CN108554407B - Nano copper-based catalyst and preparation method thereof - Google Patents

Nano copper-based catalyst and preparation method thereof Download PDF

Info

Publication number
CN108554407B
CN108554407B CN201810042396.4A CN201810042396A CN108554407B CN 108554407 B CN108554407 B CN 108554407B CN 201810042396 A CN201810042396 A CN 201810042396A CN 108554407 B CN108554407 B CN 108554407B
Authority
CN
China
Prior art keywords
copper
nano
based catalyst
mixed solution
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.)
Active
Application number
CN201810042396.4A
Other languages
Chinese (zh)
Other versions
CN108554407A (en
Inventor
王利国
刘佳驹
李会泉
杨延米
张婵娟
贺鹏
曹妍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Process Engineering of CAS
Original Assignee
Institute of Process Engineering of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201810042396.4A priority Critical patent/CN108554407B/en
Publication of CN108554407A publication Critical patent/CN108554407A/en
Application granted granted Critical
Publication of CN108554407B publication Critical patent/CN108554407B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A nanometer copper-based catalyst and a preparation method thereof are provided, wherein the preparation method of the nanometer copper-based catalyst comprises the following steps: (1) dissolving a copper source, a silicon source, a template agent and an auxiliary agent in a solvent to obtain a precursor mixed solution; (2) mixing the precursor mixed solution obtained in the step (1) with a precipitator, and stirring to obtain a mixed solution; (3) heating and evaporating the mixed liquid obtained in the step (2), and carrying out solid-liquid separation to obtain a solid compound; (4) and (4) calcining the solid compound obtained in the step (3), and then reducing and activating to obtain the nano copper-based catalyst. The nano copper-based catalyst prepared by the invention has good catalytic efficiency in the reaction of ethylene carbonate for catalytic hydrogenation and coproduction of methanol and ethylene glycol. Meanwhile, the catalyst has excellent stability in a circulation experiment.

