CN110639492A - Catalyst for preparing methyl acrylate from methyl acetate and formaldehyde and application thereof - Google Patents
Catalyst for preparing methyl acrylate from methyl acetate and formaldehyde and application thereof Download PDFInfo
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- CN110639492A CN110639492A CN201810676241.6A CN201810676241A CN110639492A CN 110639492 A CN110639492 A CN 110639492A CN 201810676241 A CN201810676241 A CN 201810676241A CN 110639492 A CN110639492 A CN 110639492A
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- 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
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- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- 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 invention relates to a catalyst for preparing methyl acrylate from methyl acetate and formaldehyde and application thereof, and mainly solves the problem of low yield of methyl acrylate in the process of preparing methyl acrylate from methyl acetate. The catalyst for preparing methyl acrylate from methyl acetate and formaldehyde comprises the following components in parts by mass: 0.1-40 parts of active component; 50-100 parts of a carrier; the technical scheme that the active component comprises at least one selected from alkali metal elements better solves the problem and can be used for producing methyl acrylate or methyl propionate by condensing methyl acetate and formaldehyde.
Description
Technical Field
The invention relates to a catalyst for preparing methyl acrylate from methyl acetate and formaldehyde and application thereof.
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.
The yield of methyl acetate in China is greatly surplus, and the green synthesis of methyl acrylate is realized by taking industrial byproduct methyl acetate as a raw material, adopting a safe, environment-friendly and nontoxic solid base catalyst and adopting a clean synthesis process.
Based on the alpha-MMA process proposed by Lucaite company, methyl acetate and formaldehyde are used as raw materials, a novel catalyst is adopted to synthesize methyl acrylate, the single-pass conversion rate of the methyl acetate is 15%, the selectivity of the methyl acrylate reaches 90%, and the yield of the methyl acrylate is 13.5%. The catalyst reaction-regeneration fluidized bed coupling system is adopted, and the problems of short one-way service life, easy carbon deposition and frequent regeneration of the catalyst are solved.
The alpha-MMA process, in which Cs is supported on silica, has high product selectivity and relatively low cost, verifies the process for producing MMA by catalyzing methyl propionate with formaldehyde, and has been industrialized. At present, the research on the synthesis of methyl acrylate by taking methyl acetate and formaldehyde as raw materials is not industrialized, the research is only in the research stage at present, but the cost advantage is very obvious as a new process route, and the process is researched and developed by large-scale transnational chemical companies by investing manpower and material resources.
In recent years, many units at home and abroad have studied the synthesis of methyl acrylate from methyl acetate and formaldehyde. Zhanggguoolang, et Al, Catal, Sci, Techninol, 2016,6,6417-2O3The yield of the catalyst, namely methyl acrylate reaches 40 percent, but the catalyst is quickly deactivated within 100 hours, and the stability needs to be improvedThe steps are increased. [ Yongsheng et al, school news of Qizihaar university, 2007, 23(1), 24-26 ] adopts K+/SiO2Solid super strong base catalyst at 300 deg.c and space velocity of 4.5 hr-1The yield of methyl acrylate is 31% under the condition of 1:3 of aldehyde-ester ratio, but the stability and selectivity results of the catalyst are not given. [ SUNWUYANG et al, oil refining and chemical industry, 2009, 20(2), 17-19 ] considers the influence of the concentration of rubidium nitrate and cesium nitrate on the performance of the catalyst at different temperatures, and finds that the effect of Cs is better than that of Rb, and the yield of methyl acrylate reaches 19.6% at 380 ℃. [ ZHIRONG ZHU et al, RSCAdv, 2015,5,32826-32834 ] Cs-La-Sb/SiO2The catalyst is used for preparing methyl acrylate by gas phase condensation of methyl acetate and formaldehyde, the yield of the methyl acrylate is 8-10%, but the yield is reduced to 5-6% after the reaction is carried out for 100 hours.
Chinese patent No. CN104703696A reports that the LouTot International British Co., Ltd adopts Cs catalyst, regenerant and freshener for preparing methyl methacrylate and methacrylic acid from methyl propionate and formaldehyde, and the total selectivity of the two reaches 95%.
Chinese patent (CN 101575290A) discloses a method for synthesizing methyl acrylate by a catalyst sectional filling mode, wherein a phosphorus vanadium catalyst and a Cs catalyst are filled in a sectional mode, and the selectivity of a product is improved by changing the acidity and alkalinity of the catalyst.
Chinese patent No. CN103506107A discloses a catalyst with cesium oxide as active component, which adopts gas phase condensation reaction, the reaction temperature is above 380 deg.C, and the product contains acrylic acid product besides methyl acrylate.
