CN113976178A - Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst - Google Patents
Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst Download PDFInfo
- Publication number
- CN113976178A CN113976178A CN202111213844.0A CN202111213844A CN113976178A CN 113976178 A CN113976178 A CN 113976178A CN 202111213844 A CN202111213844 A CN 202111213844A CN 113976178 A CN113976178 A CN 113976178A
- Authority
- CN
- China
- Prior art keywords
- cps
- ionic liquid
- heteropoly acid
- catalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of a CPS (CPS) loaded heteropoly acid ionic liquid catalyst, which comprises the following steps of: preparing heteropoly acid; preparing an intermediate CPS immobilized imidazole ionic liquid; preparing the polystyrene resin supported heteropoly acid ionic liquid catalyst by a chemical bonding method. The catalyst has high catalytic effect, and solves the problem of applying ionic liquid to catalyze CO2The ionic liquid has high viscosity during preparation, difficult separation and recovery and the like in the esterification reaction for synthesizing the cyclic carbonate. The catalyst has long service life, and after the catalyst is recycled for 6 times, the yield of the propylene carbonate can reach 80.08%, the selectivity can reach 93.81%, and a good catalytic effect is still maintained.
Description
Technical Field
The invention relates to the technical field of material preparation and catalytic reaction, in particular to a preparation method of CPS (CPS) supported heteropoly acid ionic liquid and application of CPS supported heteropoly acid ionic liquid in catalyzing CO2The application of synthesizing cyclic carbonate.
Background
In recent years, with the rapid development of Chinese economy, the industrial level is continuously improved, and CO is2The emission in the atmosphere has increased year by year, resulting in significant pollution of the environment on which we live. The proposal of the concept of 'carbon neutralization' how to treat CO in green and high efficiency2It becomes urgent. It has now been found that they can be converted by new techniques into high value-added chemicals such as products of poly cyclic carbonates, polyurethanes, etc. The cyclic carbonate has the characteristics of strong chemical stability, high ionic conductivity and the like, and is a good organic solvent. Introducing CO2As a raw material for producing the cyclic carbonate, the method not only reduces the emission of carbon dioxide in the atmosphere and slows down the greenhouse effect, conforms to the modern green chemical standard, but also can obtain chemicals with high added values, realizes the recycling of carbon, and is the fixed CO generally accepted in the world at present2One of the most promising approaches.
The ionic liquid refers to a salt which consists of anions and cations and is in a molten state at room temperature. The catalyst has the characteristics of no pollution, stable property, difficult volatilization and the like, is commonly used as a catalyst, and the ionic liquid is modified for catalyzing CO2Esterification for the synthesis of cyclic carbonatesThe reaction has high catalytic efficiency. However, the ionic liquid has the defects of high viscosity, difficult separation and recovery and the like during preparation, so that the large-scale application of the ionic liquid is limited. Therefore, it is necessary to immobilize the ionic liquid on a suitable carrier to solve these problems. The carriers reported at present are such as molecular sieve, active carbon and SiO2And the like, or the problems of complex synthetic steps, amorphous carrier and the like. Therefore, the method for preparing the immobilized ionic liquid catalyst with simple synthesis steps and well-controlled reaction conditions is urgently needed to be developed.
So far, no reports exist about a chloromethylated polystyrene resin (CPS) immobilized heteropoly acid ionic liquid catalyst which is a solid catalyst, has stable structural property, high catalytic efficiency and good recycling performance and has higher industrial application prospect.
Disclosure of Invention
The purpose of the invention is as follows:
the invention provides a preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst, aiming at connecting imidazole cations and heteropoly acid anions together through chemical bonding to prepare an organic-inorganic hybrid catalyst, realizing the synergistic catalytic action of metal and acidic active sites and effectively solving the problem that the traditional immobilized catalyst catalyzes CO (carbon monoxide)2The synthetic propylene carbonate has the problems of easy desorption, loss of active components, poor stability and the like, and further improves the catalytic performance.