Description

Nano copper-based catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a nano copper-based catalyst and a preparation method thereof.
Background
In recent years, environmental pollution and greenhouse effect caused by carbon dioxide have become serious, and the problem has caused the weight of a plurality of scientific researchers at home and abroadAttention is paid to. CO 22Is the final product of carbon-containing compounds, is the cheapest compound in the carbon family, and is the most abundant carbon resource existing in nature. Therefore, research and development of CO2The comprehensive utilization of resources has very important economic value and practical significance.
Methanol and ethylene glycol are two important products in the chemical industry. Methanol is called 'methanol economy', has wide application, is not only an important organic chemical raw material and a high-quality clean and environment-friendly liquid fuel, but also a good carrier for hydrogen storage and energy storage, and is also a good solvent. China, as a major consumer of methanol, consumes about 45% of the total methanol worldwide. Ethylene glycol is used as an important organic chemical raw material and is widely applied in industrial production, and the ethylene glycol is not only widely applied to the production of polyester resin, alkyd resin and polyester fiber in a monomer form, but also is a raw material of common chemicals such as a lubricant, a plasticizer, paint, an adhesive, a surfactant and the like. In addition, ethylene glycol can also be used as a liquid fuel in the field of fuel cells.
Thus, with CO being renewable2The resources are subjected to hydrogenation reaction to synthesize the methanol and the glycol, and the method has important significance for sustainable development of resources, energy environments and society. But CO2The direct catalytic hydrogenation synthesis of methanol is limited by its thermodynamic stability and kinetic protectiveness. And CO2The method for preparing the Ethylene Carbonate (EC) by the ethylene oxide has been industrialized and has high reaction activity and selectivity. Thus, with CO2Firstly preparing ethylene carbonate as raw material, and then using the ethylene carbonate as CO2The carrier further reacts with hydrogen under mild conditions to produce methanol and CO-produce glycol, so that CO is utilized2The purpose of high-efficiency indirect coproduction of methanol and glycol is realized, and the method has great application potential.
At present, catalyst reports related to ethylene carbonate hydrogenation mainly focus on a heterogeneous catalyst with copper as an active component, and copper-based catalysts generally have the problems of poor stability, easy sintering and the like, so that the development of the copper-based catalyst with high-temperature sintering resistance and high activity is a difficult point of the technology for preparing alcohol by ethylene carbonate hydrogenation.
In recent years SiO has been used2The stability research and application of the supported copper-based catalyst as a carrier in the preparation of alcohol by ester hydrogenation are rapidly developed. In order to improve the stability of the catalyst, it is common to modify the catalyst with a suitable promoter, which is mostly an oxide of a metal or nonmetal element.
In the research of a catalytic system for preparing alcohol by hydrogenating ethylene carbonate, the hydrogenation performance of the catalyst is greatly improved at present, but the expected development is not achieved. Therefore, the ethylene carbonate hydrogenation catalyst suitable for industrial application firstly needs to have the stability capable of meeting the requirements of industrial application, and secondly has high ethylene carbonate conversion rate, high ethylene glycol selectivity and high methanol selectivity on the basis of high stability.
Therefore, it is necessary to develop a catalyst having higher catalytic efficiency and more excellent performance to meet the demand of industrial application.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a nano copper-based catalyst and a preparation method thereof, so as to solve at least one of the above problems.
The invention is realized by the following technical scheme:
as one aspect of the present invention, there is provided a method for preparing a nano copper-based catalyst, comprising the steps of: (1) dissolving a copper source, a silicon source, a template agent and an auxiliary agent in a solvent to obtain a precursor mixed solution; (2) mixing the precursor mixed solution obtained in the step (1) with a precipitator, adjusting the pH value to 7-12, and stirring to obtain a mixed solution; (3) heating the mixed solution obtained in the step (2) to remove ammonia, and carrying out solid-liquid separation to obtain a solid compound; (4) and (4) calcining the solid compound obtained in the step (3) in protective gas, and then reducing and activating in a reducing atmosphere to obtain the nano copper-based catalyst.
Preferably, in step (1), the copper source is one or more of copper nitrate, copper sulfate or copper chloride; the silicon source is tetraethoxysilane; the solvent is water or a mixed solution of water and ethanol.
Preferably, in step (1), the template agent is one or more of cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, P123 or F127; the amount of the template agent is 5-150% of the mass of the copper component in the copper source.
Preferably, in the step (1), the auxiliary agent is beta-cyclodextrin; the amount of the auxiliary agent is 10-50% of the mass of the copper component in the copper source.
