CN112774658A - Acid-base bifunctional catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and preparation method thereof - Google Patents
Acid-base bifunctional catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and preparation method thereof Download PDFInfo
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- 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 discloses a catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and a preparation method thereof, and the catalyst mainly comprises the following steps of (1) washing a carrier, drying the carrier in an oven at 120 ℃, and roasting the carrier in a muffle furnace at 300-500 ℃ for 2-8 h; (2) respectively weighing compounds containing active components Al and Cs, preparing a solution with a certain concentration, fully soaking the active components for 2-24 h in an isovolumetric soaking mode, and drying for 4-15 h at 60-150 ℃. And finally roasting the catalyst for 2-8 hours in a muffle furnace at 400-650 ℃ to obtain the catalyst. The catalyst is an acid-base bifunctional catalyst, can effectively improve the selectivity and the conversion rate of a product, has good carbon deposition resistance, is simple and easy to prepare, and is suitable for large-scale industrial application.
Description
Technical Field
The invention relates to an acid-base bifunctional catalyst for synthesizing methyl acrylate by methyl acetate and formaldehyde and a preparation method thereof, in particular to a catalyst for preparing methyl acrylate by catalyzing methyl acetate and formaldehyde to undergo aldol condensation and a preparation method of the catalyst.
Background
Methyl acrylate is an important fine chemical raw material with wide application, and is mainly used as an organic synthesis intermediate and a high molecular monomer. The polymer synthesized by the method is widely used in the industries of coating, textile, leather making, adhesive and the like. In addition, the method also has wide application in the production of industries such as papermaking, leather making, paint, pharmacy and the like. In recent years, methyl acrylate has wide application, and although the total production amount of acrylic ester in China is large, the productivity is too dispersed, and the technology is not mature enough. More importantly, most of the acrylate process technology in China is imported, and the high-efficiency catalyst also depends on the import, so that the production cost of the methyl acrylate is greatly improved, the product price advantage of domestic chemical enterprises is further reduced, and the share of the methyl acrylate entering the international market is seriously influenced. With the development of national economy and the improvement of the living standard of people, more and more people are pursuing higher-quality life. In the modern society, the size is as small as that of clothes and housing, and the size is as large as that of national construction, and the figure of downstream products of methyl acrylate is ubiquitous. Therefore, the method has wide prospect of putting the methyl acrylate into production and has great significance.
The predominant process currently used commercially for the production of methyl acrylate is the propylene oxidation process. The method takes propylene as a raw material to prepare methyl acrylate by two routes, namely a one-step method and a two-step method, and the one-step method has a series of problems of low yield, poor stability of the catalyst, high inactivation rate and the like. The two-stage oxidation method is a main method for industrially producing methyl acrylate, and although the process flow is long, the catalytic efficiency of each step is high, and the total yield is improved. However, a large amount of concentrated sulfuric acid is required as a catalyst in the reaction, and thus there are also serious problems of equipment corrosion and environmental pollution. In recent years, with the rising of petroleum price, the production cost of propylene oxidation for preparing methyl acrylate is gradually increased, and researchers try to adopt a propane oxidation method to replace a propylene oxidation process. But because the propane property is stable, the yield of the synthesized product is low, the economic benefit is not high, and the process production is limited to a certain extent.
The process for preparing methyl acrylate by one-step condensation of methyl acetate and formaldehyde is concerned by industries and researchers, and long-term research is also carried out. The process has the advantages of simple reaction, no oxygen participation, water as a byproduct, high atom utilization rate and the like. Meanwhile, methyl acetate is used as a byproduct in a large amount in the processes of producing acetic acid, polyvinyl alcohol, phthalic acid and the like in industry. Compared with the traditional method, the synthesis of methyl acrylate by gas-phase aldolization of methyl acetate and formaldehyde is a resource-saving and environment-friendly green synthesis process, the production cost is reduced without being influenced by the price of crude oil, the emission of polluted waste liquid is effectively controlled, the resources are fully utilized, and the real green and environment-friendly effects are realized. Therefore, the method for preparing methyl acrylate by reasonably utilizing the gas phase condensation of methyl acetate and formaldehyde has great advantages and great industrial application prospects. There are also many reports of catalysts for this reaction, including CN108101767A, CN111437879A, CN10639492A, CN111437879A, CN108097324A, CN108097286, and the like. However, the problems of low catalyst activity, low conversion rate and selectivity, serious carbon deposition, short regeneration period, poor economic benefit and the like which need to be solved exist at present.
