methyl tert-butyl ether. The chemical properties of the prepared catalyst are evaluated. The molar ratio of methanol to tert-butyl alcohol is 3:1. The reaction pressure is 2.0MPa, the space velocity is 4h -1 , and the reaction temperature is 90°C. Under the fixed bed reaction conditions, the conversion rate of tert-butyl alcohol is 74.91%.

[0052] Example 3

[0053] (1) Polymerization: 100 parts of styrene, 20 parts of methyl methacrylate, 35 parts of divinylbenzene, 40 parts of tert-amyl alcohol, and 1.5 parts of benzoyl peroxide are mixed uniformly to obtain an oil phase; 400 parts of water, 8 parts of gelatin, and 0.08 parts of sodium chloride are added to a polymerization kettle, stirred, and heated to 55°C to completely dissolve, then the oil phase is added, the stirring speed is 145r / min, and then the temperature is increased to 80°C at a rate of 10°C / 20min. After 14h of reaction, the stirring is stopped, the temperature is kept constant for 7h, and then the polymer is cooled, discharged, washed with hot water and cold water three times, and separated to obtain the polymer white ball.

[0054] (2) Deswelling agent removal: The polymer white ball is added to a reaction kettle, distilled water is added, the weight ratio of white ball to distilled water is 1:10, the temperature is increased to boiling, the boiling state is maintained, after 70wt% of water is evaporated, the temperature is decreased to supplement the evaporation amount of water, and the boiling is continued to remove the tert-amyl alcohol completely by using the azeotropy of water and tert-amyl alcohol until no deswelling agent is detected in the residual water.

[0055] (3) Drying and sieving: The polymer white ball after deswelling agent removal is placed in a ventilated place to volatilize the residual water, dried to a water content of 1wt%, sieved, and the white ball with a particle size of 0.5-0.8mm is taken as the qualified white ball as the sulfonation matrix.

[0056] (4) sulfonated: the sulfonated substrate was immersed in fuming sulfuric acid, the mass ratio of the sulfonated substrate to the fuming sulfuric acid was 1:9, the sulfonated substrate was stirred to mix with the fuming sulfuric acid, 2 h of incubation at 40°C was started, then 0.5 h of incubation at 60°C was started, then 0.5 h of incubation at 80°C was started, then 0.5 h of incubation at 105°C was started, 7 h of reaction at 105°C was started, and the reaction was ended, and the reaction was cooled. The resin product was moved to a water washing column, first washed with 60% sulfuric acid, the volume ratio of the white ball to the 60% sulfuric acid was 1:8, then washed with 20% sulfuric acid, the volume ratio of the white ball to the 20% sulfuric acid was 1:8, and finally washed with a large amount of deionized water until neutral, and a resin with a water content of about 50 wt% was separated, which was the MTBE synthesis catalyst.

[0057] The above fresh MTBE synthesis catalyst 50 ml was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm to perform a synthesis test of methanol tert-butyl alcohol etherification to prepare methyl tert-butyl ether. The chemical properties of the prepared catalyst were evaluated. The molar ratio of methanol to tert-butyl alcohol was 3:1. The reaction pressure was 1.5 MPa, the space velocity was 3 h -1 -1, and the reaction temperature was 70°C. Under the fixed bed reaction conditions, the conversion rate of tert-butyl alcohol was 75.37%.

[0058] Comparative Example 1

[0059] The resin catalyst was prepared by using the preparation scheme in Example 1 disclosed in the patent CN1389297, and the same evaluation process conditions as Example 1 were used: the above fresh resin catalyst 50 ml was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm to perform a synthesis test of methanol tert-butyl alcohol etherification to prepare methyl tert-butyl ether. The chemical properties of the prepared catalyst were evaluated. The molar ratio of methanol to tert-butyl alcohol was 3:1. The reaction pressure was 0.8 MPa, the space velocity was 0.5 h -1 -1, and the reaction temperature was 60°C. Under the fixed bed reaction conditions, the conversion rate of tert-butyl alcohol was 65.71%.

[0060] Comparative Example 2

[0061] The resin catalyst was prepared by using the preparation scheme in Example 1 disclosed in the patent CN111957346A, and the same evaluation process conditions as Example 1 were used: the above fresh resin catalyst 50 ml was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm to perform a synthesis test of methanol tert-butyl alcohol etherification to prepare methyl tert-butyl ether. The chemical properties of the prepared catalyst were evaluated. The molar ratio of methanol to tert-butyl alcohol was 3:1. The reaction pressure was 0.8 MPa, the space velocity was 0.5 h -1 -1, and the reaction temperature was 60°C. Under the fixed bed reaction conditions, the conversion rate of tert-butyl alcohol was 67.84%.