The technical scheme is as follows:
a preparation method of CPS supported heteropoly acid ionic liquid catalyst comprises the following steps:
(1) preparation of heteropolyacids
According to a molar ratio of 1: 1-3: 1-3, dissolving sodium tungstate, central atom salt and coordination atom salt in distilled water, heating, adjusting the pH to 4-5 by using a pH regulator after the dissolution is finished, reacting for 2.0-6.0h at the temperature of 60-85 ℃, and washing, concentrating and drying to obtain heteropoly acid;
(2) preparation of intermediate CPS immobilized imidazole ionic liquid
CPS, N-methylimidazole, N-butyl bromide and acetonitrile are mixed according to a molar ratio of 1: 2-6: 0.8-1.2: 10-25, adding the mixture into a reactor, reacting for 24-48h at 60-80 ℃, and performing suction filtration, washing and drying to obtain CPS-MIM-Br;
(3) preparation of polystyrene resin loaded heteropoly acid ionic liquid catalyst by chemical bonding method
Dissolving heteropoly acid in solvent, adding cation exchange resin and CPS-MIM-Br, slowly stirring at 25-30 deg.C for 8-12h, stopping reaction, suction filtering, washing and drying to obtain CPS-loaded heteropoly acid ionic liquid CPS-MIM-WM.
In the step (1), the molar ratio of sodium tungstate to distilled water is 1: 80-100.
In the step (1), the pH regulator is one of acetic acid and HCl.
In the step (1), the central atom salt is one of manganese acetate and zirconium oxychloride; the coordination atom salt is one of cobalt acetate and zinc chloride, and the heteropoly acid is CoW11Mn、ZnW11Mn、CoW11Zr、ZnW11One kind of Zr.
In the step (3), the molar ratio n of heteropoly acid, cation exchange resin, CPS-MIM-Br and solvent is 1: 0.005-0.04: 0.02-0.05: 10-25; the solvent is one or two of ethanol, methanol and dichloromethane which are mixed in any proportion.
The heteropoly acid is Keggin type, and a central heteroatom and a vacancy atom and an imidazole structure can play a role in concerted catalysis.
CPS (CPS) supported heteropoly acid ionic liquid catalyst used as CO2The application of synthesizing cyclic carbonate.
The invention has the following advantages and good effects:
the catalyst has high catalytic effect, and solves the problem of applying ionic liquid to catalyze CO2The ionic liquid has high viscosity during preparation, difficult separation and recovery and the like in the esterification reaction for synthesizing the cyclic carbonate.
The catalyst has long service life, and after the catalyst is recycled for 6 times, the yield of the propylene carbonate can reach 80.08%, the selectivity can reach 93.81%, and a good catalytic effect is still maintained.
Drawings
FIG. 1 is a schematic diagram of catalyst synthesis;
FIG. 2 is an infrared spectroscopic analysis of the supported catalyst prepared;
fig. 3 is an X-ray spectrum of the prepared supported catalyst.
Detailed Description
The invention is described in more detail below with reference to the accompanying drawings.
As shown in figure 1, the invention relates to an immobilized heteropoly acid type ionic liquid catalyst, a preparation method thereof and CO catalysis by the immobilized heteropoly acid type ionic liquid catalyst2Application of synthesizing propylene carbonate. The CPS sphere is used as a carrier to carry heteropoly acid ionic liquid through chemical bonds and a method to prepare the heteropoly acid ionic liquid catalyst, the catalyst is in a solid phase state and has the characteristics of stable carrier structure, large specific surface area and the like, and heteropoly acid metal ions and an imidazole structure have a synergistic catalytic action, so that the catalytic activity can be further improved. The heteropolyacid ionic liquid and the CPS carrier can enable the immobilization structure to be firmer through chemical bonds, the stability and the strength of the catalyst are improved, the phenomena of loss and desorption of active components of the immobilized ionic liquid catalyst are further improved, and the spherical solid catalyst is more favorable for recovery and cyclic utilization.
The structure and appearance of the supported catalyst are characterized by an infrared spectrometer (FT-IR), a Scanning Electron Microscope (SEM) and the like, and propylene oxide and CO are used2The CPS sphere immobilized heteropoly acid ionic liquid is used as a catalyst to examine the catalytic performance of the CPS sphere immobilized heteropoly acid ionic liquid serving as a raw material. After the product is detected by a gas chromatograph, the percentage content of each component in the product is determined by an area normalization method, and the conversion rate, selectivity and yield of reactants and target products are calculated so as to measure and evaluate the catalytic performance.