Disclosure of Invention
Based on the existing problems of the catalyst, the invention aims to provide the acid-base bifunctional catalyst for synthesizing the methyl acrylate by the methyl acetate and the formaldehyde through the one-step method and the preparation method thereof, which can improve the selectivity and the yield of the product and have good anti-carbon deposition capability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde in one step contains active components Al and Cs and carrier SiO2
Based on the mass of the carrier, the loading amount is calculated by the mass of the oxide of the active component, the loading amount of the Cs is 5-25%, and the loading amount of the Al active component is 0.1-10%;
in the method, the main sources of active components, namely cesium and aluminum oxide, are cesium nitrate, cesium carbonate, cesium sulfate, cesium acetate, aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum silicate and one or more of aluminum sulfide;
in the method, the carrier is porous silicon dioxide spheres, the particle size of the particles is 2-5mm, and the maximum aperture is 2-10 nm;
the acid-base bifunctional catalyst for synthesizing methyl acrylate by methyl acetate and formaldehyde through one-step method is prepared by the following steps:
(1) and (3) carrier treatment: soaking the carrier in deionized water for 0.5-2h, then placing the carrier in an oven for drying at the temperature of 100-;
(2) preparing an active ingredient salt solution: weighing salts of active components Al and Cs, and preparing a salt solution with a certain concentration;
(3) loading active components: adding the carrier obtained in the step (1) into the salt solution containing the active component prepared in the step (2) in an isovolumetric impregnation mode, stirring for 0.5-3h, standing for 6-24h, and fully drying at a certain temperature of 80-150 ℃;
(4) roasting the catalyst: heating the catalyst precursor obtained in the step (3) to 650 ℃ by a program in a muffle furnace, roasting for 3-12h, and then cooling to room temperature to obtain the catalyst;
a process for the preparation of a catalyst for the synthesis of methyl acrylate from methyl acetate and formaldehyde, characterised in that the reaction conditions are such that the methyl acetate/formaldehyde molar ratio is 0.5:1-5:1, methyl acetate: the methanol is 1:5-1:1, the feeding airspeed is 0.3-1.2h-1The reaction temperature is 330-380 ℃.
Compared with the prior art for preparing the catalyst, the invention has the advantages that:
(1) al and Cs are used as active components, wherein the Al can provide an acidic active center, and the Cs provides a basic active center. The number and the strength of acid-base active centers of the catalyst can be effectively regulated and controlled by changing the loading amounts of Al and Cs, so that the catalyst has better selectivity and yield.
(2) The specific surface area of the carrier can be improved by adding Al as an active component, so that the distribution of the active component Cs is more uniform, and the formation of carbon deposition is reduced, thereby the catalyst has longer service life.
(3) The catalyst is simple in preparation method, short in steps, wide in raw materials, suitable for large-scale industrial application and environment-friendly.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, fall within the protection scope of the present invention.