Preferably, in the step (2), the precipitant is ammonium carbonate solution, and the concentration is 0.1-1.5 mol/L.
Preferably, in the step (3), the heating temperature is 50-100 ℃, and the heating is stopped when the pH value is 6-7.
Preferably, in the step (4), the protective gas is nitrogen, argon or helium, and the calcining temperature is 350-650 ℃.
Preferably, in the step (4), the reducing atmosphere is a mixed gas of hydrogen and the protective gas, wherein the volume fraction of the hydrogen is 10-100%; the temperature of reduction activation is 300-450 ℃.
As another aspect of the invention, the invention provides a nano copper-based catalyst obtained by the method, wherein the nano copper-based catalyst comprises copper and SiO2And carbon, wherein the mass fraction of copper is 0.5-45.0%, SiO245.0-89.5% by mass, and the balance carbon.
Preferably, the nano copper-based catalyst is applied to the reaction of ethylene carbonate for catalytic hydrogenation and coproduction of methanol and ethylene glycol.
According to the technical scheme, the nano copper-based catalyst and the preparation method thereof have the following beneficial effects:
(1) the Cu component is uniformly loaded on the carrier by using a precipitation method, the dispersibility of the active component is regulated by adding the template agent and the auxiliary agent, and the agglomeration of active copper species is inhibited by using the carbon deposition effect of the organic matter, so that a new solution is provided for the difficult problem that the copper-based catalyst is easy to sinter at high temperature.
(2) The nano copper-based catalyst prepared by the invention has good catalytic efficiency in the reaction of ethylene carbonate for catalytic hydrogenation and coproduction of methanol and ethylene glycol, and meanwhile, the catalyst has excellent stability in a circulation experiment.
Drawings
FIG. 1 is a graph showing the results of an experiment on the cycle performance of a catalyst in example 2 of the present invention;
FIG. 2 is a graph showing the results of the cycle performance test of the catalyst in comparative example 2 of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention provides a nano copper-based catalyst and a preparation method thereof, wherein the preparation method of the nano copper-based catalyst comprises the following steps: (1) dissolving a copper source, a silicon source, a template agent and an auxiliary agent in a solvent to obtain a precursor mixed solution; (2) mixing the precursor mixed solution obtained in the step (1) with a precipitator, and stirring to obtain a mixed solution; (3) heating and evaporating the mixed liquid obtained in the step (2), and carrying out solid-liquid separation to obtain a solid compound; (4) and (4) calcining the solid compound obtained in the step (3), and then reducing and activating to obtain the nano copper-based catalyst. The nano copper-based catalyst prepared by the invention has good catalytic efficiency in the reaction of ethylene carbonate for catalytic hydrogenation and coproduction of methanol and ethylene glycol. Meanwhile, the catalyst has excellent stability in a circulation experiment.
Specifically, as an aspect of the present invention, there is provided a method for preparing a nano copper-based catalyst, comprising the steps of: (1) dissolving a copper source, a silicon source, a template agent and an auxiliary agent in a solvent to obtain a precursor mixed solution; (2) mixing the precursor mixed solution obtained in the step (1) with a precipitator, adjusting the pH value to 7-12, and stirring to obtain a mixed solution; (3) heating the mixed solution obtained in the step (2) to remove ammonia, and carrying out solid-liquid separation to obtain a solid compound; (4) and (4) calcining the solid compound obtained in the step (3) in protective gas, and then reducing and activating in a reducing atmosphere to obtain the nano copper-based catalyst.
In the step (1), the copper source is one or a combination of more of copper nitrate, copper sulfate and copper chloride; the silicon source is tetraethoxysilane; the solvent is water or a mixed solution of water and ethanol; the template agent is one or the combination of more of hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) or polyoxyethylene and polyoxypropylene block polymer (F127); the amount of the template agent is 5-150% of the mass of the copper component in the copper source; the auxiliary agent is beta-cyclodextrin; the amount of the auxiliary agent is 10-50% of the mass of the copper component in the copper source.
In the step (2), the precipitant is ammonium carbonate solution, and the concentration is 0.1-1.5 mol/L.
In the step (3), the heating temperature is 50-100 ℃, and the heating is stopped when the pH value is 6-7.
In the step (4), the protective gas is nitrogen, argon or helium, and the calcining temperature is 350-650 ℃; the reducing atmosphere is a mixed gas of hydrogen and the protective gas, wherein the volume fraction of the hydrogen is 10-100%; the temperature of reduction activation is 300-450 ℃.
As another aspect of the invention, the invention provides a nano copper-based catalyst obtained by the method, wherein the nano copper-based catalyst comprises copper and SiO2And carbon, wherein the mass fraction of copper is 0.5-45.0%, SiO245.0-89.5% by mass, and the balance carbon.
In some embodiments of the invention, the nano copper-based catalyst is applied to the reaction of ethylene carbonate for catalytic hydrogenation and coproduction of methanol and ethylene glycol.
The following describes the copper-based nanocatalyst and the preparation method thereof in detail with reference to specific examples and drawings.
