CN113877578A - Method for preparing ternary copper catalyst from copper oxide powder - Google Patents
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- 239000010949 copper Substances 0.000 title claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 57
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 12
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000012216 screening Methods 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 239000005751 Copper oxide Substances 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- 229940112669 cuprous oxide Drugs 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
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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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing copper oxide powder, which comprises the steps of using conventional copper oxide powder or electronic-grade copper oxide powder as an initial raw material, screening the raw material, placing the raw material in a groove of a cathode plate, carrying out partial electro-reduction on the raw material under an alkaline condition, then obliquely shaking the product to fall off from the cathode plate, collecting the product, and drying the product. The preparation method of the ternary copper catalyst provided by the invention is used for catalyzing the synthesis reaction of the organic silicon monomer, is convenient to operate, does not need polluting reducing agents and solvents, does not need high-temperature calcination, is green and energy-saving in the whole preparation process, is suitable for large-scale production, and can improve the M2 selectivity and the Si conversion rate.
Description
Technical Field
The invention relates to the technical field of catalysts for synthesizing dimethyldichlorosilane, in particular to a method for preparing a ternary copper catalyst from copper oxide powder.
Background
The Rochow reaction found in the 40 th of the 20 th century was widely used for the industrial production of methylchlorosilanes. In this reaction, gaseous methyl chloride (MeCl) and solid silicon (Si) powder can react in the presence of a Cu-based catalyst to produce a series of different methylchlorosilanes, the reaction formula of which is shown below:
of the above reaction products, dimethyldichlorosilane (Me)2SiCl2M2) is the most important monomer for silicone rubber in the organosilane industry, and therefore efforts are made to improve M2 yield and selectivity. In addition to proper control of reaction conditions and selection of appropriate reactors, development of efficient copper-based catalysts is critical to improving M2 selectivity and Si conversion.
Research shows that the Cu-based catalyst (including metal Cu and Cu)2O, CuO, CuCl, Cu-Si alloy, and Cu-Cu2O-CuO) exhibit catalytic activity for the Rochow reaction in the presence of a promoter, especially Cu-Cu2The O-CuO ternary copper catalyst further shows excellent M2 yield and selectivity.
In recent years, a great deal of research is carried out on the large preparation of the ternary copper catalyst in China.
CN1008423B discloses a ternary copper catalyst prepared from copper sulfate through dehydration, drying, hydrogen reduction and partial oxidation. This process results in unstable quality of the final product due to the unstable quality of copper sulfate. And the high-temperature reduction of hydrogen has certain dangerousness.
CN102441381A discloses a ternary copper catalyst with a porous structure and a large specific surface area, which is prepared by taking copper oxide powder and electrolytic copper powder as initial raw materials and carrying out mixing, reduction, crushing, oxidation, screening and grinding, but the process is relatively complicated and the cost is high.
CN103127936A discloses a copper-based catalyst containing ternary components of copper, cuprous oxide and copper oxide, which is prepared by using copper oxide as a raw material, adding a solvent medium containing a reducing substance, performing mechanical ball milling to reduce and partially reduce copper oxide particles, performing suction filtration, drying and crushing. The existence of the solvent medium increases the subsequent treatment cost, and the final ball milling and crushing process easily causes the problem of uneven particle size distribution.
In addition, the ternary copper catalysts currently on the market are generally in a lamellar structure or a spherical structure, are easy to accumulate in a catalytic system, and cannot provide more catalytic active sites.
Therefore, an improved technique for solving the problem in the prior art is desired.
