CN114478254A - Composite catalyst bed layer, method for preparing methyl acrylate and application - Google Patents

Composite catalyst bed layer, method for preparing methyl acrylate and application Download PDF

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CN114478254A
CN114478254A CN202011146237.2A CN202011146237A CN114478254A CN 114478254 A CN114478254 A CN 114478254A CN 202011146237 A CN202011146237 A CN 202011146237A CN 114478254 A CN114478254 A CN 114478254A
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catalyst bed
catalyst
bed layer
solid base
methyl acrylate
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CN114478254B (en
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王海之
刘晓曦
余强
刘仲能
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

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Abstract

The utility model discloses a composite catalyst bed layer and a method for preparing methyl acrylate by using the same, wherein the composite catalyst bed layer comprises a first catalyst bed layer and a second catalyst bed layer which are connected in series, and the first catalyst bed layer and the second catalyst bed layer respectively and independently comprise a solid base catalyst filling section and an acid catalyst filling section; specifically, an acid catalyst is filled at the 1/3-3/4 position of the first catalyst bed layer to form the acid catalyst filling section, and the rest positions are filled with a solid base catalyst; and respectively filling acid catalysts at 1/3-3/4 positions of the second catalyst bed layer to form the acid catalyst filling section, and filling solid base catalysts at the other positions to form the solid base catalyst filling section. The composite catalyst bed layer can solve the problem of insufficient supply of aldehyde compounds in the lower bed layer, inhibit side reactions and reduce the content of acetone as a byproduct.

Description

Composite catalyst bed layer, method for preparing methyl acrylate and application
Technical Field
The utility model relates to the preparation of methyl acrylate, in particular to the preparation of methyl acrylate by condensing methyl acetate and aldehyde compounds.
Background
Methyl acrylate is an important fine chemical raw material with wide application, is mainly used for organic synthesis intermediates and high molecular monomers, and polymers prepared by taking methyl acrylate as monomers are widely used in the industries of coatings, textiles, leathers, adhesives and the like.
The acrylic acid and its ester are produced mainly by the propylene oxidation method, the acrylonitrile hydrolysis method, the vinyl ketone method, the propane oxidation method, the methyl formate method, and the like. However, the methods have the defects of serious pollution, high energy consumption, low product yield and the like. Therefore, the development of a green and efficient new production process has very important significance.
Meanwhile, the productivity of methyl acetate in China is surplus, so that the field needs to use industrial by-product methyl acetate as a raw material, adopt a safe, environment-friendly and nontoxic solid base catalyst and realize green synthesis of methyl acrylate through a clean synthesis process.
In view of this, research work for synthesizing methyl acrylate by using methyl acetate and formaldehyde as raw materials has been carried out by many scientific research units at home and abroad in recent years. The research on the application of Zhaxinyu, etc. of Qiqi Haha university, Jingtao of Harbin university, Sunwang and Zhang of Daqing petrochemical industry, Zhang Shi Zhi university, etc. in the preparation of catalyst and the synthesis of methyl acrylate from methyl acetate and formaldehyde/methylal is carried out.
In order to solve the problem that the productivity of methyl acetate in China is greatly surplus, the synthesis of methyl acrylate by taking methyl acetate and formaldehyde as raw materials is provided.
Chinese patent CN204079837U discloses a reaction apparatus for producing methyl acrylate and/or methyl methacrylate, comprising: a condensation unit, a dehydration unit, a pyrolysis unit, a methyl acrylate and/or methyl methacrylate synthesis reactor, a first pipeline, a second pipeline, a third pipeline and a fourth pipeline. According to the reactor disclosed by the utility model, gas-phase formaldehyde directly participates in the reaction for synthesizing methyl acrylate and/or methyl methacrylate, the reaction conversion rate is high, the reaction speed is high, and the reactor disclosed by the utility model can avoid the problems caused by solid feeding of trioxymethylene and paraformaldehyde, and realizes continuous chemical combination and stabilization in the reaction process.
But at present, industrialization still cannot be realized, and the key point is that the comprehensive improvement of yield, selectivity and catalyst stability cannot be achieved.
Meanwhile, in the prior art for preparing methyl acrylate by adopting methyl acetate and aldehyde compounds, the aldehyde source concentration on the upper bed layer of the reactor is high, the coking is easy to occur, the aldehyde source concentration on the lower bed layer of the reactor is low, the methyl acetate concentration is high, and the methyl acetate with high concentration can cause the methyl acetate to be condensed to generate acetone, so that the separation energy consumption is increased.