EXAMPLE 1 preparation of Nano Cu/SiO by precipitation method2-1 catalyst
The preparation method comprises the following steps:
(1) at room temperature, 8.6g of Cu (NO)3)2·3H2Dissolving O, 25g of tetraethoxysilane, 1.5g of hexadecyl trimethyl ammonium bromide and 0.5g of beta-cyclodextrin in a mixed solution of 150mL of deionized water and 50mL of ethanol, and ultrasonically stirring for 30min until the mixture is dissolvedCompletely obtaining precursor mixed liquor;
(2) simultaneously dripping 0.5mol/L ammonium carbonate solution and the precursor mixed solution obtained in the step (1), adjusting the pH value to be about 9.0, and stirring for 4 hours to obtain a mixed solution;
(3) heating the mixed solution obtained in the step (2) to 85 ℃, evaporating to remove part of liquid, stopping heating after the pH value is reduced to 6-7, filtering the obtained mixed solution, washing and filtering the obtained precipitate with deionized water and ethanol, and drying at 90 ℃ for 12 hours to obtain a solid compound;
(4) adding the solid compound obtained in the step (3) into N2Calcining at 450 deg.C for 4H, and then calcining in H2And N2In the mixed gas of (H)2Volume fraction of (1)%), and reduction activation at 350 deg.C for 4h to obtain Cu/SiO2-1 catalyst.
And (3) performance testing: 10mmol of ethylene carbonate, 0.176g of the catalyst obtained in the example, 20mL of tetrahydrofuran and 100. mu.L of p-xylene internal standard substance were placed in a stainless steel autoclave, the autoclave was closed, the air in the autoclave was replaced with nitrogen and hydrogen in this order for a plurality of times, and then 5MPa of H was charged into the autoclave2(ii) a After checking that the air tightness is good, heating the reaction kettle to 180 ℃ and preserving heat for 4 hours, and controlling the rotating speed of magnetic stirring to be 550 rpm; after the reaction is finished, cooling the autoclave to room temperature in ice-water bath, and slowly releasing residual H in the autoclave through a needle valve2The reaction vessel was opened, the catalyst and the reaction solution were centrifuged, and a small amount of the reaction solution was taken to analyze the composition by gas chromatography, and the results are shown in Table 1.
EXAMPLE 2 preparation of Nano Cu/SiO by precipitation method2-2 catalyst
The preparation method comprises the following steps:
(1) 9.6g of Cu (NO) was added at room temperature3)2·3H2Dissolving O, 25g of tetraethoxysilane, 1.5g P123 and 1.0g of beta-cyclodextrin in a mixed solution of 150mL of deionized water and 50mL of ethanol, and ultrasonically stirring for 30min until the mixture is completely dissolved to obtain a precursor mixed solution;
(2) simultaneously dripping 0.25mol/L ammonium carbonate solution and the precursor mixed solution obtained in the step (1), adjusting the pH value to be kept at about 8.5, and stirring for 4 hours to obtain a mixed solution;
(3) heating the mixed solution obtained in the step (2) to 75 ℃, evaporating to remove part of liquid, stopping heating after the pH value is reduced to 6-7, filtering the obtained mixed solution, washing and filtering the obtained precipitate with deionized water and ethanol, and drying at 95 ℃ for 14 hours to obtain a solid compound;
(4) adding the solid compound obtained in the step (3) into N2Calcining at 450 deg.C for 3H, and reducing and activating at 350 deg.C for 5H in mixed gas of H2 and N2 (volume fraction of H2 is 10%), to obtain Cu/SiO2-2 catalyst.
And (3) performance testing: the same as in example 1.
EXAMPLE 3 preparation of Nano Cu/SiO by precipitation method2-3 catalyst
The preparation method comprises the following steps:
(1) 13.5g of Cu (NO) was added at room temperature3)2·3H2Dissolving O, 25g of tetraethoxysilane, 1.5g F127 and 0.25g of beta-cyclodextrin in a mixed solution of 150mL of deionized water and 50mL of ethanol, and ultrasonically stirring for 30min until the mixture is completely dissolved to obtain a precursor mixed solution;
(2) simultaneously dripping 0.5mol/L ammonium carbonate solution and the precursor mixed solution obtained in the step (1), adjusting the pH value to be kept at about 7.5, and stirring for 5 hours to obtain a mixed solution;
(3) heating the mixed solution obtained in the step (2) to 85 ℃, evaporating to remove part of liquid, stopping heating after the pH value is reduced to 6-7, filtering the obtained mixed solution, washing and filtering the obtained precipitate with deionized water and ethanol, and drying at 90 ℃ for 12 hours to obtain a solid compound;
(4) adding the solid compound obtained in the step (3) into N2Calcining at 450 deg.C for 3.5H, and calcining in H2And N2In the mixed gas of (H)2Volume fraction of (1%) is 10%), reducing and activating at 350 deg.C for 3.5h to obtain Cu/SiO2-3 catalyst.
And (3) performance testing: the same as in example 1.
EXAMPLE 4 preparation of Nano Cu/SiO by precipitation method2-4 catalyst
The preparation method comprises the following steps:
the procedure of example 4 differs from that of example 1 only in that the pH in the procedure of (2) was changed to 10 to obtain Cu/SiO2-4 catalyst.
And (3) performance testing: the same as in example 1.
EXAMPLE 5 preparation of Nano Cu/SiO by precipitation method2-5 catalyst
The preparation method comprises the following steps:
in the same manner as in example 1, Cu/SiO was obtained2-5 catalyst.
And (3) performance testing: the difference from example 1 is only that the heating time was changed from 4h to 3 h. EXAMPLE 6 preparation of Nano Cu/SiO by precipitation method2-6 catalyst
The preparation method comprises the following steps:
the difference from example 3 is only that the template agent is changed from F-127 to cetyltrimethylammonium bromide, resulting in Cu/SiO2-6 catalysts.
