CN107694603B - Immobilized ionic liquid catalyst and preparation method and application thereof - Google Patents
Immobilized ionic liquid catalyst and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
Abstract
The invention discloses an immobilized ionic liquid catalyst which is formed by packaging ionic liquid inside an SBA-16 molecular sieve pore cage by taking mesoporous molecular sieve SBA-16 as a carrier and 1-sulfobutyl-3-methylimidazolium salt ionic liquid as an active component, wherein the mass ratio of the 1-sulfobutyl-3-methylimidazolium salt ionic liquid to the mesoporous molecular sieve SBA-16 is 1-5: 10. The catalyst of the invention is used for catalyzing the reaction of methanol and trioxymethylene to synthesize polyformaldehyde dimethyl ether, which not only can solve the problems of difficult separation and poor stability of the catalyst, but also can be recycled for many times, and can improve the reaction activity of the synthesis reaction of polyformaldehyde dimethyl ether and the selectivity of target products.
Description
Technical Field
The invention belongs to the technical field of ionic liquid catalysis, relates to an immobilized ionic liquid catalyst, and particularly relates to an ionic liquid catalyst for catalyzing methanol and trioxymethylene to synthesize low-polymerization-degree polyformaldehyde dimethyl ether.
Background
With the continuous development of economy, the number of diesel powered vehicles is increasing, the demand of diesel is greatly increased, and the limited diesel resources are gradually reduced, so that the trends of insufficient diesel supply and rising price appear. In addition, the diesel oil component has relatively high alkane molecular weight, so that the combustion rate is relatively low and the combustion performance is poor, thereby not only increasing the oil consumption, but also deepening the pollution degree of the discharged tail gas to the air. Therefore, reducing the energy consumption and pollutant emission of diesel vehicles is an important problem to be solved urgently.
Of the various solutions proposed by researchers, the development of new efficient, energy-saving diesel additives is considered to be the most effective solution. The method does not need to modify the engine, and the fuel can be fully combusted by changing the physical properties of the fuel, thereby realizing energy conservation and emission purification.
Polyoxymethylene dimethyl ethers (polyoxymethylene dimethyl ethers), the chemical structure of which is shown in the simplified formula CH3O(CH2O)nCH3Wherein n is an integer of not less than 1, PODE for shortnIt is a new diesel additive. PODEnHas very high cetane number (not less than 30) and oxygen content (not less than 42.1%), can obviously improve the combustion performance of diesel oil, effectively improve the thermal efficiency, and greatly reduce the emission of pollutants such as nitrogen oxides, so the diesel oil additive is considered to be the environment-friendly diesel oil additive with the most application prospect at present. In general, suitable as diesel fuel additive is polyoxymethylene dimethyl ether (PODE) with n being more than or equal to 3 and less than or equal to 83-8)。
US 2449269 describes a preparation method of polyoxymethylene dimethyl ether by using sulfuric acid as a catalyst and methylal and paraformaldehyde or concentrated formaldehyde solution as raw materials, and the obtained product is mainly polyoxymethylene dimethyl ether with the polymerization degree of 2-4. US5746785 takes formic acid with the mass not more than 0.1% of the total reactant as a catalyst, takes methylal and paraformaldehyde with the molar ratio of 1: 5 as raw materials, and synthesizes polyoxymethylene dimethyl ether under the conditions of reaction temperature of 150-240 ℃ and reaction time of 4-7 h. The liquid acid is used as the catalyst, which has the advantages of low cost, strong corrosion to equipment and great environmental pollution. Meanwhile, the liquid acid catalyst is in the same phase as the product, which is not conducive to separation.
CN 102786396A describes a method for synthesizing polyformaldehyde dimethyl ether by taking a cyclic amide ionic liquid as a catalyst, which takes trioxymethylene and formaldehyde in a mass ratio of 1: 0.1-5 as raw materials or trioxymethylene and methanol in a mass ratio of 1: 0.5-10 as raw materials to react at 80-150 ℃ under 0.5-4 MPa, wherein the dosage of the catalyst is 0.01-10% of the total reactant mass. The ionic liquid catalyst has the advantages of good catalytic effect, high selectivity and low corrosion to equipment, but the ionic liquid catalyst has higher cost and is difficult to realize large-scale industrial production.
