CN107051576B - Catalyst for synthesizing acrylic acid or acrylic ester from acetylene and preparation method and application thereof - Google Patents

Catalyst for synthesizing acrylic acid or acrylic ester from acetylene and preparation method and application thereof Download PDF

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CN107051576B
CN107051576B CN201710312012.1A CN201710312012A CN107051576B CN 107051576 B CN107051576 B CN 107051576B CN 201710312012 A CN201710312012 A CN 201710312012A CN 107051576 B CN107051576 B CN 107051576B
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catalyst
nickel
acetylene
acrylic acid
organic solvent
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CN107051576A (en
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吴黎阳
史雪君
余海鹏
黄伟
史东军
苏二强
吴道洪
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Beijing Huafu Engineering Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/755—Nickel
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract

The invention discloses a catalyst for synthesizing acrylic acid or acrylic ester by acetylene and a preparation method and application thereof, wherein the catalyst comprises the following components: an acidic molecular sieve; an inert oxide support; the catalyst comprises a nickel compound and a nickel compound loaded on an oxide carrier, wherein the loading amount of the nickel compound in the catalyst is 1-10 wt% calculated by nickel. The catalyst for synthesizing acrylic acid or acrylic ester by acetylene has the advantages of simple components, low cost, easy separation, good stability, high activity, strong selectivity, small corrosivity and the like, and has wide application prospect.

Description

Catalyst for synthesizing acrylic acid or acrylic ester from acetylene and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst for synthesizing acrylic acid or acrylic ester by acetylene, and a preparation method and application thereof.
Background
Acrylic acid and its ester are one of the important fine chemical raw materials, and are mainly used as organic synthesis intermediates and monomers for synthesizing high molecular materials. The polymer product formed by copolymerization of acrylic low carbon alcohol ester and many vinyl monomers has wide application in the aspects of modification of fabrics and plastics, processing of leather, fiber and the like, and the polymer product and various polymers of acrylic acid and acrylate form acrylic acid series chemical products and are important monomers for preparing high molecular compounds.
At present, the production of acrylic esters is mainly synthesized by esterification of acrylic acid with the corresponding alcoholA method and a direct carbonyl synthesis method of acetylene, carbon monoxide and alcohol. The acrylic acid in the acrylic acid esterification method is mainly prepared by a propylene partial oxidation method, cheap propylene is used as a raw material, and the production cost is low, but the method excessively depends on quite nervous petroleum resources. The acetylene carbonylation method does not depend on petroleum, and is particularly suitable for developing fine chemical engineering in countries or regions with poor oil, rich gas and rich coal. Coal and natural gas resources in China are rich, calcium carbide is produced, and the tail gas generated in the preparation of acetylene by using a calcium carbide method contains a large amount of carbon monoxide which can be used as a carbonyl source for synthesizing acrylic acid by using acetylene carbonyl, so that the development of the route in China has resource advantages. The synthesis of acrylic acid by the carbonylation of acetylene was first discovered by Reppe, a German scholars, when the catalyst used was Ni (CO)4And the catalyst has high toxicity and is difficult to solve the problem of labor protection. Subsequently, BASF corporation improved it and applied it to industrial production. The improved catalyst is mainly halide of nickel and copper, and the catalyst has good activity on synthesizing acrylic acid by acetylene carbonyl, but has serious corrosion to equipment, especially is easy to deposit carbon to block pipelines. Some catalytic systems added with phosphine ligands and weak acids have been developed since then, but have problems of corrosion of the reactor and the like.
Therefore, catalysts suitable for the synthesis of acrylic acid and its esters by acetylene carbonylation have yet to be developed.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a catalyst for synthesizing acrylic acid or acrylic ester by acetylene and a preparation method and application thereof.
According to one aspect of the present invention, there is provided a catalyst for the synthesis of acrylic acid or acrylate ester from acetylene, the catalyst comprising:
an acidic molecular sieve;
an inert oxide support;
a nickel compound supported on the oxide support,
wherein the loading amount of the nickel compound in the catalyst is 1-10 wt% in terms of nickel.