And (3) performance testing: the same as in example 1.
Comparative example 1 preparation of Cu/SiO by conventional Ammonia distillation2-7 catalyst
The preparation method comprises the following steps:
(1) 9.6g of Cu (NO) was added at room temperature3)2·3H2Dissolving O in 150mL of deionized water, adding ammonia water under stirring to adjust the pH value to 10, and continuously stirring for 10min to obtain a copper-ammonia complex solution;
(2) adding 25g of 30 wt% silica sol into the copper ammonia complex solution obtained in the step (1), adding ammonia water to adjust the pH to 11.0, and stirring for 4 hours to obtain a mixed solution;
(3) heating the mixed solution obtained in the step (2) to 85 ℃ for evaporation and ammonia removal, stopping heating after the pH value is reduced to 6-7, filtering the obtained mixed solution, washing and filtering the obtained precipitate with deionized water and ethanol, and drying at 90 ℃ for 12 hours to obtain a solid compound;
(4) calcining the solid compound obtained in the step (3) in air at 400 ℃ for 4H, and then in H2And N2In the mixed gas (H2 volume fraction of 10%), reducing and activating for 4H at 350 ℃ to obtain Cu/SiO2-7 catalysts.
And (3) performance testing: the same as in example 1.
Comparative example 2 preparation of Cu/SiO by precipitation2-8 catalyst
The preparation method comprises the following steps:
the difference from the example 1 is only that the template agent and the auxiliary agent are not added to obtain Cu/SiO2-8 catalyst.
And (3) performance testing: the same as in example 1.
The results of the performance tests of examples 1-6 and comparative examples 1-2 are shown in Table 1:
TABLE 1
Figure BDA0001549384460000081
The catalytic performance cycle test results of example 2 and comparative example 2 are shown in fig. 1 and fig. 2, respectively.
In conclusion, the nano copper-based catalyst prepared by the invention has good catalytic efficiency in the reaction of ethylene carbonate for catalytic hydrogenation and coproduction of methanol and ethylene glycol, the conversion rate of ethylene carbonate can reach 100%, the selectivity of ethylene glycol can reach 98%, and the selectivity of methanol can reach 72%. Meanwhile, the catalyst has excellent stability in a circulation experiment.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The preparation method of the nano copper-based catalyst is characterized by comprising the following steps of:
(1) dissolving a copper source, a silicon source, a template agent and an auxiliary agent in a solvent to obtain a precursor mixed solution, wherein the silicon source is tetraethoxysilane, the template agent is one or a combination of more of hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, P123 or F127, and the auxiliary agent is beta-cyclodextrin;
(2) mixing the precursor mixed solution obtained in the step (1) with a precipitator, adjusting the pH to 7-12, and stirring to obtain a mixed solution, wherein the precipitator is an ammonium carbonate solution and has the concentration of 0.1-1.5 mol/L;
(3) heating the mixed solution obtained in the step (2) to remove ammonia, and carrying out solid-liquid separation to obtain a solid compound;
(4) and (4) calcining the solid compound obtained in the step (3) in protective gas, and then reducing and activating in a reducing atmosphere to obtain the nano copper-based catalyst.
2. The method for preparing the nano copper-based catalyst according to claim 1, wherein in the step (1), the copper source is one or more of copper nitrate, copper sulfate or copper chloride; the solvent is water or a mixed solution of water and ethanol.
3. The method for preparing the nano copper-based catalyst according to claim 1, wherein in the step (1), the amount of the template is 5-150% of the mass of the copper component in the copper source.
4. The preparation method of the copper-based nano-catalyst according to claim 1, wherein in the step (1), the amount of the auxiliary agent is 10-50% of the mass of the copper component in the copper source.
5. The method for preparing the copper-based nano-catalyst according to claim 1, wherein in the step (3), the heating temperature is 50 to 100 ℃, and the heating is stopped when the pH is 6 to 7.
6. The preparation method of the copper-based nano-catalyst according to claim 1, wherein in the step (4), the protective gas is nitrogen, argon or helium, and the calcining temperature is 350-650 ℃.
7. The preparation method of the copper-based nano-catalyst according to claim 1, wherein in the step (4), the reducing atmosphere is a mixed gas of hydrogen and the protective gas, wherein the volume fraction of the hydrogen is 10-100%; the temperature of reduction activation is 300-450 ℃.
8. The nano copper-based catalyst obtained by the method of any one of claims 1 to 7, wherein the nano copper-based catalyst comprises copper and SiO2And carbon, wherein the mass fraction of copper is 0.5-45.0%, SiO245.0-89.5% by mass, and the balance carbon.
9. The application of the nano copper-based catalyst of claim 8 in the reaction of ethylene carbonate for catalytic hydrogenation and coproduction of methanol and ethylene glycol.
CN201810042396.4A 2018-01-16 2018-01-16 Nano copper-based catalyst and preparation method thereof Active CN108554407B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810042396.4A CN108554407B (en) 2018-01-16 2018-01-16 Nano copper-based catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810042396.4A CN108554407B (en) 2018-01-16 2018-01-16 Nano copper-based catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108554407A CN108554407A (en) 2018-09-21
CN108554407B true CN108554407B (en) 2020-12-04