Example 1
In this example, a silica carrier is loaded with 8% of cesium as an active component and 3% of aluminum as an active component, and the specific preparation method is as follows:
(1) weighing 20g of silicon oxide carrier with the pore diameter of 7.6nm, washing the silicon oxide carrier with deionized water for 0.5h, and then putting the silicon oxide carrier into a drying oven to dry for 12h at 120 ℃; then, heating up to 400 ℃ at the speed of 10 ℃/min in a muffle furnace and roasting for 4 h;
(2) accurately weighing 4.42g of aluminum nitrate, and adding a certain amount of deionized water to fully dissolve the aluminum nitrate to obtain an aluminum-containing aqueous solution;
(3) adding the silicon oxide carrier obtained in the step (1) into the solution obtained in the step (2), stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(4) putting the catalyst precursor obtained in the step (3) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, roasting for 4h, and cooling to obtain an aluminum-loaded catalyst;
(5) accurately weighing 2.21g of cesium nitrate, and adding a certain amount of deionized water to fully dissolve the cesium nitrate to obtain an aqueous solution containing cesium;
(6) adding the aluminum-loaded catalyst obtained in the step (4) into the aqueous solution prepared in the step (5) according to an isometric impregnation method, stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(7) and (4) putting the precursor obtained in the step (6) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, continuously roasting for 4h, and cooling to obtain the catalyst.
Evaluation of catalyst: the catalytic performance of the catalyst was evaluated on a fixed bed reactor, with a catalyst loading of 10ml and reaction conditions such that the methyl acetate/formaldehyde/methanol molar ratio was 1: 1: 3, the feeding airspeed is 1h-1The reaction temperature was 360 ℃. The evaluation results were: the conversion of methyl acetate was 17.3% and the selectivity to methyl acrylate was 95.4%.
Example 2
In this embodiment, a silica carrier is loaded with 8% of cesium as an active component and 3% of aluminum as an active component, and the specific preparation method is as follows:
(1) weighing 20g of silicon oxide carrier with the pore diameter of 7.6nm, washing the silicon oxide carrier with deionized water for 0.5h, and then putting the silicon oxide carrier into a drying oven to dry for 12h at 120 ℃; then, heating up to 400 ℃ at the speed of 10 ℃/min in a muffle furnace and roasting for 4 h;
(2) 4.42g of aluminum nitrate is weighed and added with a certain amount of deionized water to be fully dissolved to obtain an aluminum-containing aqueous solution;
(3) adding the silicon oxide carrier obtained in the step (1) into the solution obtained in the step (2), stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(4) putting the catalyst precursor obtained in the step (3) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, roasting for 4h, and cooling to obtain an aluminum-loaded catalyst;
(5) accurately weighing 1.85g of cesium carbonate, and adding a certain amount of deionized water to fully dissolve the cesium carbonate to obtain an aqueous solution containing cesium;
(6) adding the aluminum-loaded catalyst obtained in the step (4) into the aqueous solution prepared in the step (5) according to an isometric impregnation method, stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(7) and (4) putting the precursor obtained in the step (6) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, continuously roasting for 4h, and cooling to obtain the catalyst.
The performance of the catalyst was evaluated in the same manner as in example 1, and the evaluation results were: the conversion of methyl acetate was 19.2% and the selectivity to methyl acrylate was 81.9%.
Example 3
In this embodiment, a silica carrier is loaded with 8% of cesium as an active component and 3% of aluminum as an active component, and the specific preparation method is as follows:
(1) weighing 20g of silicon oxide carrier with the pore diameter of 7.6nm, washing the silicon oxide carrier with deionized water for 0.5h, and then putting the silicon oxide carrier into a drying oven to dry for 12h at 120 ℃; then, heating up to 400 ℃ at the speed of 10 ℃/min in a muffle furnace and roasting for 4 h;
(2) accurately weighing 1.57g of aluminum chloride, and adding a certain amount of deionized water to fully dissolve the aluminum chloride to obtain an aluminum-containing aqueous solution;
(3) adding the silicon oxide carrier obtained in the step (1) into the solution obtained in the step (2), stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(4) putting the catalyst precursor obtained in the step (3) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, roasting for 4h, and cooling to obtain an aluminum-loaded catalyst;
(5) accurately weighing 2.21g of cesium nitrate, and adding a certain amount of deionized water to fully dissolve the cesium nitrate to obtain an aqueous solution containing cesium;
(6) adding the cesium-loaded catalyst obtained in the step (4) into the aqueous solution prepared in the step (5) according to an isometric impregnation method, stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(7) and (4) putting the precursor obtained in the step (6) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, continuously roasting for 4h, and cooling to obtain the catalyst.