According to the catalyst for synthesizing acrylic acid or acrylic ester from acetylene, disclosed by the embodiment of the invention, the active component nickel is loaded on the oxide carrier, so that the heterogeneous phase of the homogeneous catalyst can be effectively realized, and the separation of a product and the catalyst is facilitated; meanwhile, the acidic molecular sieve is adopted to replace liquid acids such as methane sulfonic acid and the like, so that a hydrogen source required by the activated nickel catalyst can be provided, the reaction activity of the catalyst is obviously improved, and the corrosivity of a catalytic system to production equipment can be effectively reduced. Therefore, the catalyst for synthesizing acrylic acid or acrylic ester by acetylene has the advantages of simple components, low cost, easy separation, good stability, high activity, strong selectivity, low corrosivity and the like, and has wide application prospect.
In addition, the catalyst for synthesizing acrylic acid or acrylate from acetylene according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the inert oxide support is one of silica, titania, alumina and magnesia. Therefore, the stability of the catalyst can be obviously improved, and the aim of reducing the cost is fulfilled.
In some embodiments of the invention, the acidic molecular sieve is one of an H beta molecular sieve, an HY molecular sieve, HZSM-5, HZSM-22, and HZSM-35. Therefore, the reaction activity and the catalytic selectivity of the catalyst can be remarkably improved.
In some embodiments of the invention, the mass ratio of the inert oxide support to the acidic molecular sieve is (1-20): 1. thereby, the stability, reactivity and catalytic selectivity of the catalyst can be further improved.
According to the second aspect of the present invention, the present invention also provides a method for preparing the above catalyst for acetylene synthesis of acrylic acid or acrylic ester, comprising:
preparing soluble nickel salt into a nickel-containing aqueous solution;
placing the inert oxide carrier in the nickel-containing aqueous solution for dipping treatment and drying to obtain an inert oxide carrier loaded with a nickel compound;
and mixing the obtained inert oxide carrier loaded with the nickel compound with the acidic molecular sieve according to a preset ratio to obtain the catalyst.
Therefore, the method for preparing the catalyst for synthesizing acrylic acid or acrylic ester by acetylene is simple, and the prepared catalyst has the advantages of simple components, low cost, easy separation, good stability, high activity, strong selectivity, small corrosivity and the like, and has wide application prospect.
In addition, the method for preparing the catalyst for synthesizing acrylic acid or acrylate from acetylene according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the soluble nickel salt is one of a nickel halide, nickel sulfate, nickel acetate, and nickel nitrate. Thus, nickel can be smoothly supported on the carrier, and a catalyst containing nickel as an active component can be produced.
In some embodiments of the present invention, the time of the dipping treatment is 10 to 24 hours, the drying temperature is 80 to 200 ℃, and the drying time is 3 to 15 hours. This can further improve the stability and reactivity of the catalyst.
According to the third aspect of the present invention, the present invention also provides a method for synthesizing acrylic acid or acrylate from acetylene, comprising:
mixing the catalyst for synthesizing acrylic acid or acrylic ester by acetylene with an organic solvent and water or an organic solvent and alcohol, and adding the mixture into a high-pressure kettle;
and introducing acetylene and carbon monoxide into the autoclave under the stirring condition, and reacting under the catalytic action of the catalyst to obtain acrylic acid or acrylic ester.
The method for synthesizing acrylic acid or acrylic ester by acetylene in the embodiment of the invention is to dissolve the catalyst in the organic solvent and water or the organic solvent and alcohol, and react with acetylene and carbon monoxide in the high-pressure reaction kettle under the catalytic action of the catalyst to obtain acrylic acid or acrylic ester. The method for synthesizing acrylic acid or acrylic ester by acetylene can effectively prepare acrylic acid or acrylic ester with high yield.
In some embodiments of the present invention, the mass of the water is 10 to 25% of the mass of the organic solvent, and the mass of the catalyst is 0.1 to 10% of the total mass of the organic solvent and the water. This can further improve the reaction efficiency of acetylene for synthesizing acrylic acid or acrylic ester.