CN 104292084A discloses a method for preparing polyformaldehyde dimethyl ether by high silica alumina ratio molecular sieve catalysis, wherein raw materials of methylal and trioxymethylene are in contact reaction with a hydrogen type molecular sieve catalyst at the temperature of 60-200 ℃ to generate polyformaldehyde dimethyl ether, the reaction time is 0.2-48 h, the molar ratio of methylal to trioxymethylene is 1-5: 1, the catalyst dosage is 1-10% of the total reactant mass, and the catalyst is at least one of ZSM-5, MCM-41, ZSM-48 and SBA-15. Because the synthesis reaction of PODEN in the method occurs in the pore channels of the molecular sieve, the pore channels and the cavity size of the molecular sieve become main factors influencing the catalytic activity. However, MCM-41 and SBA-15 are two-dimensional hexagonal structures, ZSM-5 is a three-dimensional through channel structure, and ZSM-48 is a one-dimensional channel structure with ten-membered ring openings, so that when the molecular sieves are used as catalysts, the catalytic activity of the reaction is low although the product separation is simple.
CN 103420815A discloses a method for preparing polyoxymethylene dimethyl ether with molecular sieve as carrier and super strong solid acid as active component, wherein the carrier is selected from at least one of SBA-15, MCM-41 and MCM-22 molecular sieves, and the solid super strong acid is selected from SO4 2-/ZrO2、SO4 2-/Fe2O3、Cl-/TiO2Or Cl-/Fe2O3At least one of the above, the molar ratio of the methylal and trioxymethylene as reaction raw materials is 0.5-10: 1, the reaction temperature is 70-200 ℃, the reaction pressure is 0.2-6 MPa, and the amount of the catalyst is 0.1-5.0% of the weight of the raw materials. The product of the method is easy to separate from the catalyst, but the super-strong solid acid of the active component is easy to lose, the stability of the catalyst is poor, and the repeated utilization rate is not high.
In the various preparation methods of the polyoxymethylene dimethyl ethers, the used homogeneous catalysts are difficult to separate and cannot be recycled, while the heterogeneous catalysts can only utilize partial catalytic active points on the surfaces of the heterogeneous catalysts, and the efficiency is lower than that of the homogeneous catalysts. In view of the increasingly tense energy supply and environmental pollution problem in energy utilization in China and China, a catalyst with the advantages of homogeneous catalysis and heterogeneous catalysis is urgently needed, the high-activity catalysis efficiency is maintained, and meanwhile, the catalyst can be recycled and reused, so that the mass production of the polyoxymethylene dimethyl ether is realized, and the production cost is reduced.
Disclosure of Invention
The invention aims to provide an immobilized ionic liquid catalyst, which is used for catalyzing methanol and trioxymethylene to synthesize low-polymerization-degree polyformaldehyde dimethyl ether, can solve the problems of difficult separation and poor stability of the catalyst, and can improve the reaction activity of the synthesis reaction of the polyformaldehyde dimethyl ether and the selectivity of a target product.
The immobilized ionic liquid catalyst is an immobilized ionic liquid catalyst formed by encapsulating ionic liquid inside a pore cage of an SBA-16 molecular sieve by using mesoporous molecular sieve SBA-16 as a carrier and 1-sulfobutyl-3-methylimidazolium salt ionic liquid as an active component, wherein the mass ratio of the 1-sulfobutyl-3-methylimidazolium salt ionic liquid to the mesoporous molecular sieve SBA-16 is 1-5: 10.
Specifically, the salt of the 1-sulfonic acid butyl-3-methylimidazolium salt may be any one of a methanesulfonate salt, a p-toluenesulfonate salt, a trifluoromethanesulfonate salt or a bisulfate salt.
More specifically, the 1-sulfobutyl-3-methylimidazolium salt ionic liquid is an ionic liquid represented by any one of the following molecular structures.