Example 1
(1) Preparation of heteropolyacids
Sodium tungstate, 1mol of cobalt acetate and 1mol of manganese acetate are dissolved in 80mol of distilled water according to a molar ratio of 1mol, and heated. After the dissolution is finished, acetic acid makes the PH to be 4, the reaction is carried out for 2h at the temperature of 60 ℃, and heteropoly acid (CoW) is obtained after washing, concentration and drying11Mn)。
(2) Preparation of intermediate CPS immobilized imidazole ionic liquid (CPS-MIM-Br)
Adding 1mol CPS, 2mol N-methylimidazole, 0.8mol n-butyl bromide and 10mol acetonitrile into a reactor according to a molar ratio, reacting at 60 ℃ for 24 hours, and performing suction filtration, washing and drying to obtain CPS-MIM-Br.
(3) Impregnation method for preparing polystyrene resin supported heteropoly acid ionic liquid catalyst
1molCoW11Dissolving Mn in 10mol of methanol, adding 0.005mol of cation exchange resin and 0.02mol of CPS-MIM-Br, slowly stirring at 25 ℃ for reacting for 8h, stopping reaction, carrying out suction filtration, washing and drying to obtain CPS-loaded heteropoly acid ionic liquid CPS-MIM-CoW11Mn。
The CPS supported heteropoly acid ionic liquid catalyst in the invention is preferably CPS-MIM-CoW11Mn。
Example 2
(1) Preparation of heteropolyacids
Sodium tungstate, 1.5mol of zinc chloride and 2mol of manganese acetate are dissolved in 90mol of distilled water according to a molar ratio of 1mol, and heated. After the dissolution is finished, HCl is used for leading the pH to be 4.3, the reaction is carried out for 4.0h at the temperature of 70 ℃, and the heteropoly acid (ZnW) is obtained after washing, concentration and drying11Mn)。
(2) Preparation of intermediate CPS immobilized imidazole ionic liquid (CPS-MIM-Br)
Adding 1mol CPS, 6mol N-methylimidazole, 0.9mol n-butyl bromide and 20mol acetonitrile into a reactor according to a molar ratio, reacting at 80 ℃ for 35 hours, and performing suction filtration, washing and drying to obtain CPS-MIM-Br.
(3) Impregnation method for preparing polystyrene resin supported heteropoly acid ionic liquid catalyst
1mol of ZnW11Dissolving Mn in 15mol of ethanol and 10mol of dichloromethane, adding 0.03mol of cation exchange resin and 0.04mol of CPS-MIM-Br, slowly stirring for reaction at 26 ℃ for 9h, stopping the reaction, and obtaining CPS-loaded heteropoly acid ionic liquid CPS-MIM-ZnW by suction filtration, washing and drying11Mn。
Example 3
(1) Preparation of heteropolyacids
Sodium tungstate, 3mol of cobalt acetate and 2.5mol of zirconium oxychloride were dissolved in 100mol of distilled water at a molar ratio of 1mol, and heated. After dissolution was complete, the pH was adjusted to 4.8, 65 with acetic acidReacting for 6.0h, washing, concentrating and drying to obtain heteropoly acid (CoW)11Zr)。
(2) Preparation of intermediate CPS immobilized imidazole ionic liquid (CPS-MIM-Br)
Adding 1mol CPS, 5mol N-methylimidazole, 1.2mol n-butyl bromide and 25mol acetonitrile into a reactor according to a molar ratio, reacting for 48 hours at 75 ℃, and performing suction filtration, washing and drying to obtain CPS-MIM-Br.