In some embodiments of the invention, the mass of the alcohol is 10-25% of the mass of the organic solvent; the mass of the catalyst is 0.1-10% of the total mass of the organic solvent and the alcohol. This can further improve the reaction efficiency of acetylene for synthesizing acrylic acid or acrylic ester.
In some embodiments of the invention, the organic solvent is selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, acetone, N-methylpyrrolidone, N-dimethylformamide. Therefore, the catalyst can be completely dissolved, and the reaction efficiency of synthesizing acrylic acid or acrylic ester from acetylene is improved.
In some embodiments of the invention, the molar ratio of the acetylene to the carbon monoxide is 1 (1-15), and the reaction is performed at a pressure of 5-10 MPa and a temperature of 170-220 ℃ for 25-120 min. This can further improve the reaction efficiency of acetylene for synthesizing acrylic acid or acrylic ester.
Detailed Description
The following describes embodiments of the present invention in detail. The following described embodiments are exemplary and are intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to one aspect of the present invention, there is provided a catalyst for the synthesis of acrylic acid or acrylate ester from acetylene, the catalyst comprising:
an acidic molecular sieve;
an inert oxide support;
a nickel compound, the nickel compound being supported on an oxide support,
wherein the loading amount of the nickel compound in the catalyst is 1-10 wt% calculated by nickel.
According to the catalyst for synthesizing acrylic acid or acrylic ester from acetylene, disclosed by the embodiment of the invention, the active component nickel is loaded on the oxide carrier, so that the heterogeneous phase of the homogeneous catalyst can be effectively realized, and the separation of a product and the catalyst is facilitated; meanwhile, the acidic molecular sieve is adopted to replace liquid acids such as methane sulfonic acid and the like, so that a hydrogen source required by the activated nickel catalyst can be provided, the reaction activity of the catalyst is obviously improved, and the corrosivity of a catalytic system to production equipment can be effectively reduced. Therefore, the catalyst for synthesizing acrylic acid or acrylic ester by acetylene has the advantages of simple components, low cost, easy separation, good stability, high activity, strong selectivity, low corrosivity and the like, and has wide application prospect.
According to a specific embodiment of the present invention, the inert oxide support may be one of silica, titania, alumina and magnesia. The inert oxide is a common Fischer-Tropsch synthesis carrier and has low cost; the inventors have found that by using the above-mentioned inert oxides as a carrier for nickel as an active ingredient, the stability of use can be further improved and the object of reducing the production cost can be achieved.
According to an embodiment of the present invention, the acidic molecular sieve may be one of H β molecular sieve of H ion type, HY molecular sieve, HZSM-5, HZSM-22 and HZSM-35. The H ion type molecular sieve is prepared by replacing sodium ions with hydrogen ions in an original Na type molecular sieve through the steps of ion exchange, roasting and the like, so that the acidity of the molecular sieve is improved, and the H ion type molecular sieve can be used as solid acid for acid catalytic reaction. The inventor finds that by adopting the H ionic acid molecular sieve to replace liquid acid such as methane sulfonic acid, hydrogen source required by the activated nickel catalyst can be provided, the reaction activity of the catalyst is obviously improved, and the corrosivity of a catalytic system to production equipment can be effectively reduced. Therefore, the H-ion type acidic molecular sieve is selected as the catalyst component, so that the reaction activity and the catalytic selectivity of the catalyst for synthesizing acrylic acid or acrylic ester by acetylene can be obviously improved, the smooth reaction of synthesizing acrylic acid or acrylic ester by acetylene can be effectively promoted, and the yield of acrylic acid or acrylic ester can be improved.