The invention further provides a method for preparing the immobilized ionic liquid catalyst, which comprises the steps of dispersing the ionic liquid in an alcohol solution, adding an SBA-16 molecular sieve, carrying out reflux reaction at 60-100 ℃, removing the solvent from the reactant, placing the reactant in a dichloromethane solvent, and reacting the reactant with alkyl trimethoxy silane at 20-60 ℃ to prepare the SBA-16 immobilized ionic liquid catalyst.
Wherein, the alkyl trimethoxy silane is octyl trimethoxy silane or dodecyl trimethoxy silane.
Specifically, the dosage of the alkyl trimethoxy silane is 20-150% of the mass of the SBA-16 molecular sieve.
In the above preparation method of the present invention, the alcohol solution is preferably methanol or ethanol.
More preferably, the reaction time of the reflux reaction and the silylation reaction of the invention is not less than 24 h.
The immobilized ionic liquid catalyst prepared by the invention can be used as a catalyst to be applied to the synthesis reaction for catalytically synthesizing polyformaldehyde dimethyl ether by taking methanol and trioxymethylene as raw materials.
Specifically, under the inert atmosphere of 80-110 ℃ and 1.5-2.5 MPa, the supported ionic liquid catalyst of the invention is used for catalyzing the synthesis reaction of methanol and trioxymethylene to prepare polyoxymethylene dimethyl ether.
Wherein the molar ratio of the reaction raw material methanol to trioxymethylene is 1-3: 1, and the reaction time is 0.5-3 h.
Wherein: n represents an integer of 1 to 8.
In the synthesis reaction, the dosage of the immobilized ionic liquid catalyst is 1-8% of the total reactant mass.
The invention uses 1-sulfobutyl-3-methylimidazolium salt ionic liquid, and encapsulates the ionic liquid in a super-macroporous cage structure of an SBA-16 molecular sieve to prepare the immobilized ionic liquid catalyst. The catalyst takes a molecular sieve SBA-16 as a carrier, and the active component of the ionic liquid is in a free state, so that the activity of the homogeneous reaction catalyst can be fully exerted; meanwhile, the ionic liquid is fixed in a hole cage of the SBA-16 molecular sieve, is not easy to run off and can be recycled for multiple times. Therefore, the catalyst prepared by the invention has the advantages of both homogeneous catalysts and heterogeneous catalysts.
The SBA-16 molecular sieve has a special three-dimensional cage structure, large specific surface area and high chemical stability. The ionic liquid is encapsulated in the pore cage structure of SBA-16, so that the dosage of the ionic liquid can be obviously reduced, the dispersion of active components is facilitated, the catalyst is easy to separate and recover, the catalyst can be recycled for multiple times, and the catalytic efficiency and the recycling rate of the catalyst are obviously improved.
SBA-16 is taken as one of mesoporous molecular sieves, compared with MCM-41 and SBA-15 with straight channels, the mesoporous molecular sieve has a three-dimensional cubic hole structure which is not easy to block, is beneficial to free diffusion of reactants and products in the channels, has better transmission performance, and is an excellent carrier for immobilizing ionic liquid.
Compared with the traditional homogeneous catalyst anchored on a specific carrier, the preparation method of the immobilized ionic liquid catalyst provided by the invention is simple and easy to implement, does not relate to synthesis reaction, does not influence the catalytic activity of the ionic liquid after immobilization, and has good immobilization effect.
The immobilized ionic liquid catalyst prepared by the invention has stable physicochemical property and high catalytic efficiency, and is used in the synthesis reaction of polyformaldehyde dimethyl ether, and the product selectivity is high.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1.
0.98g of SBA-16 and 0.5g of 1-sulfobutyl-3-methylimidazolium mesylate are weighed out and added into a single-neck flask containing 35ml of methanol, N2The reaction was refluxed at 68 ℃ for 24h under an atmosphere. The solvent methanol was removed by rotary evaporation and 4mmol octyl trimethoxysilane and 10ml dichloromethane, N were added2Reacting for 24 hours at 40 ℃ under the atmosphere. And washing and vacuum drying the reaction product to obtain the catalyst a.
12.1448g trioxymethylene, 6.7303g methanol, 0.4788g catalyst a and N are added into a 100ml high-pressure reaction kettle2Heating to the pressure of 1.8MPa, slowly heating to 95 ℃, and stirring for reaction for 1 h. The reaction product was cooled to room temperature and analyzed by gas chromatography for PODE3-8Relative percentage content is 30.48%, and conversion rate of trioxymethylene is 64.43%.
Example 2.
1.3g of SBA-16 and 0.64g of 1-sulfobutyl-3-methylimidazolium p-toluenesulfonate were weighed and added to a single-neck flask containing 30ml of methanol, N2Reflux reaction is carried out for 24h at 65 ℃ under the atmosphere. The solvent methanol is removed by rotary evaporation, and 5mmol of dodecyl trimethoxy silane and 15ml of dichloromethane and N are added2Reacting for 24 hours at 40 ℃ under the atmosphere. And washing and vacuum drying the reaction product to obtain the catalyst b.
11.8807g of trioxymethylene, 6.3344g of methanol, 0.5367g of catalyst b and N charge are added into a 100ml high-pressure reaction kettle2Heating to 1.7MPa, slowly heating to 100 deg.C, and stirring for 1 hr. The reaction product was cooled to room temperature and analyzed by gas chromatography for PODE3-8The relative percentage content is 44.62 percent, and the conversion rate of trioxymethylene is 82.18 percent.
Example 3.
1.64g of SBA-16 and 0.71g of 1-sulfobutyl-3-methylimidazolium triflate are weighed into a single-neck flask containing 30ml of methanol, N2Reflux reaction is carried out for 24h at 65 ℃ under the atmosphere. The solvent methanol was removed by rotary evaporation and 5mmol octyl trimethoxysilane and 15ml dichloromethane, N were added2Reacting for 24 hours at 40 ℃ under the atmosphere. And washing and vacuum drying the reaction product to obtain the catalyst c.
8.9220g of trioxymethylene, 6.3344g of methanol and 0.4973g of catalyst c are sequentially added into a 100ml high-pressure reaction kettle and filled with N2Heating to 90 deg.C slowly until the pressure is 1.9MPa, and stirring for 0.75 hr. The reaction product was cooled to room temperature and analyzed by gas chromatography for PODE3-8The relative percentage content is 49.95 percent, and the conversion rate of trioxymethylene is 85.85 percent.
Example 4.
1.49g of SBA-16 and 0.66g of 1-sulfobutyl-3-methylimidazolium hydrogen sulfate were weighed into a single-neck flask containing 35ml of methanol, N2Reflux reaction is carried out for 24h at 65 ℃ under the atmosphere. The solvent methanol was removed by rotary evaporation and 5mmol octyl trimethoxysilane and 15ml dichloromethane, N were added2Reacting for 24 hours at 40 ℃ under the atmosphere. And washing and vacuum drying the reaction product to obtain the catalyst d.
17.8470g trioxymethylene, 12.6688g methanol, 0.9999g catalyst d and N are added into a 100ml high-pressure reaction kettle2Heating to 90 deg.C slowly until the pressure is 1.9MPa, and stirring for 0.5 h. The reaction product was cooled to room temperature and analyzed by gas chromatography for PODE3-8The relative percentage content is 20.26 percent, and the conversion rate of trioxymethylene is 50.07 percent.
Example 5.
1.0g of SBA-16, 0.5g of 1-sulfobutyl-3-methylimidazolium hydrogen sulfate are weighed into a single-neck flask containing 30ml of methanol, N2Reflux reaction at 65 ℃ in atmosphereAnd the time is 24 hours. The solvent methanol was removed by rotary evaporation and 5mmol octyl trimethoxysilane and 15ml dichloromethane, N were added2Reacting for 24 hours at 40 ℃ under the atmosphere. And washing and vacuum drying the reaction product to obtain the catalyst e.
9.0233g of trioxymethylene, 6.3344g of methanol, 0.9090g of catalyst e and N charge are added into a 100ml high-pressure reaction kettle2Heating to 1.8MPa, heating to 110 deg.c and stirring for reaction for 1 hr. The reaction product was cooled to room temperature and analyzed by gas chromatography for PODE3-8Relative percentage content 45.13%, trioxymethylene conversion 83.26%.
The used catalyst e was recovered by filtration, dried and reused, and the catalytic reaction was carried out again under the above reaction conditions, and the catalytic results are shown in table 1.
As can be seen from Table 1, the product PODE was obtained after 4 cycles of recycling the catalyst3-8The percentage content and the trioxymethylene conversion rate are not reduced greatly, which proves that the catalyst still has high catalytic activity after being used for 4 times, has stable properties and can be repeatedly utilized.
Claims (10)
1. An immobilized ionic liquid catalyst is an immobilized ionic liquid catalyst formed by taking mesoporous molecular sieve SBA-16 as a carrier and 1-sulfobutyl-3-methylimidazolium salt ionic liquid as an active component and encapsulating the ionic liquid in a pore cage of the SBA-16 molecular sieve, wherein the mass ratio of the 1-sulfobutyl-3-methylimidazolium salt ionic liquid to the mesoporous molecular sieve SBA-16 is 1-5: 10.
2. The immobilized ionic liquid catalyst as set forth in claim 1, wherein the 1-sulfobutyl-3-methylimidazolium salt is any one of methanesulfonate, p-toluenesulfonate, trifluoromethanesulfonate and bisulfate.
3. The preparation method of the immobilized ionic liquid catalyst of claim 1, which comprises the steps of dispersing ionic liquid in an alcohol solution, adding an SBA-16 molecular sieve, carrying out reflux reaction at 60-100 ℃, removing a solvent from a reactant, placing the reactant in a dichloromethane solvent, and reacting the reactant with alkyl trimethoxy silane at 20-60 ℃ to prepare the SBA-16 immobilized ionic liquid catalyst.
4. The method according to claim 3, wherein said alkyltrimethoxysilane is octyltrimethoxysilane or dodecyltrimethoxysilane.
5. The preparation method of claim 3, wherein the amount of the alkyl trimethoxy silane is 20-150% of the weight of the SBA-16 molecular sieve.
6. The method according to claim 3, wherein the alcohol solution is methanol or ethanol.
7. The use of the supported ionic liquid catalyst of claim 1 as a catalyst for the catalytic synthesis of polyoxymethylene dimethyl ethers.
8. A method for catalytically synthesizing polyoxymethylene dimethyl ethers by using the catalyst of claim 1 is to prepare polyoxymethylene dimethyl ethers by using the catalyst to catalyze the reaction of methanol and trioxymethylene under the inert atmosphere of 80-110 ℃ and 1.5-2.5 MPa.
9. The method of claim 8, wherein the molar ratio of the reaction raw material methanol to trioxymethylene is 1-3: 1, and the reaction time is 0.5-3 h.
10. The method according to claim 8, wherein the amount of the catalyst is 1 to 8% by mass based on the total reaction mass.
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| CN109225337B (en) * | 2018-09-10 | 2021-05-18 | 太原理工大学 | MOFs (metal-organic frameworks) -encapsulated ionic liquid catalyst and preparation and application thereof |
| CN110465331A (en) * | 2019-07-05 | 2019-11-19 | 江苏大学 | The preparation method and application of B-SBA-16 load silico-tungstic acid type ionic liquid composite catalyst |
| CN110449182A (en) * | 2019-07-12 | 2019-11-15 | 江苏大学 | The synthetic method of phosphotungstic acid ionic liquid inline type nanocages and its application in ketal reaction |
| CN110465329A (en) * | 2019-07-31 | 2019-11-19 | 江苏大学 | The preparation method and applications of caged mesoporous silicon support type acidic ion liquid composite catalyst |
| CN116273159B (en) * | 2022-12-05 | 2023-11-17 | 中国人民解放军军事科学院系统工程研究院 | Sulfonated immobilized binary catalyst, preparation method and application thereof |
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