Disclosure of Invention
In order to overcome the problems in the prior art, the utility model provides a composite catalyst bed layer and a method for preparing methyl acrylate (by using the composite catalyst bed layer), wherein the composite catalyst bed layer is formed by filling catalysts including a solid base catalyst and an acid catalyst, and the composite catalyst bed layer can solve the problem of insufficient supply of aldehyde compounds in a lower bed layer, simultaneously can inhibit the occurrence of side reactions and reduce the content of acetone as a byproduct.
The utility model aims to provide a composite catalyst bed layer, which comprises a first catalyst bed layer and a second catalyst bed layer which are connected in series, wherein the first catalyst bed layer and the second catalyst bed layer respectively and independently comprise a solid base catalyst filling section and an acid catalyst filling section.
In the prior art, the aldehyde source concentration on the upper part of a bed layer is high and coked, the catalyst is inactivated, and the bed layer is easy to block, so that high-concentration methyl acetate and low-concentration aldehyde source in the lower bed layer are directly caused, and the high-concentration methyl acetate can be condensed to generate acetone, so that the separation energy consumption is increased.
In the utility model, a weak acid catalyst filling section is doped in a solid base catalyst bed layer, and the weak acid catalyst can promote the decomposition of an aldehyde source, increase the concentration of the aldehyde source in a lower bed layer and provide enough formaldehyde, thereby inhibiting the generation of acetone.
In a preferred embodiment, the solid base catalyst comprises a carrier and an active component and optionally an auxiliary agent supported on the carrier.
In a further preferred embodiment, the support is selected from at least one of silica, alumina and SBA-15 molecular sieves, preferably having a specific surface area of 50 to 500m2The pore diameter is 6-30nm, and the porosity is 0.6-1 mL/g.
In a further preferred embodiment, the active component is at least one of cesium, potassium and rubidium (preferably cesium), preferably in an amount of 1 to 20 wt%, preferably 2 to 10 wt%, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%.
The source of the active component is at least one of carbonic acid compound, formic acid compound and nitric acid compound containing active component elements.
In a further preferred embodiment, the promoter is selected from at least one of zirconium, bismuth and lanthanum compounds, preferably in a loading of 0 to 5 wt.%, preferably 0.3 to 3 wt.%, for example 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%.
Wherein the sources of zirconium, bismuth and nickel are zirconium-containing compounds, bismuth-containing compounds and lanthanum-containing compounds, such as zirconyl nitrate, bismuth chloride and lanthanum nitrate, respectively.
When the solid base catalyst is prepared, if equal-volume impregnation is adopted, as the components in the impregnation liquid are basically and completely loaded on the carrier, the contents of the active components and the auxiliary agents in the product can be calculated according to the using amount of the raw materials by a theoretical calculation method.
In a preferred embodiment, the acidic catalyst is selected from alumina and/or molecular sieves.
In a further preferred embodiment, the acidic catalyst is selected from the group consisting of θ -Al2O3At least one of SAPO-34 molecular sieve and SAPO-35 molecular sieve.
In a preferred embodiment, the acid catalyst is filled in the first catalyst bed at the 1/3-3/4 position to form the acid catalyst filling section by 0.5-10% bed volume, and the solid base catalyst is filled in the other position to form the solid base catalyst filling section.
For example, the first catalyst bed may be loaded with 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% bed volume of the acidic catalyst at position 1/3, position 1/2, position 5/8 or position 3/4.
In a further preferred embodiment, the acid catalyst is packed in the first catalyst bed at positions 1/2-5/8 by 1-4% of the bed volume to form the acid catalyst packed section, and the solid base catalyst is packed in the remaining positions to form the solid base catalyst packed section.
Wherein, the positions from the top to the bottom of the bed layer are 0-1 in sequence. Specifically, in the first catalyst bed, the aldehyde source at the upper part of the bed is sufficient and does not need an acid catalyst, so that the acid catalyst is filled only in the middle and lower sections of the bed to decompose the aldehyde source which is not depolymerized, and the problem of insufficient supply of the aldehyde source at the middle and lower parts of the bed is solved.
In a preferred embodiment, the acid catalyst is loaded in the position 1/3-3/4 of the second catalyst bed to form the acid catalyst loading section by 0.5-10% bed volume respectively, and the rest positions are loaded with the solid base catalyst to form the solid base catalyst loading section.
