CN110586185B - Tert-butyl alcohol methanol etherification resin catalyst and preparation method thereof - Google Patents
Tert-butyl alcohol methanol etherification resin catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tert-butyl alcohol methanol etherification resin catalyst and a preparation method thereof, wherein a polymerized white sphere of styrene-divinylbenzene crosslinking copolymerization is used as a matrix, the polymerized white sphere is placed in a dispersed phase, then a homogeneous phase is added to wrap the polymerized white sphere matrix to obtain a copolymer white sphere, the copolymer white sphere is subjected to functional group stabilization to obtain a finished product white sphere, and the white sphere is the tert-butyl alcohol methanol etherification resin catalyst. The tert-butyl alcohol methanol etherification resin catalyst prepared by the method has the advantages of high activity, high temperature resistance, high stability and the like; the macropores on the catalyst are of a special pore structure, show special polarity, have high adsorption performance on tert-butyl alcohol and methanol, enable two materials to be more easily close to an active center, easily react and enhance the reaction activity; the special methanol adsorption capacity of the catalyst reduces the saturated vapor pressure of methanol, improves the utilization rate of methanol and reduces the production cost.
Description
Technical Field
The invention provides a tert-butyl alcohol methanol etherification resin catalyst and a preparation method thereof, and particularly provides a tert-butyl alcohol methanol etherification resin catalyst with high activity and high temperature resistance and a preparation method thereof.
Background
Methyl tert-butyl ether (MTBE) is used as a gasoline additive and an antiknock agent, and has the advantages of high octane number and the like. High-purity isobutene can be prepared by cracking MTBE, and in recent years, isobutene is used as a raw material in the fields of fine chemical engineering such as butyl rubber, methyl methacrylate and polyisobutylene, and the using amount of the isobutene is increasing.
Currently, the main production route of MTBE is to react methanol with isobutene in C4 fraction by using cationic resin as a catalyst, wherein isobutene is mainly obtained from a byproduct C4 in the ethylene industry and a byproduct C4 in an oil refining catalytic cracking unit, and it is difficult to meet the production requirement of MTBE.
The domestic ethylene oxide device is put into operation continuously, the byproduct tertiary butanol produced by the device is increased, the tertiary butanol reaches 332kt per year in a set of ethylene oxide production device producing 253kt per year, the tertiary butanol yield is excessive, the price of the tertiary butanol still has a reduced space, the economic benefit is obvious, and the problem that the isobutene cannot meet the production requirement of MTBE can be effectively solved by adopting the tertiary butanol and methanol for etherification.
The present industrially used tert-butyl alcohol and methanol etherification resin catalyst has the problem of low single pass conversion rate, a large amount of methanol and tert-butyl alcohol need to be circulated, the number of produced finished products is increased, and the conventional acidic resin catalyst is adopted, so that the operation temperature is not easy to be too high, otherwise the problems of catalyst activity reduction and obvious desulfurization can occur.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a tert-butyl alcohol methanol etherification resin catalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of tert-butyl alcohol methanol etherification resin catalyst comprises the following steps:
the method comprises the steps of taking a polymerized white ball of styrene-divinylbenzene crosslinking copolymerization as a matrix, placing the polymerized white ball in a dispersed phase, adding a homogeneous phase to the polymerized white ball matrix for coating to obtain a copolymer white ball, stabilizing the copolymer white ball through functional groups to obtain a finished product white ball, wherein the white ball is a tert-butyl alcohol methanol etherification resin catalyst.
In the above technical scheme, the preparation method specifically comprises the following steps:
(1) preparation of polymeric white ball precursor:
adding 2-55 parts by weight of styrene, 10-55 parts by weight of divinylbenzene, 45-75 parts by weight of pore-forming agent and 1 part by weight of dibenzoyl peroxide into a reaction kettle added with 1010 parts by weight of dispersed phase, stirring and adjusting into microspheres with the granularity of 0.2-0.4mm, heating to 40-98 ℃ under the stirring condition, and reacting for 10-30h to generate a polymeric white ball matrix;
(2) preparation of copolymer white balls:
adding 300 parts by weight of the polymer matrix white ball obtained in the step (1) into 1000 parts by weight of water, then adding 100-200 parts by weight of p-chlorostyrene, 5-50 parts by weight of divinylbenzene, 20-50 parts by weight of pore-forming agent and 1 part by weight of benzoyl peroxide, uniformly mixing, standing for 2-4h, then adding 1010 parts by weight of disperse phase, heating to 79-98 ℃ under the condition of stirring, then keeping the temperature for 2-30h, cooling, extracting the pore-forming agent, and drying solid materials to obtain the copolymer white ball;
(3) functional group stabilization:
adding 1000 parts by weight of fuming sulfuric acid and 40 parts by weight of dichloroethane into 100 parts by weight of the copolymer white ball obtained in the step (2) to carry out sulfonation reaction, heating to 40-115 ℃ for sulfonation reaction for 10-35h, cooling, adjusting the acid concentration, carrying out sulfonation reaction to realize functional group stabilization to obtain a finished product, wherein the finished product is the tert-butyl alcohol methanol etherification resin catalyst.