(3) Impregnation method for preparing polystyrene resin supported heteropoly acid ionic liquid catalyst
1mol of CoW11Zr is dissolved in 20mol of dichloromethane, 0.01mol of cation exchange resin and 0.03mol of CPS-MIM-Br are added, the reaction is stopped after the materials are slowly stirred and react for 10 hours at the temperature of 30 ℃, and CPS-loaded heteropoly acid ionic liquid CPS-MIM-CoW is obtained after suction filtration, washing and drying11Zr。
Example 4
(1) Preparation of heteropolyacids
Sodium tungstate, 2mol zinc chloride and 3mol zirconium oxychloride are dissolved in 85mol distilled water according to a molar ratio of 1mol, and heated. After the dissolution is finished, HCl is used for leading the pH to be 5, the reaction is carried out for 5.0h at the temperature of 80 ℃, and heteropoly acid (ZnW) is obtained after washing, concentration and drying11Zr)。
(2) Preparation of intermediate CPS immobilized imidazole ionic liquid (CPS-MIM-Br)
Adding 1mol CPS, 4mol N-methylimidazole, 1.0mol n-butyl bromide and 15mol acetonitrile into a reactor according to a molar ratio, reacting at 70 ℃ for 28h, and performing suction filtration, washing and drying to obtain CPS-MIM-Br.
(3) Impregnation method for preparing polystyrene resin supported heteropoly acid ionic liquid catalyst
1molZnW is added11Dissolving Zr in 15mol of ethanol, adding 0.04mol of cation exchange resin and 0.05mol of CPS-MIM-Br, slowly stirring at 28 ℃ for reaction for 12h, stopping reaction, carrying out suction filtration, washing and drying to obtain CPS-loaded heteropoly acid ionic liquid CPS-MIM-ZnW11Zr。
The catalysts prepared in examples 1 to 4 were applied to catalyzing CO using a tank reactor, respectively2And the propylene carbonate is synthesized by carbonylation with propylene oxide. The reaction is carried out under the conditions that the dosage of the catalyst is 3.0g, the propylene oxide is 150ml,the reaction was stopped at a temperature of 130 ℃ and a pressure of 2.5MPa for 5 hours, and the results of the catalytic evaluation are shown in Table 1.
TABLE 1 evaluation of catalytic Effect of examples 1 to 4
Table 1 shows the evaluation of the catalytic effect of the catalysts prepared in examples 1 to 4 on the synthesis of propylene carbonate by carbonylation, and the experimental results show that the catalyst CPS-MIM-CoW prepared in example 111The Mn catalytic effect is optimal, the yield reaches 91.11%, and the selectivity reaches 98.76%.
Example 5
The supported catalyst CPS-MIM-CoW prepared in example 1 is used11And (3) carrying out the recycling performance research on Mn, wherein the catalytic reaction conditions are the same, and the recycling catalytic evaluation results are shown in Table 2.
TABLE 2CPS-MIM-CoW11Mn recycling performance
Table 2 shows the supported catalyst CPS-MIM-CoW11The Mn recycling performance and experimental results show that the catalyst has a very good service life, the yield of the propylene carbonate is 80.08% and the selectivity is 93.81% after the catalyst is recycled for 6 times, and a good catalytic effect is still maintained.
As can be seen from the catalytic evaluation experiment, the catalyst CPS-MIM-CoW prepared in the example11The Mn catalytic effect is optimal, and the infrared spectrum of the catalyst is tested to obtain an infrared spectrum as shown in figure 2. From fig. 2, the Keggin structure of the heteropoly acid ionic liquid and the characteristic peak of polystyrene can be seen, wherein the Keggin structure contains metal ions, and is easier to form a complexing effect with oxygen atoms of epoxy compounds, so that the ring opening is promoted, the conversion rate is improved, and meanwhile, the structure is acidic and has a synergistic catalytic effect. Therefore, the infrared spectrogram illustrates that the heteropoly acid ionic liquid is successfully loaded on polystyrene chloride spheres (a) CoW11Mn；(b)CPS-MIM-CoW11Mn。
For the above catalyst CPS-MIM-CoW11The Mn was subjected to X-ray measurement to obtain a spectrum as shown in FIG. 3. The characteristic diffraction peaks 2 theta of W, Mn and Co metal elements of the heteropolyacid with a Keggin structure are respectively distributed within the ranges of 7-10 degrees, 16-22 degrees and 25-34 degrees, and the supported catalyst CPS-MIM-CoW can be obtained from the graph 311Diffraction peaks containing W, Mn and Co appear at 9.17, 19.79 and 28.38 of Mn respectively, and the results of infrared spectroscopy are combined to further illustrate CPS-MIM-CoW of the heteropoly acid ionic liquid catalyst11The Mn is successfully prepared.