For example, the first catalyst bed may be loaded with 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% bed volume of the acidic catalyst at position 1/3, position 1/2, position 5/8 or position 3/4.
In a further preferred embodiment, the acid catalyst is loaded in the position 1/2-5/8 of the second catalyst bed to form the acid catalyst loading section by respectively loading 1-4% of bed volume of the acid catalyst, and the rest positions are loaded with the solid base catalyst to form the solid base catalyst loading section.
Wherein, the positions from the top to the bottom of the bed layer are 0-1 in sequence. Specifically, a small amount of aldehyde source is introduced into the inlet of the second reactor, so that sufficient formaldehyde is arranged at the upper part of the reaction bed layer of the second reactor, but the aldehyde source is continuously reduced along with the reaction, the decomposed monomer formaldehyde is also continuously reduced, and the problem of insufficient formaldehyde exists in the lower bed layer, so that the acid catalyst is filled at the middle lower part of the second catalyst bed layer.
In the utility model, the two beds in series are respectively arranged in the two reactors in series.
The second purpose of the utility model is to provide the application of the composite catalyst bed layer in the first purpose of the utility model in preparing methyl acrylate.
A third object of the present invention is to provide a process for producing methyl acrylate, which is carried out using the composite catalyst bed according to one of the objects of the present invention, wherein the process comprises: and (2) sequentially passing raw materials including methyl acetate, an aldehyde source and methanol through the first catalyst bed layer and the second catalyst bed layer which are connected in series, and reacting to obtain the methyl acrylate.
In a preferred embodiment, the aldehyde source is replenished at the top of the second catalyst bed.
The supplemented aldehyde source is supplemented in a liquid state, preferably, when the supplemented aldehyde source of the second catalyst bed layer is trioxymethylene, solid trioxymethylene is heated until the trioxymethylene is in a liquid phase state (preferably, the heating is carried out at 60-80 ℃), and then the solid trioxymethylene is introduced into the second catalyst bed layer through a pump.
In a preferred embodiment, the aldehyde source is selected from trioxymethylene and/or methylal.
In a preferred embodiment, the molar ratio of methyl acetate to the aldehyde source in the feed to the first catalytic bed is (1-10):1, preferably (2-5):1, for example 2:1, 3:1, 4:1 or 5: 1.
In a preferred embodiment, the mass of methanol in the feed to the first catalytic bed is from 0.1 to 0.5 times, preferably from 0.1 to 0.4 times, for example 0.15, 0.25 or 0.3 times the weight of methyl acetate. .
In a preferred embodiment, the supplemental aldehyde source of the second catalyst bed is (0-2):1, preferably does not contain 0, and more preferably (0.2-1):1, by volume of the feed material in the first catalyst bed.
For example, the second catalyst bed may have a volume ratio of supplemental aldehyde source to feed feedstock in the first catalyst bed of 02:1, 0.5:1, 0.8:1, 1:1, 1.5:1, or 2:1, preferably 0.5:1, 0.8:1, or 1: 1.
In a preferred embodiment, the gas space velocity of the second catalyst bed is greater than the gas space velocity of the first catalyst bed.
Wherein almost all the materials (except the catalyst) in the system are in a gaseous state at the reaction temperature, and therefore, the gas space velocity herein means the space velocity of the gas including the reaction materials and nitrogen.
In a further preferred embodiment, the gas space velocity of the second catalyst bed is 1-3 times the gas space velocity of the first catalyst bed and excludes 1, preferably 1.5 to 3 times, such as 1.5, 2, 2.5 or 3 times. Wherein, because the first catalyst bed layer can generate water after reacting and carry into the second catalyst bed layer, and water can influence the catalyst activity, therefore, need to control the contact time of material and second catalyst bed layer to be shorter.
In a preferred embodiment, the reaction temperature of the first catalyst bed layer is 300-400 ℃; and/or the reaction pressure is 0-1 MPa; and/or the liquid phase volume flow rate is 0.01-1 mL/min; and/or the nitrogen flow is 20-200 mL/min.
In a further preferred embodiment, the reaction temperature of the first catalyst bed is 330 to 360 ℃ (e.g., 330 ℃, 340 ℃, 350 ℃, 360 ℃); and/or the reaction pressure is 0.1 to 0.5MPa (for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5 MPa); and/or the liquid phase volume flow rate is 0.1-0.5 mL/min; and/or the nitrogen flow is 50-150 mL/min.