Disclosure of Invention
The invention aims to provide a method for preparing a ternary copper catalyst by using copper oxide powder, which is used for selectively synthesizing dimethyldichlorosilane (M2) in organosilicon monomer synthesis, does not relate to dangerous gas in the production process, does not have polluting solvent, has simple equipment and process and is easy to produce, and solves the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing a ternary copper catalyst by using copper oxide powder comprises the following steps:
the method comprises the following steps: copper oxide powder with the particle size of 1-100um is flatly paved in a groove of a cathode copper plate, is horizontally placed with an anode titanium plate, and is injected with 1-6M KOH or NaOH electrolyte to form an electrochemical reduction system;
step two: keeping the temperature of the electrolyte at a certain temperature of 15-50 ℃, applying a reduction voltage of 1.3-2.0V to the anode and the cathode in the electrolytic cell in two steps, shaking off reactants from a cathode plate after the reduction time is 10-100min, collecting and washing to obtain a ternary copper catalyst;
wherein, the ternary copper catalyst particles in the second step comprise Cu and Cu2O and CuO, and the proportion of each component is as follows: cu: 1% -15% of Cu2O：40％-80％，CuO：15％-45％。
Preferably, the specific surface area of the ternary copper catalyst in the second step is 5-30m2 g-1(ii) a The grain diameter is 1-100 um.
Preferably, the electronic-grade copper oxide powder in the first step is used as a reaction raw material in the first step.
Preferably, the electrolytic cell in the second step consists of an insoluble anode plate, a rotatable cathode plate with a groove and an alkaline electrolyte;
wherein the anode plate is a smooth and flat titanium plate or graphite plate, and the area of the anode plate is 1.2-1.5 times that of the cathode plate;
the anode plate is made of pure copper, and dense grooves are formed in one side, close to the anode, of the anode plate;
wherein the interval between the cathode plate and the anode plate is 5-20cm in the reaction process;
wherein the electrolyte is 1-6M KOH or NaOH aqueous solution;
wherein, the electrolytic cell is made of polytetrafluoroethylene or organic glass.
Preferably, the voltage applied in the second step is divided into two stages, wherein the voltage applied in the first stage is 1.3-1.5V, and the voltage applied in the second stage is 1.5-2.0V.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for preparing the Cu-Cu2O-CuO ternary copper catalyst by electro-reduction of the copper oxide powder has the advantages of simple process, convenient operation, no need of polluting reducing agents and solvents, no need of high-temperature calcination, green and energy-saving whole preparation process and suitability for large-scale production.
(2) The preparation method provided by the invention can keep the structural morphology of the original copper oxide powder, such as the hierarchical porous structure of electronic-grade copper oxide powder, is beneficial to the contact of a catalyst and reactants, exposes more catalytic active sites, and has higher M2 selectivity and Si conversion rate compared with a commercial catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a method for preparing a ternary copper catalyst by using copper oxide powder comprises the following steps:
the method comprises the following steps: screening the copper oxide powder by selecting screens with different meshes according to requirements to obtain reaction raw materials with the particle size of 1-100 um;
step two: uniformly distributing the copper oxide powder obtained in the step one in a groove of a cathode copper plate of an electrolytic cell, adding 1-6M potassium hydroxide or sodium hydroxide electrolyte, and selecting a titanium plate or a graphite plate as an anode plate to form an electrolytic cell system;
step three: and controlling the temperature of the electrolyte in the second step to be 15-50 ℃, firstly adjusting the voltage to 1.3-1.5V for carrying out first reduction for 5-60min, then increasing the voltage to 1.5-2.0V for carrying out second reduction for 5-40min, and finishing the reaction.
Step four: and (3) rotationally shaking the cathode plate after the third step of electric reduction, shaking the copper base split bodies in the grooves at the bottom of the electrolytic cell, collecting, and drying at 60-100 ℃ to obtain the ternary copper catalyst.
The copper oxide powder selected in the first step is of electronic grade and has the particle size of 1-10 um.
The electrolyte selected in the second step is 4-6M potassium hydroxide, and the anode is a titanium plate.
And the temperature of the electrolyte selected in the third step is 25-50 ℃.
The step-by-step electroreduction conditions selected in the third step are as follows: {1.35V, 50min/1.75V, 25min }, {1.4V, 30min/1.8V,10min }, and {1.5V, 10min/1.6V,50min }, etc.