According to a specific embodiment of the present invention, the mass ratio of the inert oxide support to the acidic molecular sieve may be (1-20): 1. the inventors found through a large number of experiments that when the mass ratio of the inert oxide support to the acidic molecular sieve is greater than (1-20): 1, the content of the acidic molecular sieve is too low to play a role of an auxiliary agent for acid catalysis, the activity and yield of the reaction are hardly improved compared with the reaction without adding the acidic molecular sieve, and when the mass ratio of the inert oxide carrier to the acidic molecular sieve is less than (1-20): 1, the content of the acidic molecular sieve is too high, although the reaction rate is greatly improved, a large amount of acetylene generates byproducts such as polymers and carbon deposition, and the selectivity of a target product is reduced. Therefore, the mass ratio of the inert oxide carrier to the acidic molecular sieve is controlled to be (1-20): 1, can further improve the stability, the reaction activity and the catalytic selectivity of the catalyst for synthesizing acrylic acid or acrylic ester by acetylene, promote the smooth proceeding of the reaction for synthesizing acrylic acid or acrylic ester by acetylene and improve the yield of acrylic acid or acrylic ester.
According to the second aspect of the present invention, the present invention also provides a method for preparing the above catalyst for acetylene synthesis of acrylic acid or acrylic ester, comprising:
preparing soluble nickel salt into a nickel-containing aqueous solution;
placing the inert oxide carrier in a nickel-containing aqueous solution for dipping treatment and drying to obtain an inert oxide carrier loaded with a nickel compound;
and mixing the obtained inert oxide carrier loaded with the nickel compound with the acidic molecular sieve according to a preset proportion to obtain the catalyst.
According to the method for preparing the catalyst for synthesizing acrylic acid or acrylic ester from acetylene, disclosed by the embodiment of the invention, the active component nickel is loaded on the oxide carrier by adopting an impregnation method, so that the heterogeneous phase of the homogeneous catalyst can be effectively realized, and the separation of a product and the catalyst is facilitated; in addition, the acidic molecular sieve is adopted to replace liquid acid such as methane sulfonic acid and the like to be mixed with the inert oxide carrier loaded with the nickel compound to form a catalytic system, so that a hydrogen source required by the activation of the nickel catalyst can be provided, the reaction activity of the catalyst is obviously improved, and the corrosivity of the catalytic system to production equipment can be effectively reduced. Therefore, the method for preparing the catalyst for synthesizing acrylic acid or acrylic ester by acetylene is simple, and the prepared catalyst has the advantages of simple components, low cost, easy separation, good stability, high activity, strong selectivity, small corrosivity and the like, and has wide application prospect.
The kind of the soluble nickel salt is not particularly limited according to a specific embodiment of the present invention, and for example, the soluble nickel salt may be one of a halide of nickel, nickel sulfate, nickel acetate, and nickel nitrate according to a specific example of the present invention. Thus, the active component nickel can be smoothly supported on the carrier, and the catalyst containing nickel as the active component can be prepared.
According to the specific embodiment of the invention, the inert oxide carrier can be placed in the nickel-containing aqueous solution for soaking for 10-24h, so that nickel can be fully loaded on the inert oxide carrier, the loading amount of the active component nickel is further improved, and the catalytic activity of the catalyst is improved. According to the specific embodiment of the invention, after the impregnation treatment, the inert oxide carrier is dried to obtain the nickel compound-loaded inert oxide carrier. Specifically, the drying temperature can be 80-200 ℃, and the drying time can be 3-15 h. This can further improve the nickel supporting stability and the catalytic activity of the catalyst.
According to the third aspect of the present invention, the present invention also provides a method for synthesizing acrylic acid or acrylate from acetylene, comprising:
mixing the catalyst for synthesizing acrylic acid or acrylic ester by acetylene with an organic solvent and water or an organic solvent and alcohol, and adding the mixture into a high-pressure kettle;
under the condition of stirring, acetylene and carbon monoxide are introduced into the autoclave and react under the catalytic action of the catalyst, so as to obtain acrylic acid or acrylic ester.
In the method for synthesizing acrylic acid or acrylic ester by acetylene according to the above embodiment of the present invention, when an organic solvent and water are added into an autoclave, acetylene, carbon monoxide and water react under the action of a catalyst to obtain acrylic acid; when the organic solvent and the alcohol are added into the autoclave, under the action of the catalyst, acetylene, carbon monoxide and the alcohol react to obtain the propylene ester. Therefore, by adopting the catalyst for synthesizing acrylic acid or acrylic ester by acetylene, the acrylic acid or the acrylic ester can be effectively prepared, and the reaction efficiency and the yield can be further improved.