Wherein the liquid phase volumetric flow rate over the first catalyst bed means the flow rate of the liquid feedstock comprising methyl acetate, the aldehyde source and methanol.
In a preferred embodiment, the reaction temperature of the second catalyst bed layer is 300-400 ℃; and/or the reaction pressure is 0-1 MPa; and/or the liquid phase volume flow rate is 0.01-0.5 mL/min; and/or the nitrogen flow rate is 150-350 mL/min.
In a further preferred embodiment, the reaction temperature of the second catalyst bed is 330 to 360 ℃ (e.g., 330 ℃, 340 ℃, 350 ℃, 360 ℃); and/or the reaction pressure is 0.1 to 0.5MPa (for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5 MPa); and/or the liquid phase volume flow rate is 0.01-0.2 mL/min; and/or the nitrogen flow rate is 200-300 mL/min.
Wherein the liquid phase volumetric flow rate over the second catalyst bed is the flow rate of the supplemental aldehyde source.
The fourth object of the present invention is to provide methyl acrylate obtained by the process described in the third object of the present invention.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the utility model has the following beneficial effects:
(1) the composite catalyst bed layer can solve the problem of insufficient supply of aldehyde compounds in the lower bed layer, and can inhibit side reactions and reduce the content of acetone byproduct;
(2) the methyl acrylate prepared by the method can improve the product yield;
(3) the method of the utility model makes a feasible solution to the problem that the methyl acetate productivity in China is greatly surplus at present, and can obtain good economic effect and social benefit.
Drawings
Fig. 1 shows a schematic structure diagram of the composite catalyst bed according to the present invention.
1-a first catalyst bed; 2-a second catalyst bed; 3-a solid base catalyst loading section; 4-an acid catalyst loading section; 5-feedstock comprising methyl acetate and an aldehyde source; 6-make up the aldehyde source.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the utility model. The utility model is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
Solid base catalyst Cs/SiO used in examples 1 to 3 and comparative examples 1 to 42The preparation was as follows: weigh 0.7280gCs2CO3Dissolving in 12mL deionized water, and uniformly soaking the solution in 10gSiO2Stirring, standing for 1 hr, and steaming in 60 deg.C water bath to remove excessive water. Transferring the mixture into a vacuum drying oven, drying the mixture for 12 hours at 50 ℃, and roasting the dried mixture for 5 hours at 550 ℃ in air atmosphere to prepare the catalyst Cs/SiO2Wherein the Cs content is 5.7 wt%.
Examples 4 to 5 use solid base catalysts Cs/Zr-SiO2The preparation was as follows: weigh 0.7280gCs2CO3And 0.142gZrOCl2·8H2Dissolving O in 12mL deionized water, and uniformly soaking the solution in 10gSiO2Stirring, standing for 1 hr, and steaming in 60 deg.C water bath to remove excessive water. Transferring the mixture into a vacuum drying oven, drying the mixture for 12 hours at 50 ℃, and roasting the dried mixture for 5 hours at 550 ℃ in air atmosphere to prepare the catalyst Cs/Zr-SiO2Wherein the Cs content is 5.6 wt%, and the Zr content is 0.04 wt%.
[ example 1 ]
The first catalyst bed 3/5 is filled with acidic catalyst SAPO-34 molecular sieve with 2% bed volume, and solid base catalyst Cs/SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; the position of the second catalyst bed layer 3/5 bed layer is filled with 3 percent bed layer volume acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed of the first catalyst bed layer is 3:1, and the mass of methanol is 0.3 times of that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 120mL/min, the nitrogen flow in the second catalyst bed layer is 250mL/min, the flow rate of the mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.2mL/min, the flow rate of the supplemented aldehyde source in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 330 ℃, the reaction temperature of the second catalyst bed layer is 330 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.4 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of the methyl acrylate is 12%, the product concentration of the methyl propionate is 3%, and the content of the acetone product is 0.3%. After five days, the product concentration of methyl acrylate was 11.5%, the product concentration of methyl propionate was 2.8%, and the product content of acetone was 0.1%.
In this example, the acetone content in the obtained product is very small, and the product yield is hardly changed after 5 days of operation, which shows that the catalyst activity is stable in the system of this example.
