阅读说明：本技术 一种路易斯酸改性强酸性阳离子交换树脂模块催化剂 (Lewis acid modified strong-acid cation exchange resin modular catalyst ) 是由 毛进池 张美娟 刘巧芬 董研 于 2020-07-27 设计创作，主要内容包括：本发明公开了一种路易斯酸改性强酸性阳离子交换树脂模块催化剂,包括催化剂、金属丝网和金属丝网波纹板：金属丝网和金属丝网波纹板间隔平行设置,两片金属丝网之间盛装催化剂形成催化剂层,且该催化剂层内的催化剂被金属丝网波纹板隔开放置,模块催化剂内催化剂层间隔设置。催化剂为路易斯酸改性强酸性阳离子交换树脂催化剂,将经过干燥处理的强酸性阳离子交换树脂、二氯乙烷、无水AlCl<Sub>3</Sub>依次加入到反应器中,在搅拌条件下进行水浴加热至回流,反应后冷却至室温；将冷却后得到的物料倾入水中,以水解未反应的AlCl<Sub>3</Sub>,依次进行抽滤、乙醇洗涤、丙酮洗涤、乙醚洗涤、真空干燥处理后得乳白色珠体,即路易斯酸改性强酸性阳离子交换树脂。(The invention discloses a Lewis acid modified strong-acid cation exchange resin modular catalyst, which comprises a catalyst, a wire mesh and a wire mesh corrugated plate: wire mesh and wire mesh buckled plate interval parallel arrangement, splendid attire catalyst formation catalyst layer between two wire meshes, and the intraformational catalyst of this catalyst is separated by the wire mesh buckled plate and is placed, and catalyst layer interval sets up in the module catalyst. The catalyst is Lewis acid modified strong acid cation exchange resin catalyst, which is prepared by drying strong acid cation exchange resin, dichloroethane and anhydrous AlCl 3 Sequentially adding into a reactor, heating in water bath under stirring to reflux, reactingCooling to room temperature; the material obtained after cooling is poured into water to hydrolyze the unreacted AlCl 3 Sequentially carrying out suction filtration, ethanol washing, acetone washing, ether washing and vacuum drying treatment to obtain milky beads, namely Lewis acid modified strong-acid cation exchange resin.)

1. A Lewis acid modified strong acid cation exchange resin modular catalyst, comprising a catalyst (3), a wire mesh (1) and a wire mesh corrugated plate (2), characterized in that:

the module catalyst is arranged in parallel by the metal wire mesh and the metal wire mesh corrugated plate at intervals, a catalyst layer (4) is formed by containing the catalyst between the two metal wire meshes, and the catalyst in the catalyst layer is arranged at intervals by the metal wire mesh corrugated plate; the catalyst layers in the module catalyst are arranged at intervals;

the catalyst is a Lewis acid modified strong-acid cation exchange resin catalyst and is prepared by the following method: drying strong acid cation exchange resin, dichloroethane, and anhydrous AlCl₃Sequentially adding the materials into a reactor, heating in a water bath under the stirring condition until the materials are refluxed, reacting for 2-8h, and cooling to room temperature; the material obtained after cooling is poured into water to hydrolyze the unreacted AlCl₃Then carrying out suction filtration, ethanol washing, acetone washing, ether washing and vacuum drying treatment in sequence to obtain milky beads, namely Lewis acid modified strong-acid cation exchange resin.

2. The modular catalyst of claim 1, wherein: the outer contour of the module catalyst is wrapped, fixed and closed by a metal wire mesh to form a cylindrical or cubic shape; one or two layers of wire mesh corrugated plates are arranged between the wire meshes; the catalyst layer is preferably arranged by one or two layers of wire mesh corrugated plates; the wire mesh and the wire mesh corrugated plate are made of stainless steel materials; the wire mesh and the wire mesh corrugated plate are vertically arranged.

3. The modular catalyst of claim 1, wherein: the strong acid cation exchange resin is macroporous strong acid cation exchange resin.

4. The modular catalyst of claim 1, wherein: the strong acid cation exchange resin, dichloroethane and anhydrous AlCl₃The mass ratio of (0.5-1.5): (4-10): (0.5-1.5).