According to the specific embodiment of the invention, when the acrylic acid is prepared, the mass of water is 10-25% of that of the organic solvent; the mass of the catalyst is 0.1-10% of the total mass of the organic solvent and the water. The inventor finds through a large number of experiments that when the organic solvent, the water and the acetylene are kept in proper proportion, the dissolution of the catalyst and the dissolution of the raw material acetylene are facilitated, the better catalytic reaction effect is exerted, and otherwise, the catalytic effect is influenced, and the smooth proceeding of the reaction for synthesizing the acrylic acid is influenced. Specifically, when the mass percentage of water in the organic solvent is more than 25%, the polarity of the liquid phase solvent is changed, so that the solubility of acetylene and CO gas is reduced, the selectivity of acrylic acid is reduced, and the yield is reduced; on the contrary, when the mass percentage of the organic solvent occupied by water is less than 10%, the water quantity participating in the reaction is less, and the yield of the product is low; when the percentage of the catalyst in the total mass of the organic solvent and the water is more than 10%, the reaction yield is not improved along with the increase of the amount of the catalyst, the specific activity of the reaction is reduced, and when the percentage of the catalyst in the total mass of the organic solvent and the water is less than 0.1%, the reaction activity is not high, and the conversion rate is extremely low. Therefore, by controlling the mass of the water to be 10-25% of the mass of the organic solvent and the mass of the catalyst to be 0.1-10% of the total mass of the organic solvent and the water, the reaction efficiency of synthesizing acrylic acid from acetylene and the yield of acrylic acid can be obviously improved.
According to the specific embodiment of the invention, when preparing the acrylate, the mass of the alcohol can be 10-25% of that of the organic solvent; the mass of the catalyst can be 0.1-10% of the total mass of the organic solvent and the alcohol. Therefore, the reaction efficiency of synthesizing acrylic ester from acetylene and the yield of acrylic ester can be remarkably improved. Similar to the reaction of acetylene to acrylic acid, the use of an appropriate amount of alcohol and an appropriate amount of catalyst are required for the preparation of acrylic esters from acetylene.
According to an embodiment of the present invention, after mixing the catalyst for synthesizing acrylic acid or acrylate from acetylene with an organic solvent and water or with an organic solvent and alcohol, and adding the mixture into the autoclave, the method may further comprise: the autoclave was closed, and the air in the autoclave was replaced with nitrogen gas at a pressure of 1MPa twice. Therefore, the final product of the reaction, namely acrylic acid or acrylic ester, can be effectively prevented from being oxidized, and the purity of the acrylic acid or acrylic ester is ensured.
According to the specific embodiment of the present invention, when acetylene and carbon monoxide are introduced into the autoclave under stirring, acetylene may be first introduced into the autoclave to a pressure of 0.1 to 0.5MPa in the autoclave, followed by introduction of carbon monoxide to 3 to 6MPa, and then the temperature may be raised to the reaction temperature. Therefore, the excessive CO is introduced to ensure that the acetylene completely participates in the reaction and the conversion is complete. The gas is introduced first and then the temperature is raised, so that the phenomena of carbon deposition, temperature runaway and the like caused by introducing the reaction gas at high temperature can be avoided.
According to a specific embodiment of the present invention, the organic solvent may include at least one selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, acetone, N-methylpyrrolidone, and N, N-dimethylformamide. The inventor finds that the organic solvent has high solubility to acetylene, can ensure that the acetylene concentration in a liquid phase is high under low pressure, is easy for carbonylation reaction, and can avoid the danger of high-pressure acetylene operation. Therefore, the organic solvent can be selected to completely dissolve the catalyst, so that the reaction efficiency of synthesizing acrylic acid or acrylic ester from acetylene is improved, and the operation safety is improved.