[ example 2 ]
The bed position of the first catalyst bed 1/3 is filled with 2 percent of bed volume of acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; the position of the second catalyst bed layer 1/3 bed layer is filled with 3 percent bed layer volume acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed of the first catalyst bed layer is 3:1, and the mass of methanol is 0.3 times of that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 120mL/min, the nitrogen flow in the second catalyst bed layer is 250mL/min, the flow rate of the mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.2mL/min, the flow rate of the supplemented aldehyde source in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 330 ℃, the reaction temperature of the second catalyst bed layer is 330 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.4 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of the methyl acrylate is 10%, the product concentration of the methyl propionate is 2%, and the content of the acetone product is 1.2%. After five days, the product concentration of methyl acrylate was 9%, the product concentration of methyl propionate was 1.5%, and the product content of acetone was 1%.
In this example, the acetone content in the obtained product was small (compared with that without the acid catalyst), and the product yield was hardly changed after 5 days of operation, indicating that the catalyst activity in the system of this example was stable.
[ example 3 ] A method for producing a polycarbonate
The bed position of the first catalyst bed 3/5 is filled with 0.5 percent of bed volume of acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; the position of the second catalyst bed layer 1/3 bed layer is filled with 0.5 percent of bed layer volume acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalystCs/SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed of the first catalyst bed layer is 3:1, and the mass of methanol is 0.3 times of that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 120mL/min, the nitrogen flow in the second catalyst bed layer is 250mL/min, the flow rate of the mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.2mL/min, the flow rate of the supplemented aldehyde source in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 330 ℃, the reaction temperature of the second catalyst bed layer is 330 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.4 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of the methyl acrylate is 8%, the product concentration of the methyl propionate is 1.3%, and the content of the acetone product is 1.4%. After five days, the product concentration of methyl acrylate was 7%, the product concentration of methyl propionate was 1.28%, and the product content of acetone was 1.1%.
In this example, the acetone content in the obtained product was small (compared with that without the acid catalyst), and the product yield was hardly changed after 5 days of operation, indicating that the catalyst activity in the system of this example was stable.
[ example 4 ]
The bed position of the first catalyst bed 3/4 is filled with 4 percent of bed volume of acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/Zr-SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; the position of a second catalyst bed layer 3/4 bed layer is filled with 1 percent of bed layer volume acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/Zr-SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed of the first catalyst bed layer is 2:1, and the mass of methanol is 0.3 times of that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 100mL/min, the nitrogen flow in the second catalyst bed layer is 300mL/min, the flow rate of the mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.1mL/min, the flow rate of the supplemented aldehyde source in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 360 ℃, the reaction temperature of the second catalyst bed layer is 360 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.1 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of methyl acrylate is 8.5%, the product concentration of methyl propionate is 2.5%, and the content of acetone product is 0.9%. After five days, the product concentration of methyl acrylate was 7.2%, the product concentration of methyl propionate was 2.1%, and the product content of acetone was 0.7%.
In this example, the acetone content in the obtained product is very small, and the product yield is hardly changed after 5 days of operation, which shows that the catalyst activity is stable in the system of this example.
[ example 5 ]
The bed position of the first catalyst bed 3/4 is filled with 4 percent of bed volume of acidic catalyst theta-Al2O3The balance being solid base catalyst Cs/Zr-SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; filling the bed position of the second catalyst bed 3/4 with 1 percent of bed volume of acid catalyst theta-Al2O3The balance being solid base catalyst Cs/Zr-SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed to the first catalyst bed is 5:1, and the mass of methanol is 0.3 times that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 150mL/min, the nitrogen flow in the second catalyst bed layer is 225mL/min, the flow rate of the mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.5mL/min, the flow rate of the supplemented aldehyde source in the second catalyst bed layer is 0.2mL/min, the reaction temperature of the first catalyst bed layer is 350 ℃, the reaction temperature of the second catalyst bed layer is 350 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.5 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of methyl acrylate is 7.5%, the product concentration of methyl propionate is 2.8%, and the content of acetone product is 1.2%. After five days, the product concentration of methyl acrylate was 5%, the product concentration of methyl propionate was 2.3%, and the product content of acetone was 0.4%.
In this example, the acetone content in the obtained product is very small, and the product yield is hardly changed after 5 days of operation, which shows that the catalyst activity is stable in the system of this example.
[ example 6 ]
The procedure of example 1 was repeated except that the second catalyst bed was in exactly the same configuration as the first catalyst bed.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of the methyl acrylate is 11%, the product concentration of the methyl propionate is 2.8%, and the content of the acetone product is 0.45%. After five days, the product concentration of methyl acrylate was 10.2%, the product concentration of methyl propionate was 2.6%, and the product content of acetone was 0.3%.
In this example, the acetone content in the obtained product is very small, and the product yield is hardly changed after 5 days of operation, which shows that the catalyst activity is stable in the system of this example.
Comparative example 1
Respectively adding 10mL of solid base catalyst Cs/SiO into the first catalyst bed layer and the second catalyst bed layer2。
The molar ratio of methyl acetate to trioxymethylene in the feed of the first catalyst bed layer is 3:1, and the mass of methanol is 0.3 times of that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 120mL/min, the nitrogen flow in the second catalyst bed layer is 250mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.2mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 330 ℃, the reaction temperature of the second catalyst bed layer is 330 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.4 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of the methyl acrylate is 7%, the product concentration of the methyl propionate is 1.1%, and the content of the acetone product is 2%. Five days later, sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of methyl acrylate is 6.2%, the product concentration of methyl propionate is 0.9%, and the content of acetone product is 1.8%.
It can be seen from this comparative example 1 that, when no acidic catalyst was used, the product of methyl acrylate was low in content and contained a large amount of acetone.
Comparative example 2
The bed position of the first catalyst bed 3/5 is filled with 2 percent of bed volume of acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; the position of the second catalyst bed layer 3/5 bed layer is filled with 3 percent bed layer volume acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed of the first catalyst bed layer is 3:1, and the mass of methanol is 0.3 times of that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 120mL/min, the nitrogen flow in the second catalyst bed layer is 120mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.2mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 330 ℃, the reaction temperature of the second catalyst bed layer is 330 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.4 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of methyl acrylate is 14%, the product concentration of methyl propionate is 3%, and the content of acetone product is 2.2%. After five days, the product concentration of methyl acrylate was 8%, the product concentration of methyl propionate was 1.9%, and the product content of acetone was 1.4%.
It can be seen that when the gas space velocity of the second catalyst bed is almost equal to the gas space velocity of the first catalyst bed, the concentration of methyl acrylate in the product decreases significantly after five days of operation, because the catalyst stability is affected by the long-term contact of the second catalyst bed with water.
Comparative example 3
The bed position of the first catalyst bed 4/5 is filled with 2 percent of bed volume of acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; the position of the second catalyst bed layer 4/5 bed layer is filled with 3 percent bed layer volume acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed to the first catalyst bed is 3:1, and the mass of methanol is 0.3 times that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 120mL/min, the nitrogen flow in the second catalyst bed layer is 250mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.2mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 330 ℃, the reaction temperature of the second catalyst bed layer is 330 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.4 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of methyl acrylate is 9.5%, the product concentration of methyl propionate is 2.1%, and the content of acetone product is 1.1%. After five days, the product concentration of methyl acrylate was 8.5%, the product concentration of methyl propionate was 1.9%, and the product content of acetone was 0.9%.
In this comparative example 3, where the acidic catalyst was added at the lower part of the bed, the amount of methyl acrylate product in the product was increased as compared with that in comparative example 1, but the acetone content in the product was still higher because the acidic catalyst was located too far down.
Comparative example 4
The first catalyst bed 3/5 is filled with acidic catalyst SAPO-34 molecular sieve with 15% bed volume, and solid base catalyst Cs/SiO2The total amount of the catalyst in the first catalyst bed layer is 10 mL; the bed position of the second catalyst bed 1/3 is filled with 15 percent of bed volume acidic catalyst SAPO-34 molecular sieve, and the rest is solid base catalyst Cs/SiO2The total amount of catalyst in the second catalyst bed was 10 mL.
The molar ratio of methyl acetate to trioxymethylene in the feed of the first catalyst bed layer is 3:1, and the mass of methanol is 0.3 times of that of methyl acetate.
The nitrogen flow in the first catalyst bed layer is 120mL/min, the nitrogen flow in the second catalyst bed layer is 250mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the first catalyst bed layer is 0.2mL/min, the flow rate of a mixture of methyl acetate and trioxymethylene in the second catalyst bed layer is 0.05mL/min, the reaction temperature of the first catalyst bed layer is 330 ℃, the reaction temperature of the second catalyst bed layer is 330 ℃, and the reaction pressure of the first catalyst bed layer and the second catalyst bed layer is 0.4 MPa.
