CN114425450B - Catalyst for preparing unsaturated carbonate, preparation method and application thereof - Google Patents
Catalyst for preparing unsaturated carbonate, preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Abstract
The invention relates to a catalyst for preparing unsaturated carbonic ester, a preparation method and application thereof. The catalyst is a metal-zinc metal organic framework compound composite catalytic system; wherein the auxiliary metal is at least one selected from palladium, gold, silver, ruthenium, platinum and copper. The catalyst is used for directly preparing unsaturated carbonate from olefin and carbon dioxide, and has the characteristics of short production process, high efficiency, low energy consumption, outstanding catalytic performance, high conversion rate and high unsaturated carbonate selectivity.
Description
Technical Field
The invention relates to the technical field of unsaturated carbonate preparation, in particular to a catalyst for preparing unsaturated carbonate, a preparation method and application thereof.
Background
Global warming is caused by an increase in greenhouse gases in the atmosphere (such as carbon dioxide, freon, and methane), so that it is quite important to reduce the atmospheric concentration of carbon dioxide, which plays a great role in global warming, and some studies on emissions management, fixation, and the like have been conducted worldwide. Therefore, how to effectively fix has become one of the most challenging subjects in this century. Among these studies, copolymerization of carbon dioxide and epoxide developed by each research group has been actively studied as a reaction for solving the global warming problem, and in consideration of fixation of chemical carbon dioxide and in consideration of using carbon dioxide as a carbon source. The unsaturated carbonic ester is a solvent with excellent performance and a fine chemical intermediate, and is a potential basic raw material for organic chemical industry.
In the prior art, the epoxy compound and CO are used for preparing the epoxy resin 2 The reaction synthesis of unsaturated carbonates is one of the very good fixing methods. The process reaction equation is as follows:
wherein R is alkyl or aryl.
Among the catalytic systems, most are binary homogeneous catalysts composed of Lewis acid metal compounds and Lewis bases, wherein the earlier-used homogeneous catalytic systems mainly comprise Lewis acid metal compounds including alkali (earth) metal halides, transition metal salts, transition metals or main group metal complexes, and the Lewis bases used are organic bases (such as DMF, DMAP, etc.), quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts, crown ethers, etc. The late heterogeneous catalytic system comprises a metal oxide system (e.g., ceO 2 -ZrO 2 Basic zeolite systems (e.g., cs/KX), and the like. In the process route, the preparation process of the epoxy compound mainly results from the oxidation of olefins. Therefore, the process flow of the unsaturated carbonate is actually based on the oxidation of olefin, and the unsaturated carbonate is obtained by carbon dioxide addition reaction after obtaining an intermediate raw material epoxy compound.
The other method is to directly prepare unsaturated carbonate by taking alkene and carbon dioxide as raw materials, namely, the alkene reacts with the carbon dioxide in the presence of an oxidant to generate cyclic unsaturated carbonate, and the reaction equation is as follows:
wherein R is alkyl or aryl.
Compared with the general synthesis method which uses the epoxy compound as the initial raw material, the direct synthesis method which uses the olefin as the initial raw material has more practical application value from the aspects of economic benefit and energy utilization, on one hand, because the olefin has lower price and wider source; on the other hand, the isolation steps of the intermediate products can be greatly reduced because of the direct synthesis method. However, the present problem is that the productivity and selectivity of the product are not high for the direct synthesis, and therefore, development of a direct synthesis catalyst having high activity and selectivity is a constant problem in the art.
Disclosure of Invention
In order to solve the problems of low conversion rate and low selectivity in the preparation of unsaturated carbonate by a direct synthesis method in the prior art, the invention provides a catalyst for preparing unsaturated carbonate, and a preparation method and application thereof. The catalyst is used for directly preparing unsaturated carbonate from olefin and carbon dioxide, and has the characteristics of short production process, high efficiency, low energy consumption, outstanding catalytic performance, high conversion rate and high unsaturated carbonate selectivity.
The first aspect of the invention provides a catalyst for preparing unsaturated carbonate, wherein the catalyst is a metal-zinc metal organic framework compound composite catalyst system; wherein the auxiliary metal is at least one selected from palladium, gold, silver, ruthenium, platinum and copper.
In the above technical solution, the metal is preferably at least one selected from palladium, gold, silver, ruthenium and platinum.