5. The modular catalyst of claim 1, wherein: the water bath is heated to reflux, and the reflux temperature is 60-90 ℃.

6. The modular catalyst of claim 1, wherein: the water bath is heated to reflux, and the reaction time is 4-5 h.

7. The modular catalyst of claim 1, wherein: and (3) drying in vacuum at the temperature of 40-90 ℃.

8. The modular catalyst of claim 1, wherein: and drying in vacuum for 31-32 h.

9. The modular catalyst of claim 1, wherein: the Lewis acid modified strong-acid cation exchange resin contains 2.0-3.0% of aluminum.

10. The modular catalyst of claim 1, wherein: the Lewis acid modified strong-acid cation exchange resin contains 2.78 percent of aluminum.

Technical Field

The invention relates to a modified strong acid cation exchange resin modular catalyst and a preparation method thereof, in particular to a Lewis acid modified strong acid cation exchange resin modular catalyst and a preparation method thereof, and belongs to the technical field of modular catalysts.

Background

At present, with the speed of industrialization of polymethoxy dimethyl ether, the application of polymethoxy dimethyl ether in different fields is also the focus of research. As the application of the dimethyl ether as a diesel additive, the polyoxymethylene dimethyl ether is known as an environment-friendly diesel additive component due to excellent physicochemical properties of the dimethyl ether, DMMn can effectively improve the cetane number and oxygen content of diesel, effectively improve the combustion efficiency of the diesel, and greatly reduce the emission of pollutants such as engine tail gas particles, nitrogen oxides, hydrocarbon substances, carbon monoxide and the like, so that the emission reaches the national V emission standard; DMMn has higher boiling point, is not easy to volatilize, has lower average melting point and better low-temperature property, and can be suitable for areas with high altitude, cold, oxygen deficiency and the like; DMMn as a diesel additive can effectively improve the lubricating property of diesel, reduce the friction loss of an engine and is beneficial to prolonging the service life of the engine; DMMn has higher flash point and high safety performance, and special reconstruction of systems such as an engine, an oil tank and the like is not needed during use; DMMn is mainly synthesized by methanol, formaldehyde and derivatives thereof, can effectively relieve the problem of excess methanol production in China, and has the advantages of cheap and easily available raw materials and good economic benefit.

Since 1970, solid super acidic catalysts have been rapidly developed, and have been applied to many catalytic systems due to their special acidity and high catalytic activity, and because of their advantages of easy separation after use, easy recovery, and regeneration. There are two types of superacids commonly used at present: one is the sulfuric acid catalyst loaded by the composite of rare earth metal oxide and common metal oxide, and the other is the Lewis acid catalyst loaded by the polymer as the carrier.

Polymer catalysts have been attracting attention due to their characteristics of good reaction selectivity, no corrosion to equipment, easy separation, reusability, etc., and recently, lewis acid catalysts (AlCl3, BF3, SnCl4, TiCl4) having polystyrene as a carrier have been studied more and more, and although they have a good catalytic effect in organic synthesis, they have problems in loss of active species and reuse.

Currently, the use of AlCl₃The research on preparing the super acid by the modified strong acid resin generally adopts a reaction system taking ethanol as a solvent, but the control of the reaction process is not facilitated due to violent heat release in the reaction feeding process; although reaction systems using carbon disulfide as a solvent are also available in such reactions, the solubility of aluminum trichloride is not good enough.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a Lewis acid modified strong-acid cation exchange resin modular catalyst and a preparation method thereof aiming at the defects in the prior art, the obtained resin modular catalyst is a special resin modular catalyst for synthesizing polymethoxy dimethyl ether (DMMn), has high loading capacity, simple preparation and easy separation, is water-proof, has good catalytic action on DMMn synthesis reaction, has stable catalytic performance and can be repeatedly used for at least 10 times.