The performance of the catalyst was evaluated in the same manner as in example 1, and the evaluation results were: the conversion of methyl acetate was 20.9% and the selectivity to methyl acrylate was 80.7%.
Example 4
In this embodiment, a silica carrier is loaded with 8% of cesium as an active component and 3% of aluminum as an active component, and the specific preparation method is as follows:
(1) weighing 20g of silicon oxide carrier with the pore diameter of 7.6nm, washing the silicon oxide carrier with deionized water for 0.5h, and then putting the silicon oxide carrier into a drying oven to dry for 12h at 120 ℃; then, heating up to 400 ℃ at the speed of 10 ℃/min in a muffle furnace and roasting for 4 h;
(2) accurately weighing 2.21g of cesium nitrate, and adding a certain amount of deionized water to fully dissolve the cesium nitrate to obtain an aqueous solution containing cesium;
(3) adding the silicon oxide carrier obtained in the step (1) into the solution obtained in the step (2), stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(4) putting the catalyst precursor obtained in the step (3) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, roasting for 4h, and cooling to obtain a cesium-loaded catalyst;
(5) accurately weighing 4.42g of aluminum nitrate, and adding a certain amount of deionized water to fully dissolve the aluminum nitrate to obtain an aluminum-containing aqueous solution;
(6) adding the cesium-loaded catalyst obtained in the step (4) into the aqueous solution prepared in the step (5) according to an isometric impregnation method, stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(7) and (4) putting the precursor obtained in the step (6) into a muffle furnace, heating to 500 ℃ at the speed of 10 ℃/min, continuously roasting for 4h, and cooling to obtain the catalyst.
The performance of the catalyst was evaluated in the same manner as in example 1, and the evaluation results were: the conversion of methyl acetate was 13.6% and the selectivity to methyl acrylate was 92.7%.
Example 5
In this embodiment, a silica carrier is loaded with 8% of cesium as an active component and 3% of aluminum as an active component, and the specific preparation method is as follows:
(1) weighing 20g of silicon oxide carrier with the pore diameter of 7.6nm, washing the silicon oxide carrier with deionized water for 0.5h, and then putting the silicon oxide carrier into a drying oven to dry for 12h at 120 ℃; then, heating up to 400 ℃ at the speed of 10 ℃/min in a muffle furnace and roasting for 4 h;
(2) accurately weighing 4.42g of aluminum nitrate, and adding a certain amount of deionized water to fully dissolve the aluminum nitrate to obtain an aluminum-containing aqueous solution;
(3) adding the silicon oxide carrier obtained in the step (1) into the solution obtained in the step (2), stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(4) putting the catalyst precursor obtained in the step (3) into a muffle furnace, heating to 400 ℃ at the speed of 10 ℃/min, roasting for 4h, and cooling to obtain an aluminum-loaded catalyst;
(5) accurately weighing 2.21g of cesium nitrate, and adding a certain amount of deionized water to fully dissolve the cesium nitrate to obtain an aqueous solution containing cesium;
(6) adding the aluminum-loaded catalyst obtained in the step (4) into the aqueous solution prepared in the step (5) according to an isometric impregnation method, stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(7) and (4) putting the precursor obtained in the step (6) into a muffle furnace, heating to 400 ℃ at the speed of 10 ℃/min, continuously roasting for 4h, and cooling to obtain the catalyst.
The performance of the catalyst was evaluated in the same manner as in example 1, and the evaluation results were: the conversion of methyl acetate was 21.6% and the selectivity to methyl acrylate was 83.6%.