In the technical scheme, the particle size of the auxiliary metal in the catalyst is 0.1-20nm, preferably 1-10nm.
In the technical scheme, the catalyst is of a coating structure, and the zinc metal organic framework compound coats the auxiliary metal.
In the technical scheme, the mass fraction of the auxiliary metal in the catalyst is 0.1-10%. The molar ratio of the auxiliary metal element to the zinc element in the catalyst is (0.005-0.1): 1.
in the above technical solution, the zinc metal organic framework compound includes but is not limited to MOF-177, MOF-38 and ZIF-8, and more preferably the zinc metal organic framework compound is ZIF-8.
In a second aspect, the present invention provides a process for preparing a catalyst for preparing an unsaturated carbonate, comprising the steps of:
(1) Dissolving a metal-assisting precursor in a solvent, and stirring;
(2) Adding zinc precursor and 2-methylimidazole, stirring, sealing, performing hydrothermal reaction, filtering, and drying;
(3) And (3) placing the solid obtained in the step (2) in a reducing atmosphere for reduction treatment to obtain the catalyst.
In the above technical scheme, the solvent used in the step (1) is one or more of water, alcohol and amide. The alcohol is one or more of methanol, ethanol, propanol and butanol; the amide is N, N-dimethylformamide or N, N-dimethylacetamide.
In the above technical solution, the metal-assisting precursor in the step (1) is one or more of palladium, gold, silver, ruthenium, platinum and copper, and the types of the precursors are not limited; preferably, the metal is one or more of nitrate, chloride, sulfate and hypochlorite of the auxiliary metal.
In the above technical scheme, the zinc precursor in the step (2) is one or more of nitrate, chloride and sulfate.
In the technical scheme, the hydrothermal reaction temperature in the step (2) is 60-200 ℃ and the time is 1-24 h.
In the above technical solution, the reducing atmosphere in the step (3) is preferably hydrogen or carbon monoxide; the reduction temperature is 100-600 ℃ and the time is 1-24 h.
In the above technical scheme, the molar ratio of the metal-assisting precursor in the step (1) to the zinc precursor and the 2-methylimidazole in the step (2) is (0.01-1): (1-2): (0.8-2.5).
In the present invention, the apparatus for mixing and reacting is not limited, and may be any apparatus capable of achieving mixing or reacting existing in the art, for example, the apparatus for mixing and reacting may be a reactor or a reaction vessel.
In the present invention, the filtration, washing and drying in the step (2) are not limited, and any existing filtration, washing and drying method can be adopted. The drying temperature is preferably 60-150 deg.c, and the drying temperature is exemplified as 100 deg.c in the embodiment of the present invention, but the present invention is not limited thereto. The drying time is not particularly limited as long as the solvent can be removed, and those skilled in the art can appropriately select the drying time according to the actual situation.
In the step (2), the washing may be performed or may not be performed, and the washing is preferably performed. In the present invention, the washing in the step (2) is not limited as long as the purpose of washing can be achieved.
In a third aspect, the present invention provides a method for preparing unsaturated carbonate, which uses alkene, oxidant and carbon dioxide as raw materials, and makes them react with the catalyst of the first aspect or the catalyst prepared by the preparation method of the second aspect, so as to prepare unsaturated carbonate.
In the technical scheme, the reaction temperature is 30-200 ℃, the reaction pressure is 0.1-10.0 MPa, and the reaction time is 1-24 hours; the molar ratio of olefin, oxidant and catalyst is 1:0.5 to 5:0.0001-1.
In the above technical solution, the olefin is alkyl olefin or aryl olefin, such as ethylene, propylene, butylene, butadiene, styrene, chloropropene, chlorostyrene, etc.; the oxidizing agent is oxygen or a peroxide, wherein the peroxide includes, but is not limited to, cumene peroxide, t-butyl peroxide, hydrogen peroxide, and the like.
The catalyst provided by the invention has a specific composition, is a metal-zinc metal organic framework compound composite catalytic system, has small metal particle size, and can obtain excellent conversion rate and unsaturated carbonate selectivity when being used for directly synthesizing unsaturated carbonate. Especially when the catalyst is used for directly synthesizing unsaturated carbonic ester by using styrene and carbon dioxide under the conditions of the reaction temperature of 100 ℃ and the pressure of 3MPa and the reaction time of 12 hours, the conversion rate and the selectivity of the styrene respectively reach 99.1 percent and 99.6 percent.