Family

ID=63530819

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810042396.4A Active CN108554407B (en) 2018-01-16 2018-01-16 Nano copper-based catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108554407B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110152666B (en) * 2019-05-30 2021-07-13 福州大学 Porous carbon supported copper-based catalyst and preparation method thereof
CN110227545A (en) * 2019-06-28 2019-09-13 华东师范大学 It is a kind of for the catalyst of ethylene carbonate hydrogenation reaction and its preparation and application
CN110947382B (en) * 2019-08-27 2023-03-17 天津大学 Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof
CN114890950B (en) * 2022-05-16 2023-08-11 中国科学院过程工程研究所 Preparation method of 2-imidazolidone

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101166573A (en) * 2005-03-07 2008-04-23 金斯顿女王大学 Sol gel functionalized silicate catalyst and scavenger

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101166573A (en) * 2005-03-07 2008-04-23 金斯顿女王大学 Sol gel functionalized silicate catalyst and scavenger

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Influence of support on the performance of copper catalysts for the effective hydrogenation of ethylene carbonate to synthesize ethylene glycol and methanol;Fengjiao Li，et al;《RSC Adv.》;20160505(第51期);第45894-45906页 *
One-Pot Synthesis of Cyclodextrin-Doped Cu-SiO2 Catalysts for Efficient Hydrogenation of Dimethyl Oxalate to Ethylene Glycol;Run-Ping Ye，et al;《ChemCatChem》;20170828;第9卷(第24期);第4587-4597页 *

Also Published As

Publication number Publication date
CN108554407A (en) 2018-09-21

Similar Documents

Publication Publication Date Title
CN108554407B (en) Nano copper-based catalyst and preparation method thereof
CN108097316B (en) Preparation method of MOFs nano material loaded with nano metal particles
CN113145155B (en) Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof
CN109569695B (en) Preparation method and use method of core-shell structure catalyst for carbon dioxide hydrogenation
CN107829106B (en) Molybdenum sulfide/nitridation carbon composite preparation method and products thereof and application
CN107649157A (en) A kind of support type carbonization nickel indium alloy catalyst and its preparation method and application
CN102500381A (en) Preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis
CN111437846A (en) Porous CoO/CoP nanotube and preparation method and application thereof
CN109364931A (en) A kind of hydrogenation of carbon dioxide catalyst for methanol of core-shell structure and preparation method thereof
CN111760582A (en) MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst
CN106881143A (en) A kind of CuAu bimetallic catalysts and its preparation method and application
CN102744085B (en) Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation
CN109012743A (en) A kind of catalyst and its preparation method and application for hydrogenation of carbon dioxide gasoline directly processed
CN102416325A (en) Preparation method of isobutyl ketone synthesis catalyst
CN108816227B (en) Metal frame derived supported copper-based catalyst and preparation method thereof
CN111644169B (en) Metal composite modified nano zirconium oxide catalyst and preparation method and application thereof
CN110893346A (en) Bimetallic low-temperature methanation catalyst and preparation method and application thereof
CN111514889A (en) Ruthenium-based carbon dioxide hydromethanation catalyst and preparation method thereof
CN102942204A (en) Method for preparing cerium dioxide nanometer powder
CN114653374B (en) Double metal hydroxide and preparation method and application thereof
CN102974342B (en) Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof
CN106964369B (en) A kind of preparation method and application of heterojunction photocatalyst
CN105642289A (en) Preparation method of catalyst for complete methanation of syngas
CN114522708B (en) Preparation method of porous aza-carbon material supported cobalt-based catalyst and application of porous aza-carbon material supported cobalt-based catalyst in CO hydrogenation reaction for preparing high-carbon alcohol
CN110961136B (en) Fe with three-dimensional continuous structure3N-coated FeNCN compound and preparation method 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
GR01 Patent grant
GR01 Patent grant