Claims (7)
1. A preparation method of CPS load heteropoly acid ionic liquid catalyst is characterized in that: the method comprises the following steps:
(1) preparation of heteropolyacids
According to a molar ratio of 1: 1-3: 1-3, dissolving sodium tungstate, central atom salt and coordination atom salt in distilled water, heating, adjusting the pH to 4-5 by using a pH regulator after the dissolution is finished, reacting for 2.0-6.0h at the temperature of 60-85 ℃, and washing, concentrating and drying to obtain heteropoly acid;
(2) preparation of intermediate CPS immobilized imidazole ionic liquid
CPS, N-methylimidazole, N-butyl bromide and acetonitrile are mixed according to a molar ratio of 1: 2-6: 0.8-1.2: 10-25, adding the mixture into a reactor, reacting for 24-48h at 60-80 ℃, and performing suction filtration, washing and drying to obtain CPS-MIM-Br;
(3) preparation of polystyrene resin loaded heteropoly acid ionic liquid catalyst by chemical bonding method
Dissolving heteropoly acid in solvent, adding cation exchange resin and CPS-MIM-Br, slowly stirring at 25-30 deg.C for 8-12h, stopping reaction, suction filtering, washing and drying to obtain CPS-loaded heteropoly acid ionic liquid CPS-MIM-WM.
2. The method for preparing CPS supported heteropolyacid ionic liquid catalyst as claimed in claim 1, wherein: in the step (1), the molar ratio of sodium tungstate to distilled water is 1: 80-100.
3. The method for preparing CPS supported heteropolyacid ionic liquid catalyst as claimed in claim 1, wherein: in the step (1), the pH regulator is one of acetic acid and HCl.
4. The method for preparing CPS supported heteropolyacid ionic liquid catalyst as claimed in claim 1, wherein: in the step (1), the central atom salt is one of manganese acetate and zirconium oxychloride; the coordination atom salt is one of cobalt acetate and zinc chloride, and the heteropoly acid is CoW11Mn、ZnW11Mn、CoW11Zr、ZnW11One kind of Zr.
5. The method for preparing CPS supported heteropolyacid ionic liquid catalyst as claimed in claim 1, wherein: in the step (3), the molar ratio n of heteropoly acid, cation exchange resin, CPS-MIM-Br and solvent is 1: 0.005-0.04: 0.02-0.05: 10-25; the solvent is one or two of ethanol, methanol and dichloromethane which are mixed in any proportion.
6. The preparation method of CPS supported heteropolyacid ionic liquid catalyst as claimed in claim 1, wherein: the heteropoly acid is Keggin type.