According to the preparation method of the catalyst, an in-situ synthesis method is adopted, and a metal precursor, a zinc precursor and 2-methylimidazole are mixed and reduced to prepare the catalyst for directly synthesizing unsaturated carbonate with high activity and good selectivity.
Drawings
FIG. 1 is a TEM photograph of the catalyst prepared in example 1;
FIG. 2 is an XRD pattern for the catalyst prepared in example 1.
Detailed Description
The technical scheme of the invention is further illustrated by examples below, but the protection scope of the invention is not limited by the examples. In the invention, the weight percent is the mass fraction.
In the present invention, XRD was measured on a BrookD 8Advance SS X-ray diffractometer, with CuK alpha radiation, 40 kilovolts, 300 milliamps, at a scan rate of 2/min. The structure of the zinc metal organic framework compound can be measured by XRD characterization analysis.
In the invention, TEM is carried out on a model Tecnai 20S-TWIN with an accelerating voltage of 200kV. The particle size calculation method comprises the following steps: obtained by TEM measurement.
[ example 1 ]
Adding 50mg of sodium chloropalladate into a 50ml beaker, adding 50ml of N, N-dimethylformamide, stirring and dissolving, adding 1.4g of zinc nitrate, stirring, adding 0.4g of 2-methylimidazole, stirring, sealing, performing hydrothermal reaction at 160 ℃ for 18 hours, filtering, washing with methanol, drying at 100 ℃, placing a sample into a tube furnace, introducing 10% hydrogen/argon mixed gas, heating to 250 ℃ for 5 minutes, keeping for 2 hours, cooling to room temperature after finishing, taking out the sample to obtain a catalyst S1, wherein TEM pictures are shown in figure 1, and the average particle size of auxiliary metal in the catalyst is 2.6nm. The specific properties of the catalyst are shown in Table 1. The obtained catalyst was subjected to XRD characterization, and the characterization result is shown in the graph of FIG. 2. As can be seen from the graph in fig. 2, the resulting catalyst included zinc metal organic framework compound ZIF-8.
Comparative example 1
500mg of sodium chloropalladate is added into a 50ml beaker, 50ml of deionized water is added, stirring and dissolution are carried out, sealing is carried out after stirring, hydrothermal reaction is carried out at 100 ℃ for 8 hours, filtering, methanol washing and drying are carried out at 100 ℃, a sample is placed into a tubular furnace, 10% hydrogen/argon mixed gas is introduced, the temperature is raised to 250 ℃ for 5 minutes, the temperature is kept for 2 hours, the temperature is cooled to room temperature after the completion, and the sample is taken out to obtain the comparative catalyst D1.
Comparative example 2
1.4g of zinc nitrate is stirred and dissolved in 50ml of ethanol, 0.4g of 2-methylimidazole is added, the mixture is stirred and sealed, the mixture undergoes hydrothermal reaction at 100 ℃ for 8 hours, and then the catalyst D2 is obtained through filtration, methanol washing and drying at 100 ℃.
[ comparative example 3 ]
Adding 50mg of sodium chloropalladate into a 50ml beaker, adding 50ml of deionized water, stirring for dissolution, adding 1.4g of zinc nitrate, stirring, sealing after stirring, performing hydrothermal reaction at 100 ℃ for 8 hours, filtering, washing with methanol, drying at 100 ℃, placing a sample into a tube furnace, introducing 10% hydrogen/argon mixed gas, heating to 250 ℃ for 5 minutes, maintaining for 2 hours, cooling to room temperature after finishing, and taking out the sample to obtain a comparative catalyst D3.
[ comparative example 4 ]
50mg of sodium chloropalladate is added into a 50ml beaker, 50ml of deionized water is added, stirring is carried out, 1.4g of zinc nitrate is added, stirring is carried out, sealing is carried out after stirring, hydrothermal reaction is carried out at 100 ℃ for 8 hours, filtering, methanol washing and drying at 100 ℃, and a sample is taken out, thus obtaining the comparative catalyst D4.
[ example 2 ]
50mg of sodium chloroacetate is added into a 50ml beaker, 50ml of N, N-dimethylformamide is added for stirring and dissolving, 1.4g of zinc nitrate is added for stirring, 0.4g of 2-methylimidazole is added for stirring and sealing, the mixture is subjected to hydrothermal reaction at 160 ℃ for 18 hours, after filtration, methanol washing and drying at 100 ℃, a sample is placed into a tube furnace, 10% hydrogen/argon mixed gas is introduced, the temperature is raised to 250 ℃ for 5 minutes, the temperature is kept for 2 hours, the temperature is reduced to room temperature after the completion, and the sample is taken out to obtain a catalyst S2, and the XRD characterization curve of the catalyst is similar to that of the catalyst shown in the figure 1 of the example 1. The particle size of the co-metal in the catalyst was 3.0nm on average. The specific properties of the catalyst are shown in Table 1.
[ example 3 ]
Adding 50mg of sodium chloropalladate into a 50ml beaker, adding 50ml of methanol, stirring for dissolution, adding 1.4g of zinc nitrate, stirring, adding 0.4g of 2-methylimidazole, stirring, sealing, performing hydrothermal reaction at 160 ℃ for 18 hours, filtering, washing with methanol, drying at 100 ℃, placing a sample into a tube furnace, introducing 10% hydrogen/argon mixed gas, heating to 250 ℃ for 5 minutes, maintaining for 2 hours, cooling to room temperature after finishing, and taking out the sample to obtain a catalyst S3, wherein an XRD characterization curve is similar to that of the catalyst shown in the figure 1 of the example 1. The particle size of the co-metal in the catalyst was 1.8nm on average. The specific properties of the catalyst are shown in Table 1.
[ example 4 ]
100mg of sodium chloropalladate is added into a 50ml beaker, 50ml of N, N-dimethylformamide is added for stirring and dissolving, 1.4g of zinc nitrate is added for stirring, 0.4g of 2-methylimidazole is added for stirring and sealing, the mixture is subjected to hydrothermal reaction at 160 ℃ for 18 hours, then the mixture is filtered, washed by methanol and dried at 100 ℃, a sample is placed into a tube furnace, 10% hydrogen/argon mixed gas is introduced, the mixture is heated to 250 ℃ for 5 minutes, the temperature is kept for 2 hours, the mixture is cooled to room temperature after the completion, and the sample is taken out to obtain a catalyst S4, and the XRD characterization curve of the catalyst S4 is similar to that of the graph 1 of the example 1. The particle size of the co-metal in the catalyst was 2.1nm on average. The specific properties of the catalyst are shown in Table 1.
[ example 5 ]
50mg of sodium chloropalladate, 50ml of N, N-dimethylformamide are added into a 50ml beaker, the mixture is stirred and dissolved, 1.4g of zinc nitrate is added, 0.4g of 2-methylimidazole is added, the mixture is stirred and sealed, the mixture is subjected to hydrothermal reaction at 180 ℃ for 24 hours, the mixture is filtered, washed by methanol and dried at 100 ℃, a sample is placed into a tube furnace, 10% hydrogen/argon mixed gas is introduced, the mixture is heated to 250 ℃ for 5 minutes, the mixture is kept at 2 hours, the mixture is cooled to room temperature after the completion of the reaction, and the sample is taken out to obtain a catalyst S5, and the XRD characterization curve of the catalyst S5 is similar to that of the graph 1 of the example 1. The particle size of the co-metal in the catalyst was 2.3nm on average. The specific properties of the catalyst are shown in Table 1.
[ example 6 ]
50mg of copper nitrate is added into a 50ml beaker, 50ml of N, N-dimethylformamide is added, stirring and dissolving are carried out, 1.4g of zinc nitrate is added, stirring is carried out, 0.4g of 2-methylimidazole is added, stirring is carried out, sealing is carried out, hydrothermal reaction is carried out at 180 ℃ for 24 hours, filtering, methanol washing and drying at 100 ℃, a sample is placed into a tube furnace, 10% hydrogen/argon mixed gas is introduced, the temperature is raised to 250 ℃ for 5 minutes, the temperature is kept for 2 hours, the temperature is reduced to room temperature after the completion, and the sample is taken out to obtain a catalyst S6, wherein the XRD characterization curve of the catalyst is similar to that of the graph 1 of the example 1. The particle size of the co-metal in the catalyst was on average 7.8nm. The specific properties of the catalyst are shown in Table 1.
[ example 7 ]
The catalyst prepared in examples 1 to 6 was used in an amount of 0.05g, t-butyl peroxide 2.08g and styrene 2.08g, respectively, in terms of the molar ratio of olefin, oxidant to catalyst: 1:1.2:0.008 (calculated as Pd) was placed in a 50ml autoclave, the autoclave was heated to 100℃and then carbon dioxide was introduced, the system pressure was maintained at 3MPa, and the reaction was continued for 12 hours. After the reaction is finished, the heating is closed, the kettle cover is opened after the reaction is cooled to room temperature, the kettle liquid is taken and analyzed on gas chromatography, and the conversion rate and the selectivity of the styrene are measured, and the specific catalytic performance is shown in table 1.
Comparative example 5
The catalyst prepared in comparative examples 1-4, tert-butyl alcohol peroxide 2.08g and styrene 2.08g were placed in a 50ml autoclave, and after the autoclave was heated to 100℃the carbon dioxide was introduced to maintain the system pressure at 3MPa for reaction for 12 hours. After the reaction is finished, the heating is closed, the kettle cover is opened after the reaction is cooled to room temperature, the kettle liquid is taken and analyzed on gas chromatography, and the conversion rate and the selectivity of the styrene are measured, and the specific catalytic performance is shown in table 1.
Table 1 catalyst properties and catalytic performance of examples and comparative examples
Claims (10)
1. A method of preparing an unsaturated carbonate, comprising: using olefin, oxidant and carbon dioxide as raw materials, and enabling the raw materials to contact with a catalyst for reaction to obtain unsaturated carbonate;
wherein the catalyst is a metal-zinc-assisted metal organic framework compound composite catalytic system; wherein the auxiliary metal is selected from at least one of palladium, gold, silver, ruthenium, platinum and copper;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a metal-assisting precursor in a solvent, and stirring;
(2) Adding zinc precursor and 2-methylimidazole, stirring, sealing, performing hydrothermal reaction, filtering, and drying;
(3) And (3) placing the solid obtained in the step (2) in a reducing atmosphere for reduction treatment to obtain the catalyst.
2. The method of claim 1, wherein the co-metal is selected from at least one of palladium, gold, silver, ruthenium, and platinum.
3. The method of claim 1, wherein the particle size of the co-metal in the catalyst is from 0.1 to 20nm.
4. The method of claim 1, wherein the particle size of the co-metal in the catalyst is 1-10nm.
5. The method according to claim 1, wherein the mass fraction of the co-metal in the catalyst is 0.1-10%; the molar ratio of the auxiliary metal element to the zinc element in the catalyst is (0.005-0.1): 1.
6. the method according to any one of claims 1 to 5, wherein the method for preparing the catalyst comprises the steps of:
(1) Dissolving a metal-assisting precursor in a solvent, and stirring;
(2) Adding zinc precursor and 2-methylimidazole, stirring, sealing, performing hydrothermal reaction, filtering, and drying;
(3) And (3) placing the solid obtained in the step (2) in a reducing atmosphere for reduction treatment to obtain the catalyst.
7. The method according to claim 6, wherein the solvent used in the step (1) is one or more of water, alcohol and amide; the alcohol is one or more of methanol, ethanol, propanol and butanol; the amide is N, N-dimethylformamide or N, N-dimethylacetamide; the metal-assisting precursor in the step (1) is one or more of nitrate, chloride, sulfate and hypochlorite of metal-assisting; the zinc precursor in the step (2) is one or more of nitrate, chloride and sulfate.
8. The method according to claim 6, wherein the hydrothermal reaction temperature in step (2) is 60 to 200 ℃ for 1 to 24 hours; the reducing atmosphere in the step (3) is hydrogen or carbon monoxide; the reduction temperature is 100-600 ℃ and the time is 1-24 h.
9. The method of claim 6, wherein the molar ratio of the co-metal precursor in step (1) to the zinc precursor, 2-methylimidazole in step (2) is (0.01-1): 1-2: (0.8-2.5).
10. The method according to claim 1, wherein the reaction temperature is 30-200 ℃, the reaction pressure is 0.1-10.0 mpa, and the reaction time is 1-24 hours; the molar ratio of olefin, oxidant and co-metal in the catalyst is 1: 0.5-5: 0.0001-1.
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