According to the specific embodiment of the invention, the molar ratio of acetylene to carbon monoxide can be 1 (1-15), and the reaction can be carried out at a temperature of 170-220 ℃ for 25-120 min under a pressure of 5-10 MPa. Through a large number of experiments, the inventor finds that the conversion rate of acetylene and carbon monoxide can be remarkably improved when the molar ratio of acetylene to carbon monoxide is 1 (1-15). In addition, the inventor also finds that when the reaction is carried out under the pressure of 5-10 MPa and the temperature of 170-220 ℃, the catalytic activity of the catalyst can be improved, the reaction efficiency can be improved, and the generation of acrylic acid or acrylic ester can be promoted, so that the reaction can be completed within 25-120 min. Therefore, the reaction for synthesizing acrylic acid or acrylic ester by acetylene under the conditions can further improve the reaction efficiency and the yield of the acrylic acid or the acrylic ester, wherein the conversion rate of acetylene is more than 80 percent, and the yield of the acrylic acid or the acrylic ester is more than 70 percent. In addition, the corrosion of equipment can be significantly reduced by preparing acrylic acid or acrylic ester using the catalyst of the above example.
Example 1
Weighing Ni (CH)3COO)2·4H20.50g of O is loaded on 1g of silicon dioxide carrier, the silicon dioxide carrier is soaked for 12h, after being dried for 10h at 120 ℃, the O and the HY molecular sieve with the silicon-aluminum ratio of 5 are mixed evenly and added into 97m1THF and 12m1 methanol, the mixture is added into a 500m1 high pressure kettle, and 1MPa N is used2Replacing the air in the kettle for 2 times, and filling C2H2Saturated to 0.2MPa, then filled with CO to a certain pressure, heated to 200 ℃, reacted at 5MPa and 1000rpm for 1.5 hours. Analysis of the tail gas and the reaction solution after the reaction is finished, C2H2The conversion was 95% and the yield of methyl acrylate was 79%.
Example 2
Weighing Ni Br20.30g of the carrier is loaded on 2g of titanium dioxide, the carrier is soaked for 15h and dried at 150 ℃ for 12h, then the carrier and HZSM-5 molecular sieve with the silicon-aluminum ratio of 0.2g of 40 are evenly mixed, added into 100m1 acetone and 13m1 ethanol and added into a 500m1 high-pressure kettle with 1MPa of N2Replacing the air in the kettle for 2 times, and filling C2H2Saturated to 0.3MPa, then filled with CO to a certain pressure, heated to 210 ℃, reacted at 6MPa, and reacted for 1 hour. C2H2The conversion was 89% and the yield of ethyl acrylate was 78%.
Example 3
Weighing 0.50g of nickel nitrate to load on 3g of nickel oxideSoaking on aluminum carrier for 24H, oven drying at 100 deg.C for 5H, mixing with 1g of H beta molecular sieve with Si/Al ratio of 50, adding 100m 1N-methyl pyrrolidone and 14m 1N-butanol, adding into 500m1 autoclave, and adding into 1MPa N2Replacing the air in the kettle for 2 times, and filling C2H2Saturated to 0.3MPa, then filled with CO to a certain pressure, heated to 190 ℃, reacted at 6.5MPa for 0.5 hour. C2H2The conversion was 94% and the yield of n-butyl acrylate was 85%.
Example 4
Weighing NiSO41.00g of magnesium oxide loaded on 5g of magnesium oxide carrier, soaking for 24h, drying at 80 ℃ for 15h, then uniformly mixing with 0.5g of HZSM-35 molecular sieve with the silica-alumina ratio of 45, adding the mixture into 100m1N, N-dimethylformamide and 16m1 methanol, adding the mixture into a 500m1 autoclave, and adding 1MPa N2Replacing the air in the kettle for 2 times, and filling C2H2Saturated to 0.3MPa, then filled with CO to 6MPa, heated to 185 ℃ and reacted for 0.5 hour. C2H2The conversion was 90% and the yield of methyl acrylate was 82%.