In the above technical scheme, in the step (1), the dispersed phase is a mixture of a sodium chloride solution and polyvinyl alcohol, and 1010 parts of the dispersed phase comprises 1000 parts of a sodium chloride solution with a specific gravity of 1.2 and 10 parts of polyvinyl alcohol.
In the above technical scheme, in the step (1), the pore-forming agent is any one of 300# liquid wax, n-amyl alcohol, isoamyl alcohol and 4-methyl-2-amyl alcohol, and a mixture of two or more of them in any proportion; preferably 300# liquid wax and isoamylol are mixed in any proportion; more preferably, the wax is a mixture of 30 parts of No. 300 liquid wax and 25 parts of isoamyl alcohol.
In the technical scheme, in the step (1), the stirring is carried out at the rotating speed of 200 r/min.
In the above technical scheme, in the step (1), the prepared polymeric white sphere matrix has a crosslinking degree of 10-53, preferably 53.
In the above technical solution, in the step (1), the temperature raising process of the polymerized white ball matrix is preferably: heating to 79 ℃ and preserving heat for 10h, heating to 89 ℃ for 2h and preserving heat for 2h, heating to 98 ℃ for 2h and preserving heat for 10h, and then cooling.
In the above technical solution, in the step (2), the pore-forming agent is isoamyl alcohol.
In the above technical solution, in the step (2), preferably, 5 parts of the diethylbenzene is used.
In the above technical scheme, in the step (2), the dispersed phase is a mixture of a sodium chloride solution and polyvinyl alcohol, and 1010 parts of the dispersed phase comprises 1000 parts of a sodium chloride solution with a specific gravity of 1.2 and 10 parts of polyvinyl alcohol.
In the above technical scheme, in the step (2), the stirring is carried out at a rotation speed of 200 r/min.
In the above technical solution, in the step (2), the copolymer white ball preferably has a temperature rise process: heating to 79 deg.C, keeping the temperature for 10h, heating to 98 deg.C for 4h, reacting for 10h, and cooling.
In the above technical solution, in the step (3), the sulfonation reaction is performed to stabilize the functional group, and the specific operation is preferably: adding the materials into a reaction kettle, stirring for 2h, heating to 81 ℃ for 3h, then preserving heat for 5h, heating to 86 ℃ for 5h, then preserving heat for 4h, heating to 115 ℃ for 5h, then preserving heat for 6h, cooling, reducing the acid ratio in the kettle to 1.0 by using dilute acid, and performing functional group stabilization treatment to obtain white balls which are tert-butyl alcohol methanol etherification resin catalysts.
The technical scheme of the invention has the advantages that:
(1) the resin catalyst has the advantages of high activity, high temperature resistance, high stability and the like;
(2) the macropores on the catalyst are of a special pore structure, show special polarity, and have high adsorption performance on tert-butyl alcohol and methanol, so that two materials can be more easily close to an active center, reaction is easy to occur, and the reaction activity is enhanced;
(3) the special methanol adsorption capacity of the catalyst reduces the saturated vapor pressure of methanol, improves the utilization rate of methanol and reduces the production cost.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
the devices and materials used in the examples of the invention are as follows:
1. the device comprises the following steps: a constant-temperature water bath (0-100 ℃); an adjustable electric stirrer (0-2000 revolutions); three-necked bottles (2000 ml); a plastic stirring paddle; a thermometer (0-150 ℃); rubber stopper (No. 5); a constant temperature oil bath pan (0-300 ℃); 100ml measuring cylinder.
2. The main raw materials are as follows: divinylbenzene, outsourcing technical grade; styrene, outsourcing technical grade; p-chlorostyrene, purchased technical grade; fuming sulfuric acid, outsourcing commercial grade; water, deionized water; 93% t-butanol, jinling hensman; 99% of methanol and outsourcing industrial grade.
The process of the invention is illustrated below with reference to specific examples:
example 1:
(1) preparation of polymeric white ball precursor:
according to the weight portion, 10 portions of styrene, 55 portions of divinylbenzene, 20 portions of No. 300 liquid wax, 25 portions of isoamyl alcohol and 1 portion of benzoyl peroxide are added into a reaction kettle, and stirred (200r/min) in 1000 portions of sodium chloride solution with the specific gravity of 1.2 and 10 portions of polyvinyl alcohol to prepare microspheres with the granularity of 0.2-0.4mm, the temperature is raised to 79 ℃ and kept for 10h, the temperature is raised to 89 ℃ and kept for 2h, the temperature is raised to 98 ℃ and kept for 10h, and the temperature is lowered.
(2) Preparation of copolymer white balls:
adding 300 parts by weight of the polymer matrix white ball obtained in the step (1) into 1000 parts by weight of water, adding 200 parts by weight of p-chlorostyrene, 5 parts by weight of divinylbenzene, 50 parts by weight of isoamyl alcohol and 1 part by weight of benzoyl peroxide, standing for 2h, adding the dispersion phase same as that in the step (1), stirring (200r/min), heating to 79 ℃ and preserving heat for 10h, heating to 98 ℃ for 4h, reacting for 10h, cooling, extracting a pore-forming agent, and drying to obtain the resin white ball.
(3) Functional group stabilization:
adding 1000 parts of fuming sulfuric acid and 40 parts of dichloroethane into 100 parts of the white balls obtained in the step (2), stirring for 2 hours, heating to 81 ℃ for 3 hours, preserving heat for 5 hours, heating to 86 ℃ for 5 hours, preserving heat for 4 hours, heating to 115 ℃ for 5 hours, preserving heat for 6 hours, cooling, reducing the acid ratio in the kettle to 1.0 by using dilute acid, and performing functional group stabilization treatment to obtain the resin catalyst, wherein the number of the resin catalyst is KRC-1.
Example 2:
the amount of diethylbenzene in the preparation of copolymer white balls was increased to 10 parts, otherwise the same as in example 1. The product obtained is numbered KRC-2.
Example 3:
the amount of diethylbenzene in the copolymer white ball preparation was increased to 20 parts, otherwise as in example 1. The product obtained is numbered KRC-3.
Example 4:
the amount of diethylbenzene in the preparation of copolymer white balls was increased to 30 parts, as in example 1. The product obtained is numbered KRC-4.
The application example is as follows:
the tertiary butanol methanol etherification resin catalysts obtained in examples 1 to 4 were used for tertiary butanol methanol etherification reactions:
the test samples were the resin catalysts obtained in examples 1 to 4 of the present invention;
the control sample 1 is white ball, which uses styrene instead of p-chlorostyrene during the wrapping process, and has the sample number KRC-5.
Control sample 2 was a commercially available conventional macroporous cation exchange resin, sample number KRC-6.
100mL of the test sample obtained in examples 1 to 4 and the control samples 1 and 2 were respectively taken and placed in a catalytic distillation column, and tert-butanol and methanol were mixed at a mass space velocity of 1h-1Feeding the catalyst layer from the middle part, wherein the molar ratio of the tert-butyl alcohol to the methanol is 1:0.5, and the methanol is fed for 0.1h-1Feeding from the top of the tower, controlling the temperature of a reaction section to be 90-100 ℃ and the pressure of the top of the tower to be 0.3MPa, respectively operating for seven days, detecting the 7-day average content of methanol, isobutene, tert-butyl alcohol, MTBE at the top of the tower and tert-butyl alcohol at the bottom of the tower by chromatography, and summarizing the conversion rate of the tert-butyl alcohol and the selectivity of the MTBE as shown in Table 1.
TABLE 1 test results
Note: the data in the table are all 7-day averages
As can be seen from the above table, the resin catalyst samples of the examples of the present invention, used for 7 days, have the following effects:
the catalyst adopts p-chlorostyrene in the polymerization process, the selectivity of MTBE and the conversion rate of ethylene glycol single pass are obviously higher than those of a comparative sample adopting conventional styrene and a commercial conventional resin, and after 7 days of continuous use, the selectivity of MTBE is always more than 77%, and the conversion rate of ethylene glycol is close to 100%, so that the catalyst has higher stability and the conversion rate of ethylene glycol single pass.
The catalyst adopts p-chlorostyrene in the polymerization process, the resin desulfonation rate is close to 0, and the resin desulfonation rate is obviously superior to that of a comparative sample adopting conventional styrene and commercially available conventional resin, so that the catalyst cannot be desulfurized when being used at high temperature for a long time, and the temperature resistance is high.
The catalyst adopts p-chlorostyrene in the polymerization process, the content of the methanol component at the tower top is basically 0, and the catalyst has high adsorption performance on the tert-butyl alcohol and the methanol, so that two materials are more easily close to an active center, the reaction is easy to occur, the reaction activity is enhanced, the saturated vapor pressure of the methanol is reduced, the utilization rate of the methanol is improved, the production cost is reduced, and the catalyst activity is higher.
Therefore, the catalyst is a tert-butyl alcohol methanol etherification catalyst with high temperature resistance, high activity and high stability.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (8)
1. The preparation method of the tert-butyl alcohol methanol etherification resin catalyst is characterized by comprising the following steps:
(1) preparation of polymeric white ball matrix:
adding 2-55 parts of styrene, 10-55 parts of divinylbenzene, 45-75 parts of pore-forming agent and 1 part of dibenzoyl peroxide into a reaction kettle added with 1010 parts of dispersed phase by weight, stirring and adjusting into microspheres with the particle size of 0.2-0.4mm, heating to 40-98 ℃ under the stirring condition, and reacting for 10-30h to generate a white polymer ball matrix;
(2) preparation of copolymer white balls:
adding 300 parts by weight of the polymer matrix white ball obtained in the step (1) into 1000 parts by weight of water, then adding 100 parts by weight of p-chlorostyrene, 200 parts by weight of divinylbenzene, 5-50 parts by weight of divinylbenzene, 20-50 parts by weight of pore-forming agent and 1 part by weight of benzoyl peroxide, uniformly mixing, standing for 2-4h, then adding 1010 parts by weight of dispersion phase, heating to 79-98 ℃ under the stirring condition, then preserving heat for 2-30h, cooling, extracting the pore-forming agent, and drying solid materials to obtain the copolymer white ball;
(3) functional group stabilization:
adding 1000 parts by weight of fuming sulfuric acid and 40 parts by weight of dichloroethane into 100 parts by weight of the copolymer white ball obtained in the step (2) to carry out sulfonation reaction, heating to 40-115 ℃ to carry out sulfonation reaction for 10-35h, then cooling, adjusting the acid concentration, carrying out sulfonation reaction to realize functional group stabilization, and obtaining a finished product, wherein the finished product is the tert-butyl alcohol methanol etherification resin catalyst.
2. The method according to claim 1, wherein in the step (1) and the step (2), the dispersed phase is the same and is a mixture of sodium chloride solution and polyvinyl alcohol; 1010 parts of the dispersed phase comprise 1000 parts of a sodium chloride solution with a specific gravity of 1.2 and 10 parts of polyvinyl alcohol.
3. The method according to claim 1, wherein in the step (1), the porogen is any one of 300# liquid wax, n-amyl alcohol, isoamyl alcohol and 4-methyl-2-amyl alcohol, or a mixture of two or more of them mixed in any ratio.
4. The method of claim 1, wherein in step (1), the polymeric white sphere precursor is prepared to have a degree of crosslinking of 10 to 53.
5. The preparation method according to claim 1, wherein in the step (1), the temperature raising process of the polymerized white ball precursor comprises: heating to 79 ℃ and preserving heat for 10h, heating to 89 ℃ for 2h and preserving heat for 2h, heating to 98 ℃ for 2h and preserving heat for 10h, and then cooling.
6. The method according to claim 1, wherein in the step (2), the porogen is isoamyl alcohol.
7. The preparation method according to claim 1, wherein in the step (2), the copolymer white spheres are subjected to a temperature raising process comprising: heating to 79 deg.C, keeping the temperature for 10h, heating to 98 deg.C for 4h, reacting for 10h, and cooling.
8. The preparation method according to claim 1, wherein in the step (3), the sulfonation reaction is carried out to stabilize the functional group, and the specific operation is as follows: adding the materials into a reaction kettle, stirring for 2h, heating to 81 ℃ for 3h, then preserving heat for 5h, heating to 86 ℃ for 5h, then preserving heat for 4h, heating to 115 ℃ for 5h, then preserving heat for 6h, cooling, reducing the acid ratio in the kettle to 1.0 by using dilute acid, and performing functional group stabilization treatment to obtain white balls which are tert-butyl alcohol methanol etherification resin catalysts.
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| CN115301288A (en) * | 2021-05-06 | 2022-11-08 | 中国石油天然气股份有限公司 | Preparation method of resin catalyst for synthesizing ethyl tert-butyl ether |
| CN113813996B (en) * | 2021-09-18 | 2024-02-20 | 凯瑞环保科技股份有限公司 | Methyl ethyl carbonate strong-alkaline anion resin catalyst and preparation method thereof |
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