And step four, the electrolytic cell is selected, the bottom of the electrolytic cell is conical, and an opening valve is arranged at the top of the electrolytic cell, so that the product can be conveniently collected.
The prepared ternary copper catalyst comprises the following components in percentage by weight:
Cu：1％-15％，
Cu2O：40％-80％，
CuO：15％-45％。
example 1
The embodiment provides a preparation method of a ternary copper catalyst, which specifically comprises the following steps:
firstly, 1000g of sieved copper oxide powder is weighed, laid in a groove of a copper cathode plate and placed in parallel with a titanium plate anode, and 6M potassium hydroxide aqueous solution is added into an electrolytic cell until two electrodes are submerged.
Secondly, under normal temperature and normal pressure, firstly applying a voltage of 1.35V to the two electrodes and keeping the voltage for 50min, partially reducing the copper oxide to cuprous oxide, then increasing the voltage to 1.75V and keeping the voltage for 25min, and reducing partial copper oxide and cuprous oxide to elemental copper.
And thirdly, obliquely shaking the prepared product from the cathode plate to the bottom of the electrolytic cell, collecting and drying the product to obtain the ternary copper catalyst.
And fourthly, redistributing new copper oxide powder in the grooves of the copper cathode plate to prepare a new batch of the ternary copper catalyst under the same conditions, wherein the concentration of potassium hydroxide is kept at 6M.
Example 2
The embodiment provides a preparation method of a ternary copper catalyst, which specifically comprises the following steps:
firstly, 1000g of sieved copper oxide powder is weighed, laid in a groove of a copper cathode plate and placed in parallel with a titanium plate anode, and 4M potassium hydroxide aqueous solution is added into an electrolytic cell until two electrodes are submerged.
Secondly, under normal temperature and normal pressure, firstly applying a voltage of 1.4V to the two electrodes and keeping the voltage for 30min, partially reducing the copper oxide to cuprous oxide, then increasing the voltage to 1.8V and keeping the voltage for 10min, and reducing partial copper oxide and cuprous oxide to elemental copper.
And thirdly, obliquely shaking the prepared product from the cathode plate to the bottom of the electrolytic cell, collecting and drying the product to obtain the ternary copper catalyst.
And fourthly, redistributing new copper oxide powder in the grooves of the copper cathode plate to prepare a new batch of the ternary copper catalyst under the same conditions, wherein the concentration of potassium hydroxide is kept to be 4M.
Example 3
The embodiment provides a preparation method of a ternary copper catalyst, which specifically comprises the following steps:
firstly, 1000g of sieved copper oxide powder is weighed, laid in a groove of a copper cathode plate and placed in parallel with a titanium plate anode, and 3M potassium hydroxide aqueous solution is added into an electrolytic cell until two electrodes are submerged.
Secondly, under normal temperature and normal pressure, firstly applying a voltage of 1.5V to the two electrodes and keeping the voltage for 10min, reducing the copper oxide to cuprous oxide, then increasing the voltage to 1.6V and keeping the voltage for 50min, and reducing partial copper oxide and cuprous oxide to elemental copper.
And thirdly, obliquely shaking the prepared product from the cathode plate to the bottom of the electrolytic cell, collecting and drying the product to obtain the ternary copper catalyst.
And fourthly, redistributing new copper oxide powder in the grooves of the copper cathode plate to prepare a new batch of ternary copper catalyst under the same conditions, wherein the concentration of potassium hydroxide is kept to be 3M.