Chinese patent No. CN102941113A reports that Cs is a condensation catalyst with a main active center, at least one of nitrate or oxide of Zr, B and Ce is added, methylal is used as a raw material, the yield of methyl acrylate is 15-30%, but the stability of the catalyst and the loss condition of the main active center Cs are not given due to high-temperature gas-phase condensation.
The catalyst preparation method reported above mainly adopts an impregnation method for preparation, and for the direct preparation of methyl acrylate/methyl methacrylate by the reaction of methyl acetate/methyl propionate and formaldehyde, a solid base catalyst loaded with Cs is mainly adopted, and the optimal catalytic performance can be obtained only by requiring uniform distribution and high dispersion of the base center, so that the highly dispersed solid base catalyst needs to be prepared. Meanwhile, the high-temperature gas-phase condensation process has high requirements on the Cs catalyst, the existing reported result adopts a high-temperature gas-phase condensation form, the reaction temperature is high, the inactivation is quick, a reaction-regeneration regular switching system is generally considered, and the reaction can be continuously carried out.
Disclosure of Invention
One of the technical problems to be solved by the invention is the technical problem of low yield of methyl acrylate in the process of preparing methyl acrylate by condensing methyl acetate and formaldehyde in the prior art, and the invention provides a catalyst for condensation reaction of methyl acetate and formaldehyde, which has the advantage of high yield of methyl acrylate.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
The third technical problem to be solved by the invention is the application of the catalyst.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the catalyst for preparing methyl acrylate from methyl acetate and formaldehyde comprises the following components in parts by mass:
0.1-40 parts of active component;
50-100 parts of a carrier;
the active component includes at least one selected from alkali metal elements.
The presence of the alkali metal element increases the yield of methyl acrylate.
In the above technical solution, the active component further includes a promoter element in addition to at least one selected from alkali metal elements, and the promoter element is selected from at least one of rare earth elements or phosphorus element. In this case, the catalyst preferably comprises the following components in parts by mass:
0.1-20 parts of alkali metal elements;
0.5-20 parts of cocatalyst element;
50-100 parts of a carrier;
the promoter element is selected from at least one of rare earth elements or at least one of phosphorus elements.
The existence of the promoter element further improves the yield of the methyl acrylate.
As the most preferable technical scheme, the promoter elements simultaneously comprise rare earth elements and phosphorus, and the rare earth elements and the phosphorus have synergistic effect on the aspect of improving the yield of the methyl acrylate. In this case, the catalyst preferably comprises the following components in parts by mass:
0.1-20 parts of alkali metal elements;
0.5-10 parts of rare earth elements;
0.5-10 parts of P element;
50-100 parts of a carrier.
In the above technical solution, the alkali metal element is preferably at least one of K, Rb and Cs.
In the above technical solution, the rare earth element is preferably at least one of La and Ce.
In the technical scheme, the alkali metal element is preferably 5-15 parts.
In the technical scheme, the content of the rare earth element is preferably 1-5 parts.
In the technical scheme, the content of phosphorus is preferably 1-5 parts.
In the above technical solution, the carrier is preferably at least one of alumina, silica, activated carbon, titania and zirconia.
In the technical scheme, the content of the carrier is preferably 75-95 parts.
In the above technical scheme, the technical key of the present invention is the selection of the catalyst components, the geometric shape of the carrier is not particularly limited, and the carrier may be irregular powder or granular, or may have regular geometric shapes, such as but not limited to, spherical, elliptical, cylindrical, cloverleaf, and the like.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing a catalyst according to any of the preceding technical solutions, comprising the steps of:
(1) impregnating a carrier with a compound solution of an active component to obtain a catalyst precursor;
(2) and (4) roasting.
In the above technical solution, when the active component further includes a promoter element in addition to at least one selected from alkali metal elements, and the promoter element is selected from at least one of rare earth elements and/or phosphorus element, the preparation method of the catalyst is further preferably:
(1) impregnating the carrier with a solution of a compound of an alkali metal element and/or a compound of a promoter element to obtain the catalyst
A reagent precursor;
(2) and (4) roasting.
In the above technical solution, the compound of the alkali metal element is preferably at least one selected from nitrate, carbonate and acetate.
In the above technical solution, the compound of the rare earth element is preferably at least one selected from nitrate and acetate.
In the above technical solution, the compound of the element P is preferably at least one selected from metaphosphoric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, diammonium hydrogen phosphate, and monoammonium hydrogen phosphate.
Those skilled in the art know that a drying step is included after step (1) and before step (2) in order to obtain better strength, uniformity of dispersion of components, and the like.
In the technical scheme, the roasting temperature is preferably 500-800 ℃.
In the technical scheme, the roasting time is preferably 5-15 hours.
In the technical scheme, the drying temperature is preferably 40-70 ℃.
In the technical scheme, the drying time is preferably 12-72 hours.
To solve the third technical problem, the technical scheme of the invention is as follows:
the application of the catalyst in the technical scheme of one of the technical problems in preparing methyl acrylate by condensing methyl acetate and formaldehyde.
The technical key of the invention is the selection of the catalyst components, and under the condition of disclosing the catalyst composition, the technical personnel in the field can reasonably select the specific method and the process conditions of the specific application without creative work and can obtain the comparable technical effect. By way of non-limiting example, a specific application method of the present invention may be:
in the presence of the catalyst described in any of the technical problems of the present invention, methyl acetate and formaldehyde are subjected to a condensation reaction to obtain methyl acrylate.
In the technical scheme, the condensation reaction temperature is preferably 250-300 ℃.
In the technical scheme, the molar ratio of methyl acetate to formaldehyde is preferably 9-72.
In the technical scheme, the amount of the catalyst is preferably 3-10% of the total amount of methyl acetate and formaldehyde by weight.
In the above-mentioned embodiment, the time for the condensation reaction is preferably 210 hours.
In the above technical scheme, the source of formaldehyde is not particularly limited, but may be generally obtained by in situ depolymerization of trioxane and/or paraformaldehyde.
The yield of methyl acrylate is defined as follows:
the yield of methyl acrylate was ═ 100% by [ mole of methyl acrylate in the product/(mole of trioxymethylene in the raw material × 3) ].
By adopting the invention, the yield of the methyl acrylate reaches up to 35 percent.
The invention is further illustrated by, but is not limited to, the following examples.
Detailed Description
[ example 1]
1. Preparation of impregnation liquid
Weighing cesium acetate C2H3CsO214.4 g, 100 ml of homogeneous solution is prepared and left overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Catalyst preparation
And adding 90 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then carrying out vacuum drying for 24 hours at 70 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 2]
1. Preparation of impregnation liquid
Weighing cesium nitrate CsNO314.6 g, La (NO)3)3·6H2O12.4 g, prepared into 100 ml of uniform solution and left overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Preparation of the catalyst
And (3) adding 86 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then drying for 24 hours at 50 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 3]
1. Preparation of impregnation liquid
Weighing cesium nitrate CsNO314.6 g, Ce (NO)3)3·6H2O12.3 g, prepared into 100 ml of uniform solution and left overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Preparation of the catalyst
And (3) adding 86 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then drying for 24 hours at 50 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 4]
1. Preparation of impregnation liquid
Weighing cesium nitrate CsNO314.6 g and 15.8 g of concentrated phosphoric acid (80 percent by mass) are prepared into 100 ml of uniform solution and are kept stand overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Preparation of the catalyst
And (3) adding 86 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then drying for 24 hours at 50 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 5]
1. Preparation of impregnation liquid
Weighing cesium nitrate CsNO314.6 g, La (NO)3)3·6H2O6.2 g and concentrated phosphoric acid (80% by mass) 7.9 g, and the mixture is prepared into a uniform solution of 100 ml and kept stand overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
4. Preparation of the catalyst
And (3) adding 86 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then drying for 24 hours at 50 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
5. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 6]
1. Preparation of impregnation liquid
Weighing cesium nitrate CsNO314.6 g, Ce (NO)3)3·6H2O6.15 g and concentrated phosphoric acid (80% by mass) 7.9 g are prepared into a uniform solution of 100 ml and left overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Preparation of the catalyst
And (3) adding 86 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then drying for 24 hours at 50 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 7]
1. Preparation of impregnation liquid
Weighing potassium nitrate KNO338.7 g, La (NO)3)3·6H215.5 g of O and 7.9 g of concentrated phosphoric acid (with the mass concentration of 80 percent) are prepared into 100 ml of uniform solution and are kept stand overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Preparation of the catalyst
And adding 78 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then drying for 24 hours at 50 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 8]
1. Preparation of impregnation liquid
Weighing rubidium nitrate RbNO317.2 g of lanthanum nitrate La (NO)3)3·6H2O7.0 g and concentrated phosphoric acid (80% by mass) 9.4 g are prepared into a uniform solution of 100 ml, and the solution is left to stand overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Catalyst preparation
Adding 84 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then carrying out vacuum drying for 24 hours at 50 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out under the self-pressure of a 275 ℃ system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 9]
1. Preparation of impregnation liquid
Weighing cesium acetate CsNO321.6 g, cerium nitrate Ce (NO)3)3·6H215.0 g of O and 3.1 g of concentrated phosphoric acid (with the mass concentration of 80 percent) are prepared into 100 ml of uniform solution and are kept stand overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Catalyst preparation
And adding 79 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then carrying out vacuum drying for 24 hours at 60 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 10]
1. Preparation of impregnation liquid
Weighing cesium acetate C2H3CsO228.8 g of lanthanum nitrate La (NO)3)3·6H2O 2.4 g of concentrated phosphoric acid (with the mass concentration of 80%) 3.1 g, 100 ml of uniform solution is prepared, and the solution is kept stand overnight for use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Catalyst preparation
And adding 78 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then carrying out vacuum drying for 24 hours at 70 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
[ example 11]
1. Preparation of impregnation liquid
Weighing cesium acetate C2H3CsO214.4 g of lanthanum nitrate La (NO)3)3·6H2O2.4 g and concentrated phosphoric acid (80% by mass) 15.5 g are prepared into 100 ml of uniform solution and are left for overnight use.
2. Preparation of the support
200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose are taken, 180 g of aqueous solution containing 30 percent of nitric acid in percentage by weight is slowly added in batches and stirred uniformly, 5 g of PEG2000 is added, kneading is carried out for 40 minutes, strips are extruded and formed, drying is carried out at 100 ℃ for 18 hours, and roasting is carried out at 800 ℃ for 5 hours, thus obtaining the cylindrical carrier with the diameter of 3mm and the length of 5 mm.
3. Catalyst preparation
Adding 84 g of carrier into the prepared impregnation liquid, putting the impregnation system into a water bath at 60 ℃, rotationally stirring for 2 hours, standing and aging overnight, then carrying out vacuum drying for 24 hours at 70 ℃, and roasting for 5 hours at 550 ℃ in an air atmosphere to obtain a catalyst finished product.
4. Catalyst evaluation
3 g of catalyst is loaded into a high-pressure reaction kettle, 38 g of methyl acetate and 5 g of trioxymethylene are added, the reaction is carried out at 275 ℃ under the self-pressure of the system, the temperature and the pressure are reduced after 4 hours of reaction, the content of the product is analyzed by an internal standard gas chromatography, the internal standard substance is toluene, and the evaluation results are shown in table 1.
TABLE 1
| Alkali metal per part | La/part | Ce per part | P/portion | Carrier per part | Yield of methyl acrylate% | |
| Example 1 | Cs:10 | - | - | - | 90 | 18.4 |
| Example 2 | Cs:10 | 4 | - | - | 86 | 26.5 |
| Example 3 | Cs:10 | - | 4 | - | 86 | 25.8 |
| Example 4 | Cs:10 | -- | - | 4 | 86 | 21.8 |
| Example 5 | Cs:10 | 2 | - | 2 | 86 | 33.4 |
| Example 6 | Cs:10 | - | 2 | 2 | 86 | 34.1 |
| Example 7 | K:15 | 5 | - | 2 | 78 | 27.4 |
| Example 8 | Rb:10 | 3 | - | 3 | 84 | 25.8 |
| Example 9 | Cs:15 | - | 5 | 1 | 79 | 32.4 |
| Example 10 | Cs:20 | 1 | 1 | 78 | 31.0 | |
| Example 11 | Cs:10 | 1 | 5 | 84 | 27.3 |
Claims (10)
1. The catalyst for preparing methyl acrylate from methyl acetate and formaldehyde comprises the following components in parts by mass:
0.1-40 parts of active component;
50-100 parts of a carrier;
the active component includes at least one selected from alkali metal elements.
2. The catalyst of claim 1, wherein the alkali metal element is at least one of K, Rb and Cs.
3. The catalyst according to claim 1, wherein the alkali metal element is 5 to 15 parts.
4. The catalyst according to claim 1, characterized in that the carrier is selected from at least one of alumina, silica, activated carbon, titania and zirconia.
5. The catalyst of claim 1, wherein the support is present in an amount of 75 to 95 parts.
6. The method for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:
(1) impregnating a carrier with a compound solution of an active component to obtain a catalyst precursor;
(2) and (4) roasting.
7. The method according to claim 6, wherein the compound of an alkali metal element is at least one selected from the group consisting of a nitrate, a carbonate and an acetate.
8. The method according to claim 6, wherein a drying step is included after the step (1) and before the step (2).
9. The method according to claim 6, wherein the calcination temperature is 500 to 800 ℃.
10. Use of the catalyst of any one of claims 1 to 5 in the preparation of methyl acrylate by the condensation of methyl acetate and formaldehyde.
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| CN113877561A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Solid base catalyst and preparation method and application thereof |
| CN113877560A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Synthesis method of methyl acrylate and solid base catalyst thereof |
| CN114478244A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Method for synthesizing methyl acrylate, catalyst and application |
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| CN113877562A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Solid base catalyst for synthesizing methyl acrylate and preparation method and application thereof |
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| CN113877561B (en) * | 2020-07-03 | 2024-03-26 | 中国石油化工股份有限公司 | Solid base catalyst and preparation method and application thereof |
| CN113877562B (en) * | 2020-07-03 | 2024-05-03 | 中国石油化工股份有限公司 | Solid base catalyst for synthesizing methyl acrylate, and preparation method and application thereof |
| CN114478244A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Method for synthesizing methyl acrylate, catalyst and application |
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