Example 6
In this embodiment, a silica carrier is loaded with 8% of cesium as an active component and 3% of aluminum as an active component, and the specific preparation method is as follows:
(1) weighing 20g of silicon oxide carrier with the pore diameter of 7.6nm, washing the silicon oxide carrier with deionized water for 0.5h, and then putting the silicon oxide carrier into a drying oven to dry for 12h at 120 ℃; then, heating up to 400 ℃ at the speed of 10 ℃/min in a muffle furnace and roasting for 4 h;
(2) accurately weighing 4.42g of aluminum nitrate, and adding a certain amount of deionized water to fully dissolve the aluminum nitrate to obtain an aluminum-containing aqueous solution;
(3) adding the silicon oxide carrier obtained in the step (1) into the solution obtained in the step (2), stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(4) putting the catalyst precursor obtained in the step (3) into a muffle furnace, heating to 600 ℃ at the speed of 10 ℃/min, roasting for 4h, and cooling to obtain an aluminum-loaded catalyst;
(5) accurately weighing 2.21g of cesium nitrate, and adding a certain amount of deionized water to fully dissolve the cesium nitrate to obtain an aqueous solution containing cesium;
(6) adding the aluminum-loaded catalyst obtained in the step (4) into the aqueous solution prepared in the step (5) according to an isometric impregnation method, stirring for 0.5h, standing for 12h, and then drying at 120 ℃ for 12 h;
(7) and (4) putting the precursor obtained in the step (6) into a muffle furnace, heating to 600 ℃ at the speed of 10 ℃/min, continuously roasting for 4h, and cooling to obtain the catalyst.
The performance of the catalyst was evaluated in the same manner as in example 1, and the evaluation results were: the conversion of methyl acetate was 19.4% and the selectivity to methyl acrylate was 80.7%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde mainly comprises an active component and a carrier, and is characterized in that: the active components are Al and Cs, and the carrier is porous SiO2The loading amount is calculated by the oxide mass of the active component according to the mass of the carrier, the loading amount of the Cs is 5-25%, and the loading amount of the Al active component is 0.1-10%.
2. The catalyst according to claim 1, wherein the active component cesium source is cesium nitrate, cesium carbonate, cesium sulfate, cesium acetate, and the aluminum source is one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum silicate, and aluminum sulfide.
3. The catalyst of claim 1, wherein the carrier of the catalyst is porous silica spheres, the particle size is 2-5mm, and the maximum pore size is 2-10 nm.
4. The method for preparing the catalyst according to claim 1, comprising the following steps:
(1) and (3) carrier treatment: soaking the carrier in deionized water for 0.5-2h, then placing the carrier in an oven for drying at the temperature of 100-;
(2) preparing an active ingredient salt solution: weighing salts of active components Al and Cs, and preparing a salt solution with a certain concentration;
(3) loading active components: adding the carrier obtained in the step (1) into the salt solution containing the active component prepared in the step (2) in an isovolumetric impregnation mode, stirring for 0.5-3h, standing for 6-24h, and fully drying at a certain temperature of 80-150 ℃;
(4) roasting the catalyst: and (4) roasting the catalyst precursor obtained in the step (3) in a muffle furnace at the temperature of 400-650 ℃ by temperature programming for 3-12h, and then cooling to room temperature to obtain the catalyst.
5. A process for preparing a catalyst as claimed in claim 1 and claim 4, wherein the active component is impregnated in equal volumes, and the impregnation sequence of the active component is selected from simultaneous impregnation or impregnation with aluminium followed by caesium or caesium followed by aluminium.
6. The catalyst for synthesizing methyl acrylate from formaldehyde and methyl acetate and the preparation method thereof according to the claims 1-5, characterized in that: the catalytic reaction conditions are as follows: the molar ratio of methyl acetate to formaldehyde is 0.5:1-5:1, the molar ratio of methyl acetate to methanol is 1:5-1:1, and the feeding airspeed is 0.3-1.2h-1The reaction temperature is 330-380 ℃.
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| CN117563577A (en) * | 2023-11-16 | 2024-02-20 | 中国科学院过程工程研究所 | Preparation method of catalyst for synthesizing methyl methacrylate by using silica carrier surface hydroxyl regulation method |
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