And (3) evaluating the product performance:
the ternary copper catalyst prepared by the method and a ternary copper catalyst of a certain company are respectively used for catalyzing organosilicon monomer synthesis experiments. The specific experimental steps are as follows:
the catalyst was evaluated on a typical MCS laboratory fixed bed reactor by mixing 10g of Si powder, 0.2g of catalyst and 0.1g of Zn powder accelerator, grinding into catalyst bodies and loading into a glass reactor. The reaction system was first purged with high purity nitrogen for 0.5h, then heated to 325 ℃ over 1h, maintaining a nitrogen flow of 25 mL/min. The nitrogen was then turned off, MeCl gas was introduced at a flow rate of 25mL/min, the reaction was carried out with Si powder at 325 ℃ and the reaction was stopped after 24 h. The collected mixture was subjected to chromatographic analysis, and the conversion rate of Si powder and the product distribution were calculated, and the results are shown in table 1:
table 1 organosilicon monomer synthesis catalysis results:
the invention relates to a method for preparing a ternary copper catalyst by taking copper oxide powder as a raw material, which is prepared by taking conventional copper oxide powder or electronic-grade copper oxide powder as an initial raw material, screening the initial raw material, placing the initial raw material in a groove of a cathode plate, carrying out partial electro-reduction on the initial raw material under an alkaline condition, then obliquely shaking the product to fall off the cathode plate, collecting the product and drying the product. And the ternary copper catalyst prepared by preferably using the electronic-grade copper oxide powder as a raw material can keep the original porous structure and high specific surface area. The preparation method of the ternary copper catalyst provided by the invention can improve the selectivity of M2 and the conversion rate of Si in the synthesis reaction of catalytic organosilicon monomers.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for preparing a ternary copper catalyst by using copper oxide powder is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: copper oxide powder with the particle size of 1-100um is flatly paved in a groove of a cathode copper plate, is horizontally placed with an anode titanium plate, and is injected with 1-6M KOH or NaOH electrolyte to form an electrochemical reduction system;
step two: keeping the temperature of the electrolyte at a certain temperature of 15-50 ℃, applying a reduction voltage of 1.3-2.0V to the anode and the cathode in the electrolytic cell in two steps, shaking off reactants from a cathode plate after the reduction time is 10-100min, collecting and washing to obtain a ternary copper catalyst;
wherein, the ternary copper catalyst particles in the second step comprise Cu and Cu2O and CuO, and the proportion of each component is as follows: cu: 1% -15% of Cu2O：40％-80％，CuO：15％-45％。
2. The method for preparing a three-way copper catalyst from copper oxide powder according to claim 1, wherein the method comprises the following steps: the specific surface area of the ternary copper catalyst in the second step is 5-30m2g-1(ii) a The grain diameter is 1-100 um.
3. The method for preparing a three-way copper catalyst from copper oxide powder according to claim 1, wherein the method comprises the following steps: and taking the electronic-grade copper oxide powder in the step one as a reaction raw material in the step one.
4. The method for preparing a three-way copper catalyst from copper oxide powder according to claim 1, wherein the method comprises the following steps: the electrolytic cell in the second step consists of an insoluble anode plate, a rotatable cathode plate with a groove and alkaline electrolyte;
wherein the anode plate is a smooth and flat titanium plate or graphite plate, and the area of the anode plate is 1.2-1.5 times that of the cathode plate;
the anode plate is made of pure copper, and dense grooves are formed in one side, close to the anode, of the anode plate;
wherein the interval between the cathode plate and the anode plate is 5-20cm in the reaction process;
wherein the electrolyte is 1-6M KOH or NaOH aqueous solution;
wherein, the electrolytic cell is made of polytetrafluoroethylene or organic glass.
5. The method for preparing a three-way copper catalyst from copper oxide powder according to claim 1, wherein the method comprises the following steps: the voltage applied in the second step is divided into two stages, wherein the voltage applied in the first stage is 1.3-1.5V, and the voltage applied in the second stage is 1.5-2.0V.
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| KR20100098363A (en) * | 2010-08-19 | 2010-09-06 | 포항공과대학교 산학협력단 | Heterogeneous copper nanocatalyst and manufacturing methods thereof |
| CN105944722A (en) * | 2016-05-18 | 2016-09-21 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper catalyst and preparation method and application thereof |
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