[0062] Comparative Example 3

[0063] The resin catalyst was prepared by using the preparation scheme in Example 1 of patent CN108371956A. The same evaluation process conditions as Example 1 were used: 50 ml of the above fresh resin catalyst was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm to perform synthesis test of methanol tert-butyl alcohol etherification to prepare methyl tert-butyl ether. The chemical properties of the prepared catalyst were evaluated. The molar ratio of methanol to tert-butyl alcohol was 3:1. The reaction pressure was 0.8 MPa, the space velocity was 0.5 h -1 , and the reaction temperature was 60℃. Under the fixed bed reaction conditions, the conversion rate of tert-butyl alcohol was 54.17%.

[0064] Comparative Example 4

[0065] Methyl methacrylate was added to the white ball polymerization process in Comparative Example 3, and the other components remained unchanged. The added amount of methyl methacrylate was 10 parts. The resin catalyst was prepared under the same preparation conditions. 50 ml of the above fresh resin catalyst was loaded into a fixed bed reactor with an inner diameter of 10 mm and a length of 1000 mm to perform synthesis test of methanol tert-butyl alcohol etherification to prepare methyl tert-butyl ether. The chemical properties of the prepared catalyst were evaluated. The molar ratio of methanol to tert-butyl alcohol was 3:1. The reaction pressure was 0.8 MPa, the space velocity was 0.5 h -1 , and the reaction temperature was 60℃. Under the fixed bed reaction conditions, the conversion rate of tert-butyl alcohol was 72.85%.

[0066] The resin catalyst of the present application has good effect after comparison with the catalyst prepared according to the examples disclosed in the comparative examples.

Claims

1. A process for the preparation of a catalyst for the synthesis of MTBE, characterized in that: It comprises the following steps: The oil phase composed of styrene, methyl methacrylate, divinylbenzene, porogen and initiator, and the water phase composed of water, dispersant and auxiliary dispersant are subjected to suspension copolymerization, and then the sulfonated matrix is prepared through solidification, porogen removal, drying and screening, and then the MTBE synthesis catalyst is prepared through sulfonation, acid washing and water washing; The oil phase is composed of the following raw materials in parts by weight: Styrene 100 parts, Methyl methacrylate 5-20 parts, Divinylbenzene 30-40.5 parts, Porogen 30-50 parts, Initiator 1-2 parts; The water phase is composed of the following raw materials in parts by weight: Water 400 parts, Dispersant 4-10 parts, Auxiliary dispersant 0.05-0.1 parts; The porogen is tert-amyl alcohol. It comprises the following steps:

2. The method of claim 1, wherein the MTBE synthesis catalyst is prepared by: (1) Polymerization: uniformly mix styrene, methyl methacrylate, divinylbenzene, porogen and initiator to obtain an oil phase; mix water, dispersant and auxiliary dispersant and heat to 50-60℃ to obtain a water phase; add the oil phase to the water phase, stir and heat to 70-80℃ for suspension copolymerization reaction, stop stirring after 8-18h, and then heat for 5-10h, and then cool, discharge, and wash with water to separate out the polymer white ball; (2) Porogen removal: add the polymer white ball to water, heat to boiling and maintain the boiling state, add the same amount of water when 60-80wt% of water evaporates, and continue to boil until no porogen is detected in the residual water; (3) Drying and screening: naturally dry the polymer white ball after porogen removal to a water content of 0.5-1wt%, screen, and take the polymer white ball with a particle size of 0.5-0.8mm as the sulfonated matrix; (4) Sulfonation: immerse the sulfonated matrix in fuming sulfuric acid, stir to mix the sulfonated matrix and fuming sulfuric acid, heat to 100-120℃ in stages for 6-10h, end the reaction, and then cool, acid wash and wash with water to obtain the MTBE synthesis catalyst. The initiator is benzoyl peroxide.

3. The method of claim 1, wherein the MTBE synthesis catalyst is prepared by: The dispersant is gelatin, and the auxiliary dispersant is sodium chloride.

4. The method of claim 1, wherein the MTBE synthesis catalyst is prepared by: In step (2), the weight ratio of the polymer white ball to water is 1:10-20.

5. The method for preparing the MTBE synthesis catalyst according to claim 2, characterized in that: In step (4), the mass ratio of the sulfonated matrix to fuming sulfuric acid is 1:6-10.

6. The method of claim 2, wherein the MTBE synthesis catalyst is prepared by: Prepared by the preparation method of any one of claims 1-6.

7. An MTBE synthesis catalyst characterized by: Used for the reaction of methanol and tert-butyl alcohol to synthesize methyl tert-butyl ether.

8. Use of the MTBE synthesis catalyst according to claim 7, characterized in that: ​

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