Example 5
Weighing 0.15g of nickel acetate, loading on 2g of silicon dioxide carrier, soaking for 12h, drying at 200 ℃ for 3h, mixing with 0.4g of HZSM-22 molecular sieve with the silica-alumina ratio of 30, adding into 100m1N, N-dimethylformamide and 12m1 ethanol, adding into a 500m1 autoclave, and adding into the autoclave with 1MPa N2Replacing the air in the kettle for 2 times, and filling C2H2Saturated to 0.3MPa, then filled with CO to 4MPa, heated to 220 ℃ and reacted for 1.5 hours. C2H2The conversion was 82% and the yield of ethyl acrylate was 74%.
COMPARATIVE EXAMPLE 1(CN101633615B)
0.5g of nickel acetate, 0.18g of CuBr20.18g of methanesulfonic acid, 0.21g of triphenylphosphine and 97m1 of THF and 12m1 of methanol were weighed, the mixture was charged into a 500m1 autoclave and the pressure of the autoclave was 1MPa N2Replacing the air in the kettle for 2 times, and filling C2H2Saturated to 0.2MPa, then filled with CO to 5MPa, heated to 200 ℃ and reacted for 1.5 hours. Analysis of the tail gas and the reaction solution after the reaction is finished, C2H2The conversion was 85% and the yield of methyl acrylate was 73%. The catalyst components used in the above reaction are somewhat complex,contains organic ligand, has higher cost, contains acid component and has certain corrosivity.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A catalyst for the synthesis of acrylic acid or acrylate ester from acetylene, wherein the catalyst comprises:
an acidic molecular sieve;
an inert oxide support;
a nickel compound supported on the oxide support,
wherein the loading amount of the nickel compound in the catalyst is 1-10 wt% in terms of nickel.
2. The catalyst of claim 1, wherein the inert oxide support is one of silica, titania, alumina, and magnesia.
3. The catalyst of claim 1, wherein the acidic molecular sieve is one of an H β molecular sieve, an HY molecular sieve, HZSM-5, HZSM-22 and HZSM-35.
4. The catalyst of claim 1, wherein the mass ratio of the inert oxide support to the acidic molecular sieve is (1-20): 1.
5. a process for preparing the catalyst of any one of claims 1 to 4, comprising:
preparing soluble nickel salt into a nickel-containing aqueous solution;
placing the inert oxide carrier in the nickel-containing aqueous solution for dipping treatment and drying to obtain an inert oxide carrier loaded with a nickel compound;
and mixing the obtained inert oxide carrier loaded with the nickel compound with the acidic molecular sieve according to a preset ratio to obtain the catalyst.
6. The method of claim 5, wherein the soluble nickel salt is one of a nickel halide, nickel sulfate, nickel acetate, and nickel nitrate.
7. The method according to claim 5, wherein the time of the dipping treatment is 10-24 hours, the temperature of the drying is 80-200 ℃, and the time of the drying is 3-15 hours.
8. A method for synthesizing acrylic acid or acrylic ester by acetylene is characterized by comprising the following steps:
mixing the catalyst of any one of claims 1-4 with an organic solvent and water or with an organic solvent and an alcohol and feeding into an autoclave;
and introducing acetylene and carbon monoxide into the autoclave under the stirring condition, and reacting under the catalytic action of the catalyst to obtain acrylic acid or acrylic ester.
9. The method according to claim 8, wherein the mass of the water is 10-25% of the mass of the organic solvent, and the mass of the catalyst is 0.1-10% of the total mass of the organic solvent and the water;
the mass of the alcohol is 10-25% of that of the organic solvent; the mass of the catalyst is 0.1-10% of the total mass of the organic solvent and the alcohol;
optionally, the organic solvent is selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, acetone, N-methylpyrrolidone, N-dimethylformamide.
10. The method according to claim 8, wherein the molar ratio of the acetylene to the carbon monoxide is 1 (1-15), and the reaction is carried out at a pressure of 5-10 MPa and a temperature of 170-220 ℃ for 25-120 min.
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CN1566275A (en) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof
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CN1566275A (en) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof
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