Sampling, adding internal standard toluene, and measuring the content of each component in the reaction mixture by gas chromatography, wherein the product concentration of methyl acrylate is 14%, the product concentration of methyl propionate is 3%, and the content of acetone product is 0.05%. After five days, the product concentration of methyl acrylate was 6%, the product concentration of methyl propionate was 0.5%, and the product content of acetone was 0.01%.
In this comparative example 4, the excessive amount of the acidic catalyst employed resulted in a higher formaldehyde content in the system, but rather in more coking of the catalyst bed, eventually leading to deactivation.
The utility model has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the utility model is defined by the appended claims.

Claims (13)

1. A composite catalyst bed comprises a first catalyst bed and a second catalyst bed which are connected in series, wherein the first catalyst bed and the second catalyst bed respectively and independently comprise a solid base catalyst filling section and an acid catalyst filling section.
2. The composite catalyst bed according to claim 1, wherein the solid base catalyst comprises a carrier and an active component and an optional auxiliary agent loaded on the carrier; preferably:
the carrier is selected from at least one of silicon oxide, aluminum oxide and SBA-15 molecular sieve; and/or
The active component is at least one of cesium, potassium and rubidium, and preferably, the loading amount of the active component is 1-20 wt%; and/or
The auxiliary agent is selected from at least one of zirconium, bismuth and lanthanum, and preferably, the loading amount is 0-5 wt%.
3. The composite catalyst bed according to claim 1, wherein the acidic catalyst is selected from alumina and/or molecular sieves, preferably from θ -Al2O3At least one of SAPO-34 molecular sieve and SAPO-35 molecular sieve.
4. The composite catalyst bed according to any one of claims 1 to 3, wherein the acid catalyst is loaded in an amount of 0.5 to 10% by bed volume at positions 1/3 to 3/4 of the first catalyst bed to form the acid catalyst loading section, and the solid base catalyst is loaded at the remaining positions to form the solid base catalyst loading section.
5. The composite catalyst bed of claim 4, wherein the second catalyst bed is charged with 0.5-10% bed volume of the acidic catalyst at positions 1/3-3/4 to form the acidic catalyst loading section, and the remaining positions are charged with the solid base catalyst to form the solid base catalyst loading section.
6. Use of the composite catalyst bed according to any one of claims 1 to 5 in the preparation of methyl acrylate.
7. A process for producing methyl acrylate by using the composite catalyst bed according to any one of claims 1 to 5, wherein the process comprises: and (3) sequentially passing raw materials including methyl acetate, an aldehyde source and methanol through the first catalyst bed layer and the second catalyst bed layer which are connected in series, and reacting to obtain the methyl acrylate.
8. The method of claim 7,
replenishing an aldehyde source at the top of the second catalyst bed; and/or
The aldehyde source is selected from at least one of trioxymethylene and/or methylal.
9. The method of claim 8,
the molar ratio of the methyl acetate to the aldehyde source in the feed to the first catalytic bed is (1-10): 1; and/or
The mass of the methanol in the first catalyst bed layer feeding is 0.1-0.5 times of the weight of the methyl acetate; and/or
The volume ratio of the supplementary aldehyde source in the second catalyst bed layer to the feeding raw material in the first catalyst bed layer is (0-2) to 1; and/or
When the aldehyde source supplemented by the second catalyst bed layer is trioxymethylene, solid trioxymethylene is heated until the trioxymethylene is in a liquid phase state, and then is introduced into the second catalyst bed layer through a pump.
10. The process of claim 7 wherein the gas space velocity of the second catalyst bed is greater than the gas space velocity of the first catalyst bed.
11. The method according to any one of claims 7 to 10, wherein the reaction temperature of the first catalyst bed is 300 to 400 ℃; and/or the reaction pressure is 0-1 MPa; and/or the liquid phase volume flow rate is 0.01-1 mL/min; and/or the nitrogen flow is 20-200 mL/min.
12. The method according to claim 11, wherein the reaction temperature of the second catalyst bed is 300-400 ℃; and/or the reaction pressure is 0-1 MPa; and/or the liquid phase volume flow rate is 0.01-0.5 mL/min; the nitrogen flow rate was 150-350 mL/min.
13. Methyl acrylate obtained by the process of claims 7 to 12.
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