In order to achieve the purpose, the invention adopts the following technical scheme:

the utility model provides a strong acid cation exchange resin module catalyst of Lewis acid modification, includes catalyst, wire mesh and wire mesh buckled plate, its characterized in that:

the module catalyst is arranged in parallel by the metal wire mesh and the metal wire mesh corrugated plate at intervals, a catalyst layer is formed by containing the catalyst between the two metal wire meshes, and the catalyst in the catalyst layer is arranged by the metal wire mesh corrugated plate at intervals; the catalyst layers in the module catalyst are arranged at intervals;

the catalyst is a Lewis acid modified strong-acid cation exchange resin catalyst and is prepared by the following method: drying strong acid cation exchange resin, dichloroethane, and anhydrous AlCl₃Sequentially adding the materials into a reactor, heating in a water bath under the stirring condition until the materials are refluxed, reacting for 2-8h, and cooling to room temperature; the material obtained after cooling is poured into water to hydrolyze the unreacted AlCl₃Then carrying out suction filtration, ethanol washing, acetone washing, ether washing and vacuum drying treatment in sequence to obtain milky beads, namely Lewis acid modified strong-acid cation exchange resin.

In the technical scheme, the outline of the module catalyst is wrapped, fixed and closed by a metal wire mesh to form a cylindrical or square shape.

In the above technical scheme, one or two layers of wire mesh corrugated plates are preferably arranged between the wire mesh and the wire mesh.

In the technical scheme, the catalyst layer is preferably arranged at intervals of one layer or two layers of wire mesh corrugated plates, namely the catalyst layer is arranged between two layers of wire meshes at intervals of one layer or two layers of wire mesh corrugated plates and is internally filled with the catalyst.

In the technical scheme, the wire mesh and the wire mesh corrugated plate are made of stainless steel materials.

In the technical scheme, the wire mesh and the wire mesh corrugated plate are vertically arranged.

In the above technical solution, the strong acid cation exchange resin is preferably a macroporous strong acid cation exchange resin, more preferably a macroporous strong acid polystyrene cation exchange resin, and still more preferably a D006 type resin catalyst produced by the keli environmental protection technologies gmbh.

In the technical scheme, the strong acid cation exchange resin, dichloroethane and anhydrous AlCl₃The mass ratio of (0.5-1.5): (4-10): (0.5-1.5), the mass ratio is preferably 1: 6: 1

In the technical scheme, the water bath is heated to reflux, and the reflux temperature is 60-90 ℃, preferably 80 ℃.

In the above technical scheme, the water bath is heated to reflux, and the reaction time is preferably 4-5h, and more preferably 4.5 h.

In the technical scheme, the vacuum drying is carried out at the temperature of 40-90 ℃, and is preferably 78 ℃.

In the technical scheme, the vacuum drying time is 31-32h, preferably 30 h.

In the technical scheme, the Lewis acid modified strong-acid cation exchange resin contains 2.0-3.0 percent of aluminum (mass fraction).

In the above technical solution, the content of aluminum in the lewis acid modified strong acid cation exchange resin is preferably 2.78% (mass fraction). For example, under the conditions of the reaction temperature of 78 ℃, the reaction time of 6 hours in the step (1) and the drying time of 30 hours in the step (2), the aluminum content of the catalyst can reach 2.78% (mass fraction), and a PS-1 type echelle grating spectrometer is adopted for measuring the aluminum content in the catalyst; according to D006 resin with AlCl₃The theoretical complexation amount of aluminum in the reaction can be calculated to be 5.4% by a reaction equation, but actually, because the resin has a framework and the aluminum trichloride solution is difficult to enter all micropores of the resin, the actual complexation rate is far lower than the theoretical complexation rate.

The invention also provides application of the Lewis acid modified strong-acid cation exchange resin module catalyst as a catalyst in the aspect of synthesizing polymethoxy dimethyl ether (DMMn).

On the basis of a large amount of experimental researches, the invention discovers that a reaction system which takes dichloroethane as a solvent is selected to prepare AlCl₃The reaction process of preparing the super acidic catalyst by the modified strong acid resin is stable and has high load capacity. In the invention, macroporous strong-acid polystyrene cation exchange resin and AlCl₃At CS₂The catalyst is water-proof, has good catalytic action on DMMn synthesis reaction, has stable catalytic performance, and can be repeatedly used for at least 10 times.

Drawings

FIG. 1 is a schematic diagram (cross-sectional view) of the structure of a Lewis acid-modified strong acid cation exchange resin modular catalyst of the present invention; wherein: 1-wire mesh, 2-wire mesh corrugated plate, 3-catalyst, 4-catalyst layer.

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 invention will now be illustrated with reference to specific examples: