CN111185239A - CO (carbon monoxide)2Preparation method and application of epoxidation fixed catalyst - Google Patents
CO (carbon monoxide)2Preparation method and application of epoxidation fixed catalyst Download PDFInfo
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- CN111185239A CN111185239A CN202010107154.6A CN202010107154A CN111185239A CN 111185239 A CN111185239 A CN 111185239A CN 202010107154 A CN202010107154 A CN 202010107154A CN 111185239 A CN111185239 A CN 111185239A
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- 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
- 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
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Abstract
The invention discloses a CO2Firstly, a template agent is introduced in the preparation process by a hydrothermal method, and then the template agent is removed by calcination to obtain ZnWO with larger specific surface area4And (3) solid powder. Then the prepared ZnWO is put into4Dissolving in organic solvent, and grafting 2-methylimidazole to ZnWO through in-situ growth under solvothermal condition4Of (2) is provided. After centrifugation and washing, the ZnWO grafted with 2-methylimidazole4The powder is dissolved in an organic solvent, and simultaneously zinc salt is added, and zinc ions are anchored on the surface of the material through coordination bond action through solvothermal reaction. Sequentially and repeatedly adding 2 methylimidazole and zinc salt to synthesize ZnWO4The core is a layered structure material with 2 methylimidazole and zinc ions alternately appearing. By passingThe catalytic material prepared by the method not only has a better microstructure, but also has Lewis acid-alkali active sites, and the quantity and the distribution of the active sites can be accurately regulated and controlled by the quantity of the introduced 2 methylimidazole and zinc ions.
Description
Technical Field
The invention discloses a CO2A method for preparing an epoxidation fixed catalyst. More particularly, the invention relates to the introduction of basic groups on a modified support by an in-situ growth technique, wherein the basic groups are uniformly distributed on the surface of the catalyst, and the catalyst prepared by the method not only has CO selectivity2The epoxidation process has higher activity and stability, and simultaneously has higher selectivity on a target product.
Background
With the rapid advance of industry, the combustion utilization of various energy sources promotes the carbon dioxide in the air to show an increasing trend year by year, and serious harm is brought to the climate and the environment. The carbon dioxide has the characteristics of no toxicity, easy acquisition, low price and the like, and is C with abundant and natural reserves1And (4) resources. In recent years, the synthesis of other fine chemicals using carbon dioxide as a starting material has attracted attention from countries around the world, and a large number of reaction routes have been reported.
Researchers in various countries around the world have attempted to chemically convert carbon dioxide to chemicals such as dimethyl carbonate, diphenyl carbonate, cyclic carbamates, formic acid, and cyclic carbonates. Among these chemicals, cyclic carbonates have excellent physicochemical properties and can be used as ideal polar solvents, intermediates and compounds for synthesizing drugs, dielectrics for lithium ion batteries, precursors for synthesizing polycarbonates and polyurethanes, and the like. Therefore, the carbon dioxide is converted into the cyclic carbonate by a chemical method, and the method has wide application prospect and very important significance.
So far, researchers at home and abroad are in the oxygenNumerous studies have been made on oxidative immobilization of carbocyclic rings. The researched catalyst mainly comprises homogeneous ionic liquid, functional polyester, quaternary ammonium salt, quaternary phosphonium salt, heterogeneous metal oxide, Schiff base metal complex, metal organic framework material and other catalytic materials. For example, professor Qinghai Cai, university of Harbin university, modifies the surface of benzyl bromide polymer with N-methylimidazole as an active group, synthesizes a functionalized polymer, and applies the polymer to a coupling process of carbon dioxide and propylene oxide to obtain 71.4% propylene oxide conversion rate and 96.8% propylene carbonate selectivity. In order to research the difference of imidazole ionic liquid with oxygen-containing group on the catalytic carbon dioxide epoxidation, the carbon dioxide epoxidation process is catalyzed by the professor Jianmin Sun of Harbin university of industry, which respectively adopts two imidazole-based ionic liquids containing hydroxyl and carboxyl, and the research shows that: the ionic liquid containing hydroxyl can better promote the reaction of carbon dioxide and propylene oxide. The university of east China's university of Z henshan Hou professor team loads imidazolyl ionic liquid to carboxymethyl cellulose through a chemical method, and NbCl5Is loaded into CO together with the supported catalyst2The catalytic system with propylene oxide shows that: the reaction is carried out for 3h under the system pressure of 1.5MPa and the reaction temperature of 130 ℃, and the conversion rate of 98.1 percent and the selectivity of 98.3 percent cyclic carbonate are obtained. The Dae-Won Park team of the Korean kettle mountain national university respectively uses ionic liquid loaded by silicon containing different metal ions (Zn, Ni, Mn, Cu and Co) to catalyze the reaction of carbon dioxide and allyl glycidyl ether, and the results show that: under the same reaction conditions (0.86MPa, 110 ℃, 6h), the supported catalyst comprising Zn had the highest catalyst activity, corresponding to a yield of cyclic carbonic acid of up to 71.7%. Functional modification is respectively carried out on UIO-66, MIL-101 and MIL-125 by amino, and styrene oxide and epichlorohydrin are respectively used as probes to react with carbon dioxide, and the comparative study shows that: functionalized modified metal organic framework material pair CO2The catalytic activity of epoxidation is obviously improved. When ZIF-8 and MOF-5 are added into a mixed system of carbon dioxide and epichlorohydrin at the same time, the catalytic effect is higher than that of a single material. In the catalytic epoxidation of olefins using these catalystsIn the case of the reaction, most systems require the addition of a cocatalyst and an organic solvent, and the reaction is carried out at high temperature and high pressure. For a homogeneous system, catalyst separation is difficult, and a subsequent product purification process is complicated. The mechanism research shows that: the reaction of carbon dioxide with epoxy compounds to form cyclic carbonates is mainly divided into epoxide ring opening, CO2The insertion of ring-opened intermediate, the ring-closing of intermediate to form cyclic carbonate and other processes, and these three key processes are determined by Lewis acid-base active site. Therefore, a catalyst which has Lewis acid-base active sites and is stable in structure is developed to catalyze CO2The synthesis of cyclic carbonates is of great importance.
Disclosure of Invention
The technical problem is as follows: in order to solve the problems of the activity and stability of the catalyst for catalyzing the carbon dioxide epoxy addition in the prior art, a novel catalyst for catalyzing the carbon dioxide epoxy addition is provided2A preparation method and application of a cyclized immobilized catalyst. The catalyst prepared by the method is used for CO2In the epoxy addition reaction, the catalyst has higher catalytic activity and stability.
The technical scheme is as follows: one kind of CO of the present invention2The preparation method of the epoxidation fixed catalyst comprises the following steps:
step 1: synthesis of zinc tungstate ZnWO4
Sodium tungstate NaWO4Adding the mixture into deionized water solution with 0.01-10 g/L dissolved with surfactant according to the solid-to-liquid ratio of 0.01-10 mmol/L, stirring for 1-12 hours at the temperature of 20-70 ℃, and then adding the mixture and NaWO4Continuously stirring zinc salt with equal molar weight at the temperature of 20-70 ℃ for 1-12 hours, then transferring the zinc salt into a hydrothermal reaction kettle, statically reacting at the temperature of 120-180 ℃ for 12-48 hours, then cooling to room temperature, filtering and washing the obtained precipitate for 3 times, drying at the temperature of 80 ℃ for 24 hours, and calcining at the temperature of 500-900 ℃ for 3-10 hours to obtain ZnWO4；
Step 2: in-situ growth method for introducing layered metal organic structure
ZnWO prepared in the step 14Putting the mixture into a hydrothermal reaction kettle, adding an organic solvent with a solid-to-liquid ratio of 0.01-10 mmol/L into the hydrothermal reaction kettle, and stirring the mixture at the temperature of 20-60 DEG C0.1-2 hours;
a) adding ZnWO into the hydrothermal reaction kettle4Stirring 2 methylimidazole with an equal molar amount at the temperature of 20-60 ℃ for 1-6 hours, sealing, carrying out static reaction at the temperature of 120-180 ℃ for 12-48 hours, cooling to room temperature, filtering and washing precipitates in a hydrothermal kettle for 3 times, and dissolving in an organic solvent;
b) adding zinc salt with the same molar weight as 2-methylimidazole into the hydrothermal reaction kettle, stirring for 0.1-2 hours at the temperature of 20-60 ℃, sealing, carrying out static reaction for 12-48 hours at the temperature of 120-180 ℃, cooling to room temperature, filtering and washing precipitates in the hydrothermal reaction kettle for 3 times;
synthesizing ZnWO by regulating and controlling the repeated times of the procedures a) and b) and controlling the quantity of the layers42-methylimidazole and zinc ion alternately appearing layered structure CO as core2The catalyst is fixed by epoxidation.
Wherein the content of the first and second substances,
the surfactant in the step 1 is one or more of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, hexamethylene tetramine, tetraethyl ammonium bromide, tetrapropyl ammonium bromide or tetrabutyl ammonium bromide.
The zinc salt in the step 1 is one or more of zinc nitrate, zinc chloride, zinc acetate, zinc perchlorate, zinc bromide or zinc sulfate.
The solvent for washing in the step 1 is one or more of deionized water, methanol, ethanol or nitrogen-nitrogen dimethyl formamide.
The calcination process in the step 1 is to adopt a programmed heating rate of 5 ℃/min to reach a target temperature in an air atmosphere.
The organic solvent in the step 2 is one or more of methanol, ethanol, nitrogen-nitrogen dimethylformamide, nitrogen-nitrogen diethylformamide or tetrahydrofuran.
The washing solution for washing the 2-methylimidazole in the step 2 is one or more of methanol, ethanol, nitrogen-nitrogen dimethylformamide, nitrogen-nitrogen diethylformamide, dichloromethane, trichloromethane, tetrachloromethane or tetrahydrofuran; the washing solution for washing the zinc salt is one or more of deionized water, methanol, ethanol and nitrogen-nitrogen dimethyl formamide.
The zinc salt in the step 2 is one or more of zinc nitrate, zinc chloride, zinc acetate, zinc perchlorate, zinc bromide or zinc sulfate.
After the first circulation of a) and b) in step 2, in ZnWO4The surface of the metal organic structure is provided with a layer of metal organic structure, and the thickness of the layer of metal organic structure is equal to the distance between two zinc ions and different nitrogen atoms in 2 methylimidazole to form a stable structure.
CO prepared by the method of the invention2The epoxidation fixed catalyst can promote CO2And reacting with epoxy compound, wherein the epoxy compound is one or more of propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, cyclohexene oxide and allyl glycidyl ether.
Has the advantages that: prepared by the method for CO2Fixed epoxidation catalyst having a structure represented by ZnWO4The layered structure of the organic ligand and the metal ions alternately appears outside the core is the inner core, and the diffusion of reactants and products in the reaction process is promoted. ZnWO4The core structure can provide Lewis acid active sites required by the epoxidation process, and the organic ligand of the outer layer has Lewis basic site function and promotes CO in the epoxidation process2And (4) activating. By controlled introduction of ZnWO4The quantity of the external lamellar structure, the quantity and the proportion of the synthesized catalyst Lewis acid and alkali are regulated and controlled, and the CO with high catalytic activity and stable reaction is synthesized2An ideal catalyst for epoxidation. CO was catalyzed by 0.75% epoxide weight catalyst at 100 ℃ for 7 hours2The reaction with epoxy chloropropane shows epoxy chloropropane converting rate as high as 97.84% and cyclic carbonate yield as high as 95.58%.
Detailed Description
The invention is further illustrated by the following examples, which are to be construed as: the following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1: preparation of the compound with ZnWO4Catalyst with 1-layer structure introduced into surface of inner core
1) Adding 10mmol ofNaWO4Dissolving in 100mL of deionized water solution containing 2g/L of dodecyl trimethyl ammonium bromide, stirring for 1 hour at the temperature of 50 ℃, then adding zinc nitrate with equal molar weight, continuously stirring for 1 hour at the temperature of 50 ℃, then transferring into a hydrothermal reaction kettle, carrying out static reaction for 12 hours at the temperature of 120 ℃, then cooling to room temperature, filtering, and washing for 3 times by using deionized water; drying at 80 ℃ for 24h, calcining at 600 ℃ for 3h to obtain ZnWO with rich pore channel structure and large specific surface area4；
2) ZnWO prepared in the step (1)4Taking out 5mmol of the product, dissolving the product in 100mL of methanol solution, stirring the solution at the temperature of 20 ℃ for 0.1 hour, adding 2 methylimidazole with the same molar amount, continuously stirring the solution at the temperature of 20 ℃ for 1 hour, transferring the solution into a hydrothermal reaction kettle, carrying out static reaction at the temperature of 120 ℃ for 12 hours, cooling the reaction product to room temperature, filtering the reaction product, and washing the reaction product with methanol for 3 times; dissolving in methanol solution containing zinc nitrate in equal molar weight again, stirring for 0.1 hour at the temperature of 20 ℃, transferring into a hydrothermal reaction kettle, carrying out static reaction for 12 hours at the temperature of 120 ℃, cooling to room temperature, filtering, and washing with deionized water for 3 times to obtain the composite catalyst taking ZnWO4 as an inner core and organic ligand and metal ions as a laminated structure.
CO prepared by the method of the invention2The epoxidation fixed catalyst can promote CO2And reacting with epoxy compound, wherein the epoxy compound is one or more of propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, cyclohexene oxide and allyl glycidyl ether.
Example 2:
the preparation procedure and method were the same as in example 1 except that 10mmol of zinc nitrate in step 1) of example 1 was changed to 10mmol of zinc chloride.
Example 3:
the procedure and method were the same as in example 1 except that the 2g/L dodecyltrimethylammonium bromide solution in step 1) of example 1 was changed to a 2g/L hexamethylenetetramine solution.
Example 4: preparation of the compound with ZnWO4The preparation procedure and method of the catalyst for introducing 2 layered structures into the surface of the core are the same as in example 1 except that the introduced layered structures in step 2) of example 1 are added to 2 layers.
Example 5: preparation of the compound with ZnWO4The preparation procedure and method of the catalyst for introducing 3 layers of structure into the surface of the core are the same as in example 1 except that the introduced layer structure in step 2) of example 1 is added to 3 layers.
Example 6: preparation of the compound with ZnWO4Catalyst with 1-layer structure introduced into surface of inner core
1) The procedure and method were the same as in example 1 except that the 2g/L dodecyltrimethylammonium bromide solution in step 1) of example 1 was changed to a 2g/L hexamethylenetetramine solution.
2) ZnWO prepared in the step (1)4Taking out 5mmol of the product, dissolving the product in 100mL of methanol solution, stirring the solution at the temperature of 20 ℃ for 0.1 hour, adding 2 methylimidazole with the same molar amount, continuously stirring the solution at the temperature of 20 ℃ for 1 hour, transferring the solution into a hydrothermal reaction kettle, carrying out static reaction at the temperature of 120 ℃ for 24 hours, cooling the reaction product to room temperature, filtering the reaction product, and washing the reaction product with methanol for 3 times; dissolving in methanol solution containing zinc bromide with equal molar weight again, stirring for 1 hour at the temperature of 20 ℃, transferring into a hydrothermal reaction kettle, carrying out static reaction for 24 hours at the temperature of 120 ℃, cooling to room temperature, filtering, and washing for 3 times by deionized water to obtain the composite catalyst with ZnWO4 as an inner core and an organic ligand and metal ions as a laminated structure.
Evaluation of catalytic Properties
The catalyst activities of examples 1-6 were compared using epichlorohydrin as the substrate. The reaction conditions were as follows: adding 20g of epoxy chloropropane and 0.15g of catalyst into a 100mL stainless steel reaction kettle, sealing, and adding CO2Washing the internal gas for 3 times, and introducing CO again2And (3) enabling the initial gas pressure to reach 3.0MPa, then heating to 100 ℃, reacting for 7 hours, quickly cooling to room temperature by using ice water, taking out a mixture after reaction, carrying out centrifugal separation to obtain an organic liquid without a catalyst, and carrying out gas phase analysis by using ethylene glycol butyl ether as an internal standard. CO catalysis of the catalysts of examples 1-6, respectively2The test result of the test with epichlorohydrin is shown in table 1.
TABLE 1 examples 1-6CO2Compared with the catalytic performance of the conversion of the epichlorohydrin into the cyclic carbonate
As can be seen from the data in Table 1, of the catalysts prepared in examples 1-6, ZnWO4Introduction of metal-organic layered structure to CO2The catalytic activity of the coupling process with epichlorohydrin is significantly enhanced and shows a decreasing trend with increasing introduced lamellar structure, probably due to the ZnWO in the structure with increasing lamellar structure4The proportion of the active sites with Lewis acid functions is reduced, which is not beneficial to the ring-opening process of epoxide and leads to the reduction of catalytic activity. In conclusion, in ZnWO4The external surface of the catalyst is introduced with a proper amount of metal organic layered structure, so that the catalytic activity can be obviously improved.
Claims (10)
1. CO (carbon monoxide)2A process for preparing an epoxidation fixed catalyst, which process comprises the steps of:
step 1: synthesis of zinc tungstate ZnWO4
Sodium tungstate NaWO4Adding the mixture into deionized water solution with 0.01-10 g/L dissolved with surfactant according to the solid-to-liquid ratio of 0.01-10 mmol/L, stirring for 1-12 hours at the temperature of 20-70 ℃, and then adding the mixture and NaWO4Continuously stirring zinc salt with equal molar weight at the temperature of 20-70 ℃ for 1-12 hours, then transferring the zinc salt into a hydrothermal reaction kettle, statically reacting at the temperature of 120-180 ℃ for 12-48 hours, then cooling to room temperature, filtering and washing the obtained precipitate for 3 times, drying at the temperature of 80 ℃ for 24 hours, and calcining at the temperature of 500-900 ℃ for 3-10 hours to obtain ZnWO4；
Step 2: in-situ growth method for introducing layered metal organic structure
ZnWO prepared in the step 14Putting the mixture into a hydrothermal reaction kettle, adding an organic solvent with a solid-to-liquid ratio of 0.01-10 mmol/L into the hydrothermal reaction kettle, and stirring the mixture for 0.1-2 hours at the temperature of 20-60 ℃;
a) to the water is subjected to heat reactionAdding ZnWO into the reactor4Stirring 2 methylimidazole with an equal molar amount at the temperature of 20-60 ℃ for 1-6 hours, sealing, carrying out static reaction at the temperature of 120-180 ℃ for 12-48 hours, cooling to room temperature, filtering and washing precipitates in a hydrothermal kettle for 3 times, and dissolving in an organic solvent;
b) adding zinc salt with the same molar weight as 2-methylimidazole into the hydrothermal reaction kettle, stirring for 0.1-2 hours at the temperature of 20-60 ℃, sealing, carrying out static reaction for 12-48 hours at the temperature of 120-180 ℃, cooling to room temperature, filtering and washing precipitates in the hydrothermal reaction kettle for 3 times;
synthesizing ZnWO by regulating and controlling the repeated times of the procedures a) and b) and controlling the quantity of the layers42-methylimidazole and zinc ion alternately appearing layered structure CO as core2The catalyst is fixed by epoxidation.
2. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that the surfactant in the step 1 is one or more of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl amine bromide, hexamethylene tetramine, tetraethyl ammonium bromide, tetrapropyl ammonium bromide or tetrabutyl ammonium bromide.
3. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that the zinc salt in the step 1 is one or more of zinc nitrate, zinc chloride, zinc acetate, zinc perchlorate, zinc bromide or zinc sulfate.
4. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that the solvent for washing in the step 1 is one or more of deionized water, methanol, ethanol or nitrogen-nitrogen dimethyl formamide.
5. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that the calcination process in the step 1 is to adopt a programmed heating rate of 5 ℃/min to a target in an air atmosphereAnd (3) temperature.
6. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that the organic solvent in the step 2 is one or more of methanol, ethanol, nitrogen-nitrogen dimethyl formamide, nitrogen-nitrogen diethyl formamide or tetrahydrofuran.
7. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that the washing solution for washing 2-methylimidazole in the step 2 is one or more of methanol, ethanol, nitrogen-nitrogen dimethylformamide, nitrogen-nitrogen diethylformamide, dichloromethane, trichloromethane, tetrachloromethane or tetrahydrofuran; the washing solution for washing the zinc salt is one or more of deionized water, methanol, ethanol and nitrogen-nitrogen dimethyl formamide.
8. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that the zinc salt in the step 2 is one or more of zinc nitrate, zinc chloride, zinc acetate, zinc perchlorate, zinc bromide or zinc sulfate.
9. CO according to claim 12The preparation method of the epoxidation fixed catalyst is characterized in that after the circulation of a) and b) in the step 2, ZnWO is added4The surface of the metal organic structure is provided with a layer of metal organic structure, and the thickness of the layer of metal organic structure is equal to the distance between two zinc ions and different nitrogen atoms in 2 methylimidazole to form a stable structure.
10. CO produced by the process of claim 12Use of an epoxidation fixed catalyst, characterized in that the catalyst is capable of promoting CO2And reacting with epoxy compound, wherein the epoxy compound is one or more of propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, cyclohexene oxide and allyl glycidyl ether.
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Cited By (2)
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| CN112920187A (en) * | 2021-01-27 | 2021-06-08 | 湖南工程学院 | Method for simultaneously removing formaldehyde and synthesizing metal complex and application thereof |
| CN115025817A (en) * | 2022-06-17 | 2022-09-09 | 河南大学 | MIL-101(Cr) -supported hydroxyimidazole ionic liquid and method for catalytically synthesizing cyclic carbonate by using same |
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| CN105949129A (en) * | 2016-06-06 | 2016-09-21 | 辽宁大学 | Imidazolium bromide ionic liquid containing amine groups and preparation method and application of ionic liquid |
| CN107299417A (en) * | 2017-06-01 | 2017-10-27 | 济南大学 | A kind of WO3/ZnWO4Preparation method of composite micro-nano rice fiber and products thereof |
| CN109746022A (en) * | 2019-01-18 | 2019-05-14 | 南开大学 | A kind of preparation method and its application method of the high dispersing copper zinc catalyst for carbon dioxide reduction |
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| CN105949129A (en) * | 2016-06-06 | 2016-09-21 | 辽宁大学 | Imidazolium bromide ionic liquid containing amine groups and preparation method and application of ionic liquid |
| CN107299417A (en) * | 2017-06-01 | 2017-10-27 | 济南大学 | A kind of WO3/ZnWO4Preparation method of composite micro-nano rice fiber and products thereof |
| CN109746022A (en) * | 2019-01-18 | 2019-05-14 | 南开大学 | A kind of preparation method and its application method of the high dispersing copper zinc catalyst for carbon dioxide reduction |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112920187A (en) * | 2021-01-27 | 2021-06-08 | 湖南工程学院 | Method for simultaneously removing formaldehyde and synthesizing metal complex and application thereof |
| CN115025817A (en) * | 2022-06-17 | 2022-09-09 | 河南大学 | MIL-101(Cr) -supported hydroxyimidazole ionic liquid and method for catalytically synthesizing cyclic carbonate by using same |
| CN115025817B (en) * | 2022-06-17 | 2024-01-19 | 河南大学 | MIL-101 (Cr) loaded hydroxy imidazole ionic liquid and method for synthesizing cyclic carbonate by using same |
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