7. CPS supported heteropolyacid ionic liquid catalyst as claimed in claim 1 as CO2The application of synthesizing cyclic carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111213844.0A CN113976178A (en) | 2021-10-19 | 2021-10-19 | Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111213844.0A CN113976178A (en) | 2021-10-19 | 2021-10-19 | Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113976178A true CN113976178A (en) | 2022-01-28 |
Family
ID=79739280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111213844.0A Pending CN113976178A (en) | 2021-10-19 | 2021-10-19 | Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113976178A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781598A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for preparing resin assembled heteropoly acid salt catalyst |
| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
| US20150259318A1 (en) * | 2012-10-08 | 2015-09-17 | Council of Scientfic & Industrial Research an Indian Registered Body Incorporated | One step process for synthesis of cyclic carbonates |
| CN105367541A (en) * | 2014-08-11 | 2016-03-02 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate through polyionic liquid nanometer catalysis cycloaddition reaction |
| CN109174202A (en) * | 2018-08-03 | 2019-01-11 | 江苏大学 | A kind of Preparation method and use for the Sn-SBA-15 catalyst that heteropoly acid is ionic liquid loaded |
-
2021
- 2021-10-19 CN CN202111213844.0A patent/CN113976178A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781598A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for preparing resin assembled heteropoly acid salt catalyst |
| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
| US20150259318A1 (en) * | 2012-10-08 | 2015-09-17 | Council of Scientfic & Industrial Research an Indian Registered Body Incorporated | One step process for synthesis of cyclic carbonates |
| CN105367541A (en) * | 2014-08-11 | 2016-03-02 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate through polyionic liquid nanometer catalysis cycloaddition reaction |
| CN109174202A (en) * | 2018-08-03 | 2019-01-11 | 江苏大学 | A kind of Preparation method and use for the Sn-SBA-15 catalyst that heteropoly acid is ionic liquid loaded |
Non-Patent Citations (3)
| Title |
|---|
| SEYED MOHSEN SADEGHZADEH: "A heteropolyacid-based ionic liquid immobilized onto fibrous nano-silica as an efficient catalyst for the synthesis of cyclic carbonate from carbon dioxide and epoxides", 《GREEN CHEMISTRY》 * |
| XIN KOU ET A: "Properties and mechanism for selective adsorption of Au(III) on an ionic liquid adsorbent by grafting N-methyl imidazole onto chloromethylated polystyrene beads", 《RSC ADVANCES》 * |
| 孙佳昆等: "K8[Co(H2O)W11MnO39]/PANI/ZrO2复合材料的制备及其光催化性能研究", 《化学研究与应用》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | Visible-light-driven prompt and quantitative production of lactic acid from biomass sugars over a N-TiO 2 photothermal catalyst | |
| CN113000049B (en) | Method for preparing Ni-Al-based oxide catalyst | |
| CN112371189A (en) | Hydroxide-coated ZIF (zinc-oxygen-doped organic framework) MOFs (metal-organic frameworks) heterogeneous catalyst and preparation and application thereof | |
| CN106694030B (en) | Catalyst for preparing cyclic carbonate through cycloaddition reaction, preparation method and application | |
| CN113061221B (en) | Covalent organic framework material and preparation method and application thereof | |
| CN116586093B (en) | Preparation method and application of ZIF-67@ZIF-8 cobalt-based catalyst with core-shell structure | |
| CN114588910A (en) | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization | |
| CN114029070A (en) | In-situ hydrogenolysis aryl ether bond catalyst and preparation method and application thereof | |
| CN114558620B (en) | Metal organic framework immobilized ionic liquid catalyst and preparation method and application thereof | |
| CN103127957B (en) | Mesoporous PW/MoO3-TiO2-SiO2 catalyst and preparation method and application thereof | |
| CN113769790B (en) | Carboxyl functionalized ILs@MOFs composite material and preparation method and application thereof | |
| CN109046382B (en) | Preparation method of biomass carbon-based solid super acid | |
| CN112206808B (en) | Catalyst for synthesizing isobutyl isobutyrate and preparation method and application thereof | |
| CN102698762A (en) | Method for preparing dimethyl ether (DME) catalyst from synthesis gas | |
| CN113976178A (en) | Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN114425367B (en) | Catalyst system for preparing acrylic ester by carbonylation of acetylene, preparation and application thereof | |
| CN110075916B (en) | Supported metal-acidic ionic liquid catalyst and application thereof | |
| CN111203275B (en) | Series reaction catalyst and preparation method and application thereof | |
| CN110639554B (en) | Method for preparing ultrahigh-thermal-stability carbon-silicon composite solid superacid and reversibly regulating and controlling thermal stability of ultrahigh-thermal-stability carbon-silicon composite solid superacid | |
| Wan et al. | Influence of calcination temperature on the cooperative catalysis of base sites and gold nanoparticles on hydrotalcite-supported gold materials for the base-free oxidative esterification of 1, 3-propanediol with methanol to methyl 3-hydroxypropionate | |
| CN114433228A (en) | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid | |
| CN117399022B (en) | Lignin-based composite catalytic material and preparation method and application thereof | |
| CN108636430B (en) | Preparation method and application of vanadium-modified zirconium phosphate heterogeneous catalyst | |
| CN112958129B (en) | Solid acid catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |