WO2014117464A1 - Method for preparing catalyst through ball-milling and partial reduction in liquid phase and ternary copper catalyst - Google Patents

Method for preparing catalyst through ball-milling and partial reduction in liquid phase and ternary copper catalyst Download PDF

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WO2014117464A1
WO2014117464A1 PCT/CN2013/076874 CN2013076874W WO2014117464A1 WO 2014117464 A1 WO2014117464 A1 WO 2014117464A1 CN 2013076874 W CN2013076874 W CN 2013076874W WO 2014117464 A1 WO2014117464 A1 WO 2014117464A1
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copper
microns
based catalyst
catalyst
ternary
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PCT/CN2013/076874
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French (fr)
Chinese (zh)
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苏发兵
王莹利
翟世辉
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中国科学院过程工程研究所
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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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing

Definitions

  • the present invention relates to the field of catalysts for the synthesis reaction of dimethyldichlorosilane, and in particular, the present invention relates to a method for preparing a copper-based catalyst by a liquid phase ball milling partial reduction method.
  • Silicone materials combine the dual properties of inorganic materials (Si-O) and organic materials (Si-CH 3 ). They are not only widely used in civilian applications, but also have special military applications. They are extremely important in national economic and social development. Important role. Dimethyldichlorosilane (Me 2 SiCl 2 , M 2 for short) is the most important and most used monomer in the preparation of silicone products, and is the foundation and important pillar of the silicone industry. M 2 is synthesized by the reaction of a copper-based catalyst with Si powder and monochloromethane (MeCl) as a raw material. This is the direct synthesis method invented by EG Rochow in 1940.
  • the reaction may also be accompanied by side reactions such as thermal decomposition, disproportionation and hydrolysis of chlorosilane, resulting in complex reaction products and low selectivity of the target product.
  • Catalysts play a particularly important role in the direct synthesis reaction.
  • the reactivity of copper-based catalysts is closely related to their chemical composition, particle size distribution, surface morphology and preparation methods. It has been a hot issue of research and practice to improve the preparation method of the catalyst and the structure of the structure to improve the yield and selectivity of the target product M 2 .
  • the copper-based catalyst used in the synthesis of dimethyldichlorosilane is a copper powder comprising a metal copper powder, a particulate copper, a copper sheet or a combination thereof.
  • Zhejiang University CN1583571A, Tsinghua University CN1597107A and Qingdao University of Science and Technology CN102211031A have carried out related research on the preparation technology of high activity cuprous chloride catalyst. The results show that the cuprous chloride catalyst has high activity and short catalytic induction period, but in actual production. There are disadvantages such as difficulty in preservation and by-product SiCl 4 .
  • US SCM company CN85103904 uses copper powder
  • the ternary copper powder catalyst was prepared by partial oxidation treatment; CN1072870A of Jilin Chemical Industry Co., Ltd. studied the use of copper salt solution and active metal than copper as raw material, and used in the reactor with gas bubbling device, using reduced precipitation
  • a ternary copper-based catalyst rich in cuprous oxide, copper oxide and copper was directly prepared by a suspension oxidation-ruthenium method; CN87104211A, a branch of the Chenguang Research Institute of Chemical Industry, studied the dehydration, drying and reduction of copper salt and copper powder.
  • a partial oxidation process to prepare a ternary copper-based catalyst Kunming Silicon Ring Catalytic Technology Co., Ltd.
  • CN101811057A uses a predetermined ratio of copper, cuprous oxide and copper oxide powder for ball milling to obtain a ternary copper-based catalyst; Han Shuquan CN102059117A
  • the metal copper powder is used as a raw material, and two kinds of ternary copper-based catalysts with different compositions and different uses are prepared by surface oxidation, deep oxidation and partial reduction.
  • ternary copper-based catalysts are the most used catalysts in the production of methyl chlorosilane.
  • the above-mentioned ternary copper-based catalysts are produced in a complicated process, require special equipment and equipment, or have strong dependence on raw materials. The preparation conditions and the catalyst component content and the particle size are difficult to control, resulting in unstable catalyst performance.
  • the liquid phase reduction method is mostly applied to the preparation of ultrafine platinum powder, nano nickel powder, flake silver powder, palladium nanosphere and nickel cobalt alloy powder.
  • Jinchuan Group Co., Ltd. CN101279377A uses spherical reduction method to prepare spherical ultrafine copper powder.
  • CN1384055A of Nanjing University uses polyethylene glycol and acrylate to prepare copper oxide nanowire by reduction method.
  • Changzhou University CN102251278A uses ethylenediamine to reduce divalent Copper salt is used to prepare single crystal copper nanowires.
  • the above studies all use copper salt as raw material, the product easily carries the corresponding acid ion, and other metal ions are introduced in the process of adjusting the pH, so that the reaction process is long and the purity of the product is affected. Moreover, the obtained products are single phase.
  • the copper or cuprous oxide material is difficult to directly obtain the ternary copper composite material in which copper, cuprous oxide and copper oxide are simultaneously present.
  • one of the objects of the present invention is to provide a method for preparing a ternary copper-based catalyst.
  • the method comprises: adding copper oxide and a reducing substance to a solvent, grinding the reaction, removing impurities, and pulverizing to obtain a ternary copper-based catalyst.
  • the raw material copper oxide is an analytically pure copper oxide powder or a technical grade copper oxide powder; the copper oxide is commercially available, and can also be prepared by a person skilled in the art according to the prior art/new technology, for example, various types. Copper oxide obtained by calcination of copper salt, copper oxide oxidized by elemental copper and/or low-cost copper, copper oxide extracted by industrial copper-containing scrap, and copper oxide obtained by various other methods.
  • the raw material copper oxide has a particle size of 600 microns or less, such as 0.1 micron, 0.2 micron, 0.9 micron, 1.1 micron, 2 micron, 3 micron, 4 micron, 6 micron, 10 micron, 20 micron, 50 micron, 100.
  • Micron, 150, 200, 300, 400, 450, 490, 499, 501, 510, 520, 530, 540, 548, 549, etc. preferably 1 ⁇ 550 microns, particularly preferably 5 to 500 microns.
  • a cocatalyst is added to the reaction system; preferably, the cocatalyst is a combination of one or at least two of elemental elements, oxides, halides or copper alloys of elements, such as zinc, tin or One or a combination of at least two of phosphorus, such as: zinc elemental, zinc oxide, zinc halide, copper-zinc alloy, tin element, tin oxide, tin halide, copper-tin alloy, phosphorus elemental, phosphorus pentoxide, phosphorus halide Or a combination of one or at least two of copper-phosphorus alloys, for example: zinc, tin, white phosphorus, red phosphorus, zinc oxide, tin dioxide, phosphorus pentoxide, zinc halide, tin halide, phosphorus halide, zinc-copper alloy a combination of one or at least two of a copper-tin alloy, a copper-tin-zinc alloy, a phosphor bronze
  • typical but non-limiting examples of the cocatalyst include: a mixture of zinc and tin, a zinc-tin alloy, a phosphorus-tin alloy, a combination of tin, white phosphorus and red phosphorus, zinc fluoride, chlorination Tin and pentoxide Phosphorus combination, combination of zinc oxide, tin dioxide and tin tetrabromide, tin, white phosphorus, red phosphorus, combination of zinc oxide and tin dioxide, zinc-copper alloy, copper-tin alloy, copper-tin-zinc alloy, pentoxide a combination of phosphorus and white phosphorus, and the like.
  • the promoter has a particle size of 600 microns or less, such as 0.1 microns, 0.2 microns, 0.9 microns, 1.1 microns, 2 microns, 3 microns, 4 microns, 6 microns, 10 microns, 20 microns, 50 microns, 100 microns.
  • the mass ratio of the cocatalyst to the raw material copper oxide is 15:100 or less, for example, 0.01:100, 0.1:100, 0.2:100, 1:100, 2:100, 5:100, 7:100, 9 : 100, 11:100, 13:100, 14:100, 14.5: 100, 14.8: 100, 14.9: 100, etc., further preferably 12:100 or less, particularly preferably 10:100 or less.
  • the reducing substance is one or a combination of at least two of hydrazine hydrate, glucose, formaldehyde, ascorbic acid or sodium borohydride, such as a combination of hydrazine hydrate and glucose, a combination of formaldehyde and ascorbic acid, glucose, formaldehyde and a combination of sodium borohydride, a combination of hydrazine hydrate, glucose, formaldehyde and sodium borohydride, a combination of hydrazine hydrate, glucose, formaldehyde, ascorbic acid and sodium borohydride; and the reducing substance means a substance which can reduce copper oxide.
  • the mass ratio of the reducing substance to the raw material copper oxide is 0.01:15:1, for example, 0.02:1, 0.05:1, 0.09:1, 0.11:1, 0.15:1, 0.2:1, 0.5: 1, 1:1, 1.5:1, 1.9:1, 2.1:1, 3:1, 5:1, 8:1, 9:1, 9.9:1, 10.1:1, 11:1, 12:1 14:1, 14.5:1, 14.8:1, 14.9:1, etc., further preferably 0.01:1-10:1, particularly preferably 0.1:1 to 2:1.
  • the solvent is water and/or an organic solvent, for example: alcohols, ketones, aromatics, ethers, anthrahydrocarbons, etc., such as C ⁇ do alcohols (such as methanol, ethanol, n-propanol, Isopropanol, ethylene glycol, 1,3-propanediol, n-butanol, n-pentanol, n-hexanol, cyclohexanol, etc.), C 2 ⁇ C 1Q ethers (eg methyl ether, methyl ethyl ether, diethyl ether, n-propyl) Ether, n-butyl ether, tetrahydrofuran, etc.), C 3 ⁇ C 1Q ketones (acetone, butanone, 2-pentanone, propiophenone, etc.), C 6 ⁇ C 2Q saturated anthracene (such as n-glycan, hex
  • the mass ratio of the solvent to the raw material copper oxide is 0.8: 1 to 15: 1, for example, 0.81: 1, 0.82:1, 0.9:1, 0.99:1, 1.1:1, 1.2:1, 1.5:1 , 2: 1, 4:1, 6: 1, 7: 1, 8:1, 9:1, 11:1, 12:1, 14:1, 14.5:1, 14.8:1, 14.9:1, etc. Further, it is preferably from 1:1 to 10: 1, particularly preferably from 1:1 to 5:1.
  • the apparatus used for the grinding is any one of a planetary ball mill, a barrel mill, a stirring mill, a vibration mill or a sand mill.
  • the grinding time is greater than 0 hours, such as 0.001 hours, 0.01 hours, 0.1 hours, 0.4 hours, 1 hour, 1.5 hours, 1.9 hours, 2.1 hours, 3 hours, 5 hours, 9 hours, 11 hours, 15
  • the hour, the 20 hour, the 23 hour, the 25 hour, the 30 hour, and the like are preferably 0.5 to 24 hours, particularly preferably 2 to 10 hours.
  • the grinding can make the copper oxide particles smaller and partially reduced.
  • the grinding time can be the same as the reaction time, that is, the reaction is carried out while grinding, and the end of the reaction is completed, and the grinding time can also be less than the reaction time. For example, after the grinding reaction for a period of time, the reaction is allowed to stand for a while, or the reaction is for a period of time. Thereafter, grinding is carried out to carry out the reaction while grinding.
  • the impurity removal comprises sequential filtration and drying; preferably, the filtration is suction filtration.
  • the copper-based catalyst prepared by the present method comprises metallic copper powder, cuprous oxide powder, and copper oxide powder.
  • the copper-based catalyst of different composition can be prepared by adjusting parameters such as the type and concentration of the reducing substance and the milling conditions as needed.
  • the method of the invention uses copper oxide as a raw material, and simultaneously completes grinding and partial reduction by liquid phase ball milling reduction to prepare a composite material containing copper, cuprous oxide and copper oxide ternary components. Under the action of high-energy grinding force, the material is continuously ground and continuously reduced, so that the particles become smaller and smaller, and the reinforcement is enhanced.
  • the ability of the copper oxide powder to participate in the reduction reaction causes the copper oxide raw material to be reduced layer by layer from the outside to the inside, forming a layered multiphase mosaic structure; strengthening the interaction between copper, cuprous oxide and copper oxide,
  • the distribution of the three constituent elements Cu, Cu 2 0 and CuO in the catalyst is more uniform, and the reaction of the methyl chlorosilane target is enhanced in the reaction of the silicon powder and the chloroformamide to form a methyl chlorosilane group monomer.
  • new impurity elements are not introduced, the product purity is high, the composition of the obtained ternary copper-based catalyst component is adjustable, and the particle size is controllable.
  • the method is simple, mild, and easy to control, and the phase composition, morphology and particle size of the product are easily controlled.
  • the copper-based catalyst according to the present invention controls the particle size by the action of the grinding force, and at the same time, adjusts the content of each component under the action of the reducing substance and the grinding force, and makes each group under the action of the grinding force.
  • the interaction between the divisions is strengthened.
  • One of the objects of the present invention is to provide a ternary copper-based catalyst which is prepared by the above method and contains elemental copper, cuprous oxide and copper oxide.
  • the copper-based three-way catalyst has a particle diameter of 0.1 to 70 ⁇ m, such as 0.11 ⁇ m, 0.12 ⁇ m, 0.15 ⁇ m, 0.19 ⁇ m, 0.21 ⁇ m, 0.25 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.6 ⁇ m, 1 ⁇ m, 5 Micron, 9 microns, 11 microns, 20 microns, 40 microns, 49 microns, 51 microns, 60 microns, 65 microns, 68 microns, 69 microns, etc., further preferably from 0.2 to 50 microns, particularly preferably from 0.5 to 10 microns.
  • the content of elemental copper in the ternary copper-based catalyst is 0.5 to 95 wt%, for example, 0.51 wt%, 0.52 wt%, 0.6 wt%, 0.7 wt%, 0.9 wt%, 1.1 wt%, 1.5 wt%. 2 wt%, 10 wt%, 40 wt%, 60 wt%, 80 wt%, 85 wt%, 89 wt%, 91 wt%, 92 wt%, 94 wt%, 94.8 wt%, 94.9 wt%, etc., further preferably 0.8 to 93 wt%, particularly It is preferably from 1 to 90% by weight.
  • the content of cuprous oxide in the ternary copper-based catalyst is 2-95 wt%, for example 2.1 wt%, 2.2 wt% 2.5 wt%, 2.9 wt%, 3.1 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 4.9 wt%, 5.1 wt%, 6 wt%, 10 wt%, 30 wt%, 60 wt%, 80 wt%, 85 wt %, 89 wt%, 91 wt%, 92 wt%, 94 wt%, 94.5 wt%, 94.8 wt%, 94.9 wt%, etc., further preferably from 3 to 93 wt%, particularly preferably from 5 to 90 wt%
  • the content of copper oxide in the ternary copper-based catalyst is 2 to 95 wt%, for example, 2.1 wt%, 2.2 wt%, 2.5 wt%, 2.9 wt%, 3.1 wt%, 3.5 wt%, 4 wt%, 4.5 wt% %, 4.9 wt%, 5.1 wt%, 6 wt%, 10 wt%, 30 wt%, 60 wt%, 80 wt%, 85 wt%, 89 wt%, 91 wt%, 92 wt%, 94 wt%, 94.5 wt%, 94.8 wt%, 94.9 wt% %, etc., further preferably from 3 to 93% by weight, particularly preferably from 5 to 90%
  • the catalyst may further contain a cocatalyst, for example, the cocatalyst is a combination of one or at least two of an elemental substance, an oxide, a halide or a copper alloy of an element, and the element is one of zinc, tin or phosphorus.
  • the cocatalyst is a combination of one or at least two of an elemental substance, an oxide, a halide or a copper alloy of an element, and the element is one of zinc, tin or phosphorus.
  • At least two combinations such as: zinc, tin, white phosphorus, red phosphorus, zinc oxide, tin dioxide, phosphorus pentoxide, zinc halide, tin halide, phosphorus halide, zinc copper alloy, copper tin alloy, copper tin a combination of one or at least two of a zinc alloy, a phosphor bronze alloy, or a phosphorus copper tin alloy, and the halide may be one or at least two of a fluoride, a chloride, a bromide or an iodide.
  • typical but non-limiting examples of the cocatalyst include: a mixture of zinc and tin, a zinc-tin alloy, a phosphorus-tin alloy, a combination of tin, white phosphorus, and red phosphorus, zinc fluoride, tin chloride, and phosphorus pentoxide.
  • Combination combination of zinc oxide, tin dioxide and tin tetrabromide, tin, white phosphorus, red phosphorus, a combination of zinc oxide and tin dioxide, zinc-copper alloy, copper-tin alloy, copper-tin-zinc alloy, phosphorus pentoxide and White phosphorus Combination, etc.
  • the ternary copper-based catalyst can be used as a catalyst for the synthesis reaction of dimethyldichlorosilane, has high catalytic activity and selectivity of dimethyldichlorosilane, and can greatly improve dimethyldichlorosilane. Yield.
  • the advantages of the present invention over the prior art are: (1) The present invention uses a liquid phase ball milling partial reduction method to prepare a ternary copper-based catalyst containing copper, cuprous oxide and copper oxide. This method does not introduce any impurity ions, and the catalyst composition and particle size are simultaneously controlled.
  • the preparation method of the copper-based catalyst according to the present invention is simple in process, mild in condition, simple in operation, and easy to realize large-scale production.
  • the copper-based catalyst prepared by the present invention exhibits a high selectivity for dimethyldichlorosilane and a conversion ratio of the silicon powder raw material.
  • Figure 1 is an XRD chart of a copper-based catalyst prepared in Example 1.
  • Figure 2 is a particle size analysis of the copper-based catalyst prepared in Example 1.
  • Figure 3 is an SEM image of the copper-based catalyst prepared in Example 1.
  • Figure 4 is an XRD pattern of the copper-based catalyst prepared in Example 2.
  • Figure 5 is a particle size analysis of the copper-based catalyst prepared in Example 2.
  • Figure 6 is an SEM image of the copper-based catalyst prepared in Example 2.
  • a ternary copper catalyst can be obtained; after chemical analysis, the composition is: 10.1% Cu, 51.5% Cu 2 0 and 38.4% CuO.
  • the ternary copper catalyst material prepared above was produced at Panalytical (Panaco), the Netherlands. XRD testing was performed on a X'Pert PRO MPD multi-function X-ray diffractometer.
  • the ternary copper catalyst material prepared above was subjected to particle size analysis on a Dandong Baxter BT-9300Z laser particle size distribution analyzer.
  • the surface morphology of the ternary copper catalyst material prepared above was observed by a JSM7100F field emission scanning electron microscope manufactured by JEOL.
  • Fig. 2 is a particle size analysis of the copper-based catalyst obtained in Example 1. As is apparent from the figure, the particle diameter of the copper-based catalyst was all less than 30 ⁇ m, and most of the particle diameter was 3 ⁇ m.
  • Fig. 3 is a SEM image of the copper catalyst obtained in Example 1. As is apparent from the figure, the particles of the copper-based catalyst were amorphous, and most of them were less than 10 ⁇ m.
  • the copper oxide powder obtained by calcining lO.Og from copper oxalate, 0.25 g of zinc oxide powder and 25 g of grinding beads were placed in a grinding jar, and 20.0 g of water and 5.0 g of formaldehyde were sequentially added; the mixture was ground for 8 h on a stirring mill to obtain the obtained product. After suction filtration, drying and dispersion, a ternary copper catalyst can be obtained; after chemical analysis, the composition is: 20.2% Cu, 33.3% Cu 2 0 and 46.5% CuO.
  • Figure 5 is a particle size analysis of the copper-based catalyst obtained in Example 2, which shows that the copper-based catalyst The particle size is all less than 20 microns, with most of the particle size being 2-3 microns.
  • Fig. 6 is a SEM image of the copper-based catalyst obtained in Example 2. As is apparent from the figure, the particles of the copper-based catalyst were in the form of flakes having a small sheet size and a large particle size of less than 10 ⁇ m.
  • a copper-based catalyst can be obtained; after chemical analysis, the composition is: 90.0% Cu, 5.0% Cu 2 O and 5.0% CuO, the particle diameters are all less than 50 micrometers, and most of the particle diameter is 10-20 micrometers;
  • the copper-based catalyst has a sheet-like structure having a large diameter of about 10 to 20 ⁇ m and a sheet thickness of substantially less than 1 ⁇ m.
  • the ternary copper catalyst can be obtained; after chemical analysis, the composition is: 11.6% Cu, 53.1% Cu 2 0 and 35.3% CuO, the particle size is less than 20 microns, and most of the particle size is 2- 3 microns, the particle morphology is amorphous.
  • the composition is: 33.5% Cu, 48.9% Cu 2 0 and 17.6% CuO, the particle size is less than 20 microns, most of the particle size is 2-3 microns, and the particles are amorphous.
  • the lO.Og analytical pure copper oxide powder, 0.9635 g metal zinc powder, 0.0015 g metal tin powder and 0.0350 g copper phosphorus alloy powder were placed in a beaker, and 10 g of water and 5.0 g of hydrazine hydrate were sequentially added; on a magnetic stirrer After reacting for 2 h, grinding on a vibration mill for 0.5 h, the obtained product was suction filtered, dried and dispersed to obtain a ternary copper catalyst; after chemical analysis, the composition was: 20.6% Cu, 28.2% Cu 2 0 and 51.2% CuO has a particle size of less than 30 microns, most of which has a particle size of 10 microns, and the particles have an amorphous structure.
  • the ternary copper catalyst can be obtained; after chemical analysis, the composition is: 24.9% Cu, 54.3% Cu 2 0 and 20.8% CuO, the particle size is less than 20 microns, most of the particle size is 2-3 microns, the particle morphology is amorphous.
  • Example 10 5.0 g of copper oxide powder oxidized by cuprous oxide and 25 g of grinding beads were placed in a roller mill, and 10 g of water and 6.0 g of glucose were sequentially added; the mixture was ground for 8 h on a roller mill, and the obtained product was suction filtered and dried. After dispersion, a copper-based catalyst can be obtained; after chemical analysis, the composition is: 10.5% Cu, 47.8% Cu 2 0 and 41.7% CuO, the particle size is about 0.2 ⁇ m, and the particles have an amorphous structure.
  • Catalyst performance evaluation was carried out using a micro-fixed bed apparatus: Si powder and copper-based catalyst were uniformly mixed at a ratio of 10:1, and then filled into a fixed bed reactor ( ⁇ 20 ⁇ 50) to form a mixed contact; The reaction system is purged with N 2 , and then switched to MeCl gas. After preheating, it is contacted with the mixed contact body at a reaction temperature of 325 ° C. The reacted product flows out from the lower end of the reactor, is condensed through a condenser, and is collected by using toluene.
  • the selectivity of dimethyldichlorosilane is only 65.1%, wherein monomethyltrichloro The silicon germanium is 14.0%, the monomethyldichlorosilane is 13.2%, and the Si powder conversion is 20.2%; therefore, the commercial catalyst has a large amount of by-produced monomethyltrichlorosilane and monomethyldichlorosilane. ⁇ , the selectivity of the target product dimethyldichlorosilane is low.
  • the catalytic performance is different due to the different content of the ternary component in the copper catalyst, and the most important index of dimethyldichlorosilane is from 69.0% to 86.8%.
  • Etc. the conversion rate of silicon powder varies from 26.4% to 65.7%; the catalytic performance of the copper-based catalyst is greatly improved, the selectivity of dimethyldichlorosilane is up to 86.8%, and the conversion rate of Si powder is also 42.1%.
  • Example 1 9.8 81.5 4.0 2.0 1.5 0.7 0.5 34.8
  • Example 2 16.3 69.0 1.4 11.7 0.4 0.9 0.3 26.4
  • Example 3 14.4 76.5 2.5 2.5 2.3 0.5 1.3 53.6
  • Example 4 6.6 86.8 1.6 1.9 0.9 1.5 0.7 42.1
  • Example 5 12.5 76.7 1.4 6.1 1.4 1.0 0.9 45.6
  • Example 6 9.2 81.0 2.3 3.7 0.9 0.1 2.8 60.0
  • Example 7 15.8 72.1 2.2 4.4 1.3 1.5 2.7 26.5
  • Example 8 8.8 83.8 1.3 4.2 0.7 0.4 0.8 42.5
  • Example 9 11.4 70.3 1.4 13.1 3.1 0.2 0.5 34.5
  • Example 10 8.5 80.3 1.5 5.6 0.9 0.6 2.6 30.1
  • Example 11 8.4 79.1 1.8 5.8 0.7 1.0 3.2 65.7
  • Example 12 11.6 73.5 2.0 9.1 1.3 0.4 2.1 41.2
  • Example 13 11.0 76.2 1.8 6.8 1.5 0.8 1.9 39
  • M 1 -methyltrichlorosilane
  • M 2 dimethyldichlorosilane
  • M 3 trimethylsilyl phosphonium
  • ⁇ Methyl dichlorohydrosilane
  • M 2 H dimethyl-chlorohydrosilane
  • LBR low-boiling substance
  • HBR high-boiling substance
  • s is the chromatographic peak area of the substance and is the weight of the substance.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Abstract

A ternary copper-based catalyst, a preparation method therefor and application thereof. The preparation method of the catalyst comprises: adding copper oxide and reduction material into solvent, milling, reacting, removing impurity and crushing to obtain a copper-based catalyst comprising ternary components of copper, cuprous oxide and copper oxide. When being used for synthesizing an organosilicon monomer, the catalyst has higher catalytic activity and selectivity, can improve the processing capacity of present organosilicon monomer equipment, reduce the production costs and improve the yield of target products. The preparation method is simple, can be performed easily under mild conditions, and can be used to realize large-scale production.

Description

一种液相球磨部分还原法制备催化剂的方法及三元铜催化剂 技术领域  Method for preparing catalyst by liquid phase ball milling partial reduction method and ternary copper catalyst
本发明涉及用于二甲基二氯硅垸合成反应的催化剂的领域， 具体地， 本发 明涉及一种液相球磨部分还原法制备铜基催化剂的方法。  The present invention relates to the field of catalysts for the synthesis reaction of dimethyldichlorosilane, and in particular, the present invention relates to a method for preparing a copper-based catalyst by a liquid phase ball milling partial reduction method.
背景技术 Background technique
有机硅材料兼具无机材料（Si-O)和有机材料（Si-CH3) 的双重性能， 不仅 在民用方面用途广泛， 而且还有特殊的军事用途， 在国民经济和社会发展中起 着极其重要的作用。 二甲基二氯硅垸 （Me2SiCl2， 简称 M2) 作为制备有机硅产 品中最重要、 用量最大的单体， 是有机硅工业的基础和重要支柱。 M2是以 Si 粉和一氯甲垸 （MeCl) 为原料， 在铜基催化剂的作用下， 通过加热反应而合成 的，这就是 1940年 E. G. Rochow发明的直接合成法。反应中还可能伴生热分解、 歧化及氯硅垸水解等副反应， 致使反应产物复杂， 目的产物选择性较低。 催化 剂在直接合成反应中占有特别重要的地位， 铜基催化剂的反应性能与其化学组 成、 粒径分布、 表面形貌及其制备方法均有很大关系。 通过改进催化剂的制备 方法及其结构的构筑方式以提高目标产物 M2的产率和选择性，一直是研究和实 践关注的热点问题。 Silicone materials combine the dual properties of inorganic materials (Si-O) and organic materials (Si-CH 3 ). They are not only widely used in civilian applications, but also have special military applications. They are extremely important in national economic and social development. Important role. Dimethyldichlorosilane (Me 2 SiCl 2 , M 2 for short) is the most important and most used monomer in the preparation of silicone products, and is the foundation and important pillar of the silicone industry. M 2 is synthesized by the reaction of a copper-based catalyst with Si powder and monochloromethane (MeCl) as a raw material. This is the direct synthesis method invented by EG Rochow in 1940. The reaction may also be accompanied by side reactions such as thermal decomposition, disproportionation and hydrolysis of chlorosilane, resulting in complex reaction products and low selectivity of the target product. Catalysts play a particularly important role in the direct synthesis reaction. The reactivity of copper-based catalysts is closely related to their chemical composition, particle size distribution, surface morphology and preparation methods. It has been a hot issue of research and practice to improve the preparation method of the catalyst and the structure of the structure to improve the yield and selectivity of the target product M 2 .
通用电气公司 CN18200014A、 信越化学工业株式会社 US6686312 和 US6365766在合成二甲基二氯硅垸中使用的铜基催化剂为铜粉， 包括金属铜粉、 微粒铜、 铜片或其组合物。 浙江大学 CN1583571A、 清华大学 CN1597107A和 青岛科技大学 CN102211031A曾对高活性氯化亚铜催化剂的制备技术进行了相 关的研究， 结果表明氯化亚铜催化剂活性较高， 催化诱导期短， 但在实际生产 中存在不易保存、 副产 SiCl4等缺点。 美国 SCM公司 CN85103904采用铜粉进 行部分氧化处理后制得三元铜粉催化剂；吉林化学工业公司研究院 CN1072870A 研究了以铜盐溶液及比铜活泼的金属为原料， 在带有气体鼓泡装置的反应釜中， 采用还原沉淀一悬浮氧化一歩法直接制得富含氧化亚铜、 氧化铜、 铜的三元铜 基催化剂； 化学工业部晨光化工研究院一分院 CN87104211A研究了以铜盐和铜 粉为原料经脱水干燥、 还原和部分氧化等工艺制备三元铜基催化剂； 昆明硅环 催化科技有限责任公司 CN101811057A采用将既定配比的铜、 氧化亚铜和氧化 铜粉末进行球磨， 得到了三元铜基催化剂； 韩树全 CN102059117A 以金属铜粉 为原料， 经过表面氧化、 深度氧化和部分还原的方法制备两种不同组成不同用 途的三元铜基催化剂。 目前该类三元铜基催化剂是甲基氯硅垸生产中使用最多 的一种催化剂， 上述三元铜基催化剂的生产过程中， 或者工艺复杂， 需要特殊 装置和设备， 或者原料依赖性较强， 其制备条件和催化剂组分含量和粒度大小 难以控制， 从而造成催化剂的性能不稳定。 The copper-based catalyst used in the synthesis of dimethyldichlorosilane is a copper powder comprising a metal copper powder, a particulate copper, a copper sheet or a combination thereof. Zhejiang University CN1583571A, Tsinghua University CN1597107A and Qingdao University of Science and Technology CN102211031A have carried out related research on the preparation technology of high activity cuprous chloride catalyst. The results show that the cuprous chloride catalyst has high activity and short catalytic induction period, but in actual production. There are disadvantages such as difficulty in preservation and by-product SiCl 4 . US SCM company CN85103904 uses copper powder The ternary copper powder catalyst was prepared by partial oxidation treatment; CN1072870A of Jilin Chemical Industry Co., Ltd. studied the use of copper salt solution and active metal than copper as raw material, and used in the reactor with gas bubbling device, using reduced precipitation A ternary copper-based catalyst rich in cuprous oxide, copper oxide and copper was directly prepared by a suspension oxidation-ruthenium method; CN87104211A, a branch of the Chenguang Research Institute of Chemical Industry, studied the dehydration, drying and reduction of copper salt and copper powder. And a partial oxidation process to prepare a ternary copper-based catalyst; Kunming Silicon Ring Catalytic Technology Co., Ltd. CN101811057A uses a predetermined ratio of copper, cuprous oxide and copper oxide powder for ball milling to obtain a ternary copper-based catalyst; Han Shuquan CN102059117A The metal copper powder is used as a raw material, and two kinds of ternary copper-based catalysts with different compositions and different uses are prepared by surface oxidation, deep oxidation and partial reduction. At present, such ternary copper-based catalysts are the most used catalysts in the production of methyl chlorosilane. The above-mentioned ternary copper-based catalysts are produced in a complicated process, require special equipment and equipment, or have strong dependence on raw materials. The preparation conditions and the catalyst component content and the particle size are difficult to control, resulting in unstable catalyst performance.
液相还原法大部分应用于制备超细铂粉、 纳米镍粉、 片状银粉、 钯纳米球 以及镍钴合金粉等。 金川集团有限公司 CN101279377A使用两歩还原法制备球 形超细铜粉， 南京大学 CN1384055A使用聚乙二醇和丙烯酸酯将铜盐采用还原 法制备氧化亚铜纳米线， 常州大学 CN102251278A使用乙二胺还原二价铜盐制 备单晶铜纳米线。 上述研究均采用铜盐为原料， 产物中易携带相应的酸根离子， 酸碱度的调整过程中又引入了其它金属离子， 使反应工艺流程较长， 产品纯度 受到影响； 而且， 所得产物均为单相的铜或氧化亚铜材料， 很难直接得到铜、 氧化亚铜和氧化铜同时存在的三元铜复相材料。  The liquid phase reduction method is mostly applied to the preparation of ultrafine platinum powder, nano nickel powder, flake silver powder, palladium nanosphere and nickel cobalt alloy powder. Jinchuan Group Co., Ltd. CN101279377A uses spherical reduction method to prepare spherical ultrafine copper powder. CN1384055A of Nanjing University uses polyethylene glycol and acrylate to prepare copper oxide nanowire by reduction method. Changzhou University CN102251278A uses ethylenediamine to reduce divalent Copper salt is used to prepare single crystal copper nanowires. The above studies all use copper salt as raw material, the product easily carries the corresponding acid ion, and other metal ions are introduced in the process of adjusting the pH, so that the reaction process is long and the purity of the product is affected. Moreover, the obtained products are single phase. The copper or cuprous oxide material is difficult to directly obtain the ternary copper composite material in which copper, cuprous oxide and copper oxide are simultaneously present.
发明内容 Summary of the invention
针对现有技术的不足， 本发明的目的之一在于提供一种三元铜基催化剂的 制备方法。 所述方法包括： 将氧化铜与还原性物质加入至溶剂中， 研磨反应， 除杂， 粉碎， 得到三元铜基催化剂。 In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a method for preparing a ternary copper-based catalyst. The method comprises: adding copper oxide and a reducing substance to a solvent, grinding the reaction, removing impurities, and pulverizing to obtain a ternary copper-based catalyst.
优选地， 所述原料氧化铜为分析纯氧化铜粉末或工业级氧化铜粉末； 所述 氧化铜可以通过市售获得， 也可由所属领域技术人员根据现有技术 /新技术制备 得到， 例如各类铜盐煅烧获得的氧化铜， 单质铜和 /或低价铜氧化而成的氧化铜， 工业含铜废料提取回收的氧化铜， 以及其它各种方法得到的氧化铜。  Preferably, the raw material copper oxide is an analytically pure copper oxide powder or a technical grade copper oxide powder; the copper oxide is commercially available, and can also be prepared by a person skilled in the art according to the prior art/new technology, for example, various types. Copper oxide obtained by calcination of copper salt, copper oxide oxidized by elemental copper and/or low-cost copper, copper oxide extracted by industrial copper-containing scrap, and copper oxide obtained by various other methods.
优选地， 所述原料氧化铜的粒度为 600微米以下， 例如 0.1微米、 0.2微米、 0.9微米、 1.1微米、 2微米、 3微米、 4微米、 6微米、 10微米、 20微米、 50微 米、 100微米、 150微米、 200微米、 300微米、 400微米、 450微米、 490微米、 499微米、 501微米、 510微米、 520微米、 530微米、 540微米、 548微米、 549 微米等， 进一歩优选为 1~550微米， 特别优选为 5~500微米。  Preferably, the raw material copper oxide has a particle size of 600 microns or less, such as 0.1 micron, 0.2 micron, 0.9 micron, 1.1 micron, 2 micron, 3 micron, 4 micron, 6 micron, 10 micron, 20 micron, 50 micron, 100. Micron, 150, 200, 300, 400, 450, 490, 499, 501, 510, 520, 530, 540, 548, 549, etc., preferably 1 ~550 microns, particularly preferably 5 to 500 microns.
优选地， 在反应体系中加入助催化剂； 优选地， 所述助催化剂为元素的单 质、 氧化物、 卤化物或铜合金中的 1种或至少 2种的组合， 所述元素为锌、 锡 或磷中的 1种或至少 2种的组合， 例如： 锌单质、 氧化锌、 卤化锌、 铜锌合金、 锡单质、 氧化锡、 卤化锡、 铜锡合金、 磷单质、 五氧化二磷、 卤化磷或铜磷合 金中的 1种或至少 2种的组合， 例如： 锌、 锡、 白磷、 红磷、 氧化锌、 二氧化 锡、 五氧化二磷、 卤化锌、 卤化锡、 卤化磷、 锌铜合金、 铜锡合金、 铜锡锌合 金、 磷铜合金或磷铜锡合金等种的 1种或至少 2种的组合， 所述卤化物可以为 氟化物、 氯化物、 溴化物含或碘化物中的 1种或至少 2种的组合， 所述助催化 剂典型但非限制性的实例包括： 锌和锡混合物， 锌锡合金， 磷锡合金， 锡、 白 磷和红磷的组合， 氟化锌、 氯化锡和五氧化二磷的组合， 氧化锌、 二氧化锡和 四溴化锡的组合， 锡、 白磷、 红磷、 氧化锌和二氧化锡的组合， 锌铜合金、 铜 锡合金、 铜锡锌合金、 五氧化二磷和白磷的组合等。 优选地， 所述助催化剂的粒度为 600微米以下， 例如 0.1微米、 0.2微米、 0.9微米、 1.1微米、 2微米、 3微米、 4微米、 6微米、 10微米、 20微米、 50微 米、 100微米、 150微米、 200微米、 300微米、 400微米、 450微米、 490微米、 499微米、 501微米、 510微米、 520微米、 530微米、 540微米、 548微米、 549 微米等， 进一歩优选为 1~550微米， 特别优选为 5~500微米。 Preferably, a cocatalyst is added to the reaction system; preferably, the cocatalyst is a combination of one or at least two of elemental elements, oxides, halides or copper alloys of elements, such as zinc, tin or One or a combination of at least two of phosphorus, such as: zinc elemental, zinc oxide, zinc halide, copper-zinc alloy, tin element, tin oxide, tin halide, copper-tin alloy, phosphorus elemental, phosphorus pentoxide, phosphorus halide Or a combination of one or at least two of copper-phosphorus alloys, for example: zinc, tin, white phosphorus, red phosphorus, zinc oxide, tin dioxide, phosphorus pentoxide, zinc halide, tin halide, phosphorus halide, zinc-copper alloy a combination of one or at least two of a copper-tin alloy, a copper-tin-zinc alloy, a phosphor bronze alloy, or a phosphor bronze-tin alloy, wherein the halide may be fluoride, chloride, bromide or iodide. 1 or a combination of at least 2, typical but non-limiting examples of the cocatalyst include: a mixture of zinc and tin, a zinc-tin alloy, a phosphorus-tin alloy, a combination of tin, white phosphorus and red phosphorus, zinc fluoride, chlorination Tin and pentoxide Phosphorus combination, combination of zinc oxide, tin dioxide and tin tetrabromide, tin, white phosphorus, red phosphorus, combination of zinc oxide and tin dioxide, zinc-copper alloy, copper-tin alloy, copper-tin-zinc alloy, pentoxide a combination of phosphorus and white phosphorus, and the like. Preferably, the promoter has a particle size of 600 microns or less, such as 0.1 microns, 0.2 microns, 0.9 microns, 1.1 microns, 2 microns, 3 microns, 4 microns, 6 microns, 10 microns, 20 microns, 50 microns, 100 microns. 150 μm, 200 μm, 300 μm, 400 μm, 450 μm, 490 μm, 499 μm, 501 μm, 510 μm, 520 μm, 530 μm, 540 μm, 548 μm, 549 μm, etc., further preferably 1~ 550 microns, particularly preferably 5 to 500 microns.
优选地，所述助催化剂与原料氧化铜的质量比为 15:100以下，例如 0.01:100、 0.1:100、 0.2:100、 1:100、 2:100、 5:100、 7:100、 9:100、 11:100、 13:100、 14:100、 14.5:100、 14.8:100、 14.9:100等，进一歩优选为 12:100以下，特别优选为 10:100 以下。  Preferably, the mass ratio of the cocatalyst to the raw material copper oxide is 15:100 or less, for example, 0.01:100, 0.1:100, 0.2:100, 1:100, 2:100, 5:100, 7:100, 9 : 100, 11:100, 13:100, 14:100, 14.5: 100, 14.8: 100, 14.9: 100, etc., further preferably 12:100 or less, particularly preferably 10:100 or less.
优选地， 所述还原性物质为水合肼、 葡萄糖、 甲醛、 抗坏血酸或硼氢化钠 中的 1种或至少 2种的组合， 例如水合肼和葡萄糖的组合， 甲醛和抗坏血酸的 组合， 葡萄糖、 甲醛和硼氢化钠的组合， 水合肼、 葡萄糖、 甲醛和硼氢化钠的 组合， 水合肼、 葡萄糖、 甲醛、 抗坏血酸和硼氢化钠的组合等； 所述还原性物 质指可以还原氧化铜的物质。  Preferably, the reducing substance is one or a combination of at least two of hydrazine hydrate, glucose, formaldehyde, ascorbic acid or sodium borohydride, such as a combination of hydrazine hydrate and glucose, a combination of formaldehyde and ascorbic acid, glucose, formaldehyde and a combination of sodium borohydride, a combination of hydrazine hydrate, glucose, formaldehyde and sodium borohydride, a combination of hydrazine hydrate, glucose, formaldehyde, ascorbic acid and sodium borohydride; and the reducing substance means a substance which can reduce copper oxide.
优选地，所述还原性物质与原料氧化铜的质量比为 0.01:1 15:1，例如 0.02:1、 0.05:1、 0.09:1、 0.11:1、 0.15:1、 0.2:1、 0.5:1、 1:1、 1.5:1、 1.9:1、 2.1:1、 3:1、 5:1、 8:1、 9:1、 9.9:1、 10.1:1、 11:1、 12:1、 14:1、 14.5:1、 14.8:1、 14.9:1 等， 进一歩 优选为 0.01:1-10:1, 特别优选 0.1:1~2:1。  Preferably, the mass ratio of the reducing substance to the raw material copper oxide is 0.01:15:1, for example, 0.02:1, 0.05:1, 0.09:1, 0.11:1, 0.15:1, 0.2:1, 0.5: 1, 1:1, 1.5:1, 1.9:1, 2.1:1, 3:1, 5:1, 8:1, 9:1, 9.9:1, 10.1:1, 11:1, 12:1 14:1, 14.5:1, 14.8:1, 14.9:1, etc., further preferably 0.01:1-10:1, particularly preferably 0.1:1 to 2:1.
优选地， 所述溶剂为水和 /或有机溶剂， 例如： 醇类、 酮类、 芳香族类、 醚 类、 垸烃类等， 例如 C^do醇类 （如甲醇、 乙醇、 正丙醇、 异丙醇、 乙二醇、 1,3-丙二醇、 正丁醇、 正戊醇、 正己醇、 环己醇等）、 C2~C1Q醚类 （例如甲醚、 甲***、 ***、 正丙醚、 正丁醚、 四氢呋喃等）、 C3~C1Q酮类 （丙酮、 丁酮、 2- 戊酮、 苯丙酮等）、 C6~C2Q饱和垸烃（如正庚垸、 正己垸等）、 C6~C2Q环垸烃（如 环己垸等）、 甲苯、 二甲苯、 Ν,Ν-二甲基甲酰胺、 四氯化碳、 氯仿或二氯乙垸等 中的 1种或至少 2种的组合， 更优选为水、 d~C5醇类、 C3~C5酮类中的 1种或 至少 2种的组合， 特别优选为水和 /或乙醇。 所述溶剂具有两个作用， 一方面， 可以分散氧化铜原料， 另一方面， 可以调节还原性物质的浓度。 Preferably, the solvent is water and/or an organic solvent, for example: alcohols, ketones, aromatics, ethers, anthrahydrocarbons, etc., such as C^do alcohols (such as methanol, ethanol, n-propanol, Isopropanol, ethylene glycol, 1,3-propanediol, n-butanol, n-pentanol, n-hexanol, cyclohexanol, etc.), C 2 ~C 1Q ethers (eg methyl ether, methyl ethyl ether, diethyl ether, n-propyl) Ether, n-butyl ether, tetrahydrofuran, etc.), C 3 ~C 1Q ketones (acetone, butanone, 2-pentanone, propiophenone, etc.), C 6 ~C 2Q saturated anthracene (such as n-glycan, hexamidine, etc.) ), C 6 ~ C 2Q cyclic hydrocarbons (such as One or a combination of at least two of cyclohexane or the like, toluene, xylene, hydrazine, hydrazine-dimethylformamide, carbon tetrachloride, chloroform or dichloroacetamidine, more preferably water, d One or a combination of at least two of ~C 5 alcohols and C 3 -C 5 ketones is particularly preferably water and/or ethanol. The solvent has two functions, on the one hand, it is possible to disperse the copper oxide raw material, and on the other hand, the concentration of the reducing substance can be adjusted.
优选地，所述溶剂与原料氧化铜的质量比为 0.8: 1~15: 1，例如 0.81 : 1、 0.82:1、 0.9:1、 0.99:1、 1.1 : 1、 1.2:1、 1.5:1、 2: 1、 4:1、 6: 1、 7: 1、 8:1、 9:1、 11 :1、 12:1、 14:1、 14.5:1、 14.8:1、 14.9:1等， 进一歩优选为 1 :1~10: 1， 特别优选 1 :1~5:1。  Preferably, the mass ratio of the solvent to the raw material copper oxide is 0.8: 1 to 15: 1, for example, 0.81: 1, 0.82:1, 0.9:1, 0.99:1, 1.1:1, 1.2:1, 1.5:1 , 2: 1, 4:1, 6: 1, 7: 1, 8:1, 9:1, 11:1, 12:1, 14:1, 14.5:1, 14.8:1, 14.9:1, etc. Further, it is preferably from 1:1 to 10: 1, particularly preferably from 1:1 to 5:1.
优选地， 所述研磨所采用设备为行星球磨机、 滚筒研磨机、 搅拌研磨机、 振动磨或砂磨机中的任意 1种。  Preferably, the apparatus used for the grinding is any one of a planetary ball mill, a barrel mill, a stirring mill, a vibration mill or a sand mill.
优选地， 所述研磨时间为大于 0小时， 例如 0.001小时、 0.01小时、 0.1小 时、 0.4小时、 1小时、 1.5小时、 1.9小时、 2.1小时、 3小时、 5小时、 9小时、 11小时、 15小时、 20小时、 23小时、 25小时、 30小时等，进一歩优选为 0.5~24 小时， 特别优选为 2~10小时。 所述研磨可以使氧化铜颗粒变小并部分还原。 所 述研磨时间可以与反应时间相同， 即边研磨边反应， 研磨结束则反应结束， 所 述研磨时间也可以小于反应时间， 例如研磨反应一段时间后， 再静置反应一段 时间， 或者反应一段时间后， 再进行研磨， 在研磨的同时进行反应。  Preferably, the grinding time is greater than 0 hours, such as 0.001 hours, 0.01 hours, 0.1 hours, 0.4 hours, 1 hour, 1.5 hours, 1.9 hours, 2.1 hours, 3 hours, 5 hours, 9 hours, 11 hours, 15 The hour, the 20 hour, the 23 hour, the 25 hour, the 30 hour, and the like are preferably 0.5 to 24 hours, particularly preferably 2 to 10 hours. The grinding can make the copper oxide particles smaller and partially reduced. The grinding time can be the same as the reaction time, that is, the reaction is carried out while grinding, and the end of the reaction is completed, and the grinding time can also be less than the reaction time. For example, after the grinding reaction for a period of time, the reaction is allowed to stand for a while, or the reaction is for a period of time. Thereafter, grinding is carried out to carry out the reaction while grinding.
优选地， 所述除杂包括依次过滤和干燥； 优选地， 所述过滤为抽滤。  Preferably, the impurity removal comprises sequential filtration and drying; preferably, the filtration is suction filtration.
使用本法制得的铜基催化剂包含金属铜粉、 氧化亚铜粉以及氧化铜粉。 根 据需要， 可以通过调整还原性物质的种类和浓度、 球磨条件等参数， 从而制得 不同组成的铜基催化剂。  The copper-based catalyst prepared by the present method comprises metallic copper powder, cuprous oxide powder, and copper oxide powder. The copper-based catalyst of different composition can be prepared by adjusting parameters such as the type and concentration of the reducing substance and the milling conditions as needed.
本发明所述方法采用氧化铜为原料， 通过液相球磨还原一歩法同时完成研 磨和部分还原， 制备含有铜、 氧化亚铜和氧化铜三元组分的复合材料。 在高能 研磨力的作用下， 物料不断研磨和不断还原， 使颗粒不断变小的同时， 增强了 氧化铜粉末参与还原反应的能力， 使得氧化铜原料从外到内逐层被还原， 形成 一种层层包裹的多相镶嵌结构； 强化了铜、 氧化亚铜和氧化铜之间的相互作用， 使该催化剂中 Cu、 Cu20和 CuO三种组成元素的分布更加均匀， 在硅粉和氯甲 垸反应生成甲基氯硅垸系列单体的反应中， 提高了甲基氯硅垸反应的活性、 二 甲基二氯硅垸的选择性和硅粉的转化率。 该催化剂的制备过程中， 不会引入新 的杂质元素， 产品纯度高， 所得三元铜基催化剂组分组成可调， 粒度大小可控。 该方法简单、 条件温和， 而且易于控制， 产物的物相组成、 形貌和颗粒尺寸易 于控制。 The method of the invention uses copper oxide as a raw material, and simultaneously completes grinding and partial reduction by liquid phase ball milling reduction to prepare a composite material containing copper, cuprous oxide and copper oxide ternary components. Under the action of high-energy grinding force, the material is continuously ground and continuously reduced, so that the particles become smaller and smaller, and the reinforcement is enhanced. The ability of the copper oxide powder to participate in the reduction reaction causes the copper oxide raw material to be reduced layer by layer from the outside to the inside, forming a layered multiphase mosaic structure; strengthening the interaction between copper, cuprous oxide and copper oxide, The distribution of the three constituent elements Cu, Cu 2 0 and CuO in the catalyst is more uniform, and the reaction of the methyl chlorosilane target is enhanced in the reaction of the silicon powder and the chloroformamide to form a methyl chlorosilane group monomer. Activity, selectivity of dimethyldichlorosilane and conversion of silicon powder. During the preparation of the catalyst, new impurity elements are not introduced, the product purity is high, the composition of the obtained ternary copper-based catalyst component is adjustable, and the particle size is controllable. The method is simple, mild, and easy to control, and the phase composition, morphology and particle size of the product are easily controlled.
本发明所涉及的铜基催化剂， 通过研磨力的作用控制其粒度大小， 同时， 在还原物质和研磨力的作用下， 对其各组成成分的含量进行调整， 并在研磨力 作用下使各组分间的相互作用得到强化。  The copper-based catalyst according to the present invention controls the particle size by the action of the grinding force, and at the same time, adjusts the content of each component under the action of the reducing substance and the grinding force, and makes each group under the action of the grinding force. The interaction between the divisions is strengthened.
本发明的目的之一在于提供一种三元铜基催化剂， 所述三元铜基催化剂由 上述方法制备， 含有单质铜、 氧化亚铜和氧化铜。  One of the objects of the present invention is to provide a ternary copper-based catalyst which is prepared by the above method and contains elemental copper, cuprous oxide and copper oxide.
优选地， 所述铜基三元催化剂粒径为 0.1-70微米， 例如 0.11微米、 0.12微 米、 0.15微米、 0.19微米、 0.21微米、 0.25微米、 0.3微米、 0.4微米、 0.6微米、 1微米、 5微米、 9微米、 11微米、 20微米、 40微米、 49微米、 51微米、 60微 米、 65微米、 68微米、 69微米等，进一歩优选为 0.2-50微米，特别优选为 0.5-10 微米。  Preferably, the copper-based three-way catalyst has a particle diameter of 0.1 to 70 μm, such as 0.11 μm, 0.12 μm, 0.15 μm, 0.19 μm, 0.21 μm, 0.25 μm, 0.3 μm, 0.4 μm, 0.6 μm, 1 μm, 5 Micron, 9 microns, 11 microns, 20 microns, 40 microns, 49 microns, 51 microns, 60 microns, 65 microns, 68 microns, 69 microns, etc., further preferably from 0.2 to 50 microns, particularly preferably from 0.5 to 10 microns.
优选地，所述三元铜基催化剂中单质铜的含量为 0.5~95wt%，例如 0.51wt%、 0.52wt%、 0.6wt%、 0.7wt%、 0.9wt%、 l .lwt%、 1.5wt%、 2wt%、 10wt%、 40wt%、 60wt%、 80wt%、 85wt%、 89wt%、 91wt%、 92wt%、 94wt%、 94.8wt%、 94.9wt% 等， 进一歩优选为 0.8~93wt%， 特别优选为 l~90wt%。  Preferably, the content of elemental copper in the ternary copper-based catalyst is 0.5 to 95 wt%, for example, 0.51 wt%, 0.52 wt%, 0.6 wt%, 0.7 wt%, 0.9 wt%, 1.1 wt%, 1.5 wt%. 2 wt%, 10 wt%, 40 wt%, 60 wt%, 80 wt%, 85 wt%, 89 wt%, 91 wt%, 92 wt%, 94 wt%, 94.8 wt%, 94.9 wt%, etc., further preferably 0.8 to 93 wt%, particularly It is preferably from 1 to 90% by weight.
优选地， 所述三元铜基催化剂中氧化亚铜的含量为 2-95wt%， 例如 2.1wt%、 2.2wt% 2.5wt%、 2.9wt%、 3.1wt%、 3.5wt%、 4wt%、 4.5wt%、 4.9wt%、 5.1wt%、 6wt%、 10wt%、 30wt%、 60wt%、 80wt%、 85wt%、 89wt%、 91wt%、 92wt%、 94wt%、 94.5wt%、 94.8wt%、 94.9wt%等， 进一歩优选为 3~93wt%， 特别优选为 5-90wt Preferably, the content of cuprous oxide in the ternary copper-based catalyst is 2-95 wt%, for example 2.1 wt%, 2.2 wt% 2.5 wt%, 2.9 wt%, 3.1 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 4.9 wt%, 5.1 wt%, 6 wt%, 10 wt%, 30 wt%, 60 wt%, 80 wt%, 85 wt %, 89 wt%, 91 wt%, 92 wt%, 94 wt%, 94.5 wt%, 94.8 wt%, 94.9 wt%, etc., further preferably from 3 to 93 wt%, particularly preferably from 5 to 90 wt%
优选地， 所述三元铜基催化剂中氧化铜的含量为 2-95wt%， 例如 2.1wt%、 2.2wt% 2.5wt%、 2.9wt%、 3.1wt%、 3.5wt%、 4wt%、 4.5wt%、 4.9wt%、 5.1wt%、 6wt%、 10wt%、 30wt%、 60wt%、 80wt%、 85wt%、 89wt%、 91wt%、 92wt%、 94wt%、 94.5wt%、 94.8wt%、 94.9wt%等， 进一歩优选为 3~93wt%， 特别优选为 5-90wt  Preferably, the content of copper oxide in the ternary copper-based catalyst is 2 to 95 wt%, for example, 2.1 wt%, 2.2 wt%, 2.5 wt%, 2.9 wt%, 3.1 wt%, 3.5 wt%, 4 wt%, 4.5 wt% %, 4.9 wt%, 5.1 wt%, 6 wt%, 10 wt%, 30 wt%, 60 wt%, 80 wt%, 85 wt%, 89 wt%, 91 wt%, 92 wt%, 94 wt%, 94.5 wt%, 94.8 wt%, 94.9 wt% %, etc., further preferably from 3 to 93% by weight, particularly preferably from 5 to 90%
所述催化剂还可以含有助催化剂， 例如所述助催化剂为元素的单质、 氧化 物、 卤化物或铜合金中的 1种或至少 2种的组合， 所述元素为锌、 锡或磷中的 1 种或至少 2种的组合， 例如： 锌、 锡、 白磷、 红磷、 氧化锌、 二氧化锡、 五氧 化二磷、 卤化锌、 卤化锡、 卤化磷、 锌铜合金、 铜锡合金、 铜锡锌合金、 磷铜 合金或磷铜锡合金等种的 1种或至少 2种的组合， 所述卤化物可以为氟化物、 氯化物、 溴化物含或碘化物中的 1种或至少 2种的组合， 所述助催化剂典型但 非限制性的实例包括： 锌和锡混合物， 锌锡合金， 磷锡合金， 锡、 白磷和红磷 的组合， 氟化锌、 氯化锡和五氧化二磷的组合， 氧化锌、 二氧化锡和四溴化锡 的组合， 锡、 白磷、 红磷、 氧化锌和二氧化锡的组合， 锌铜合金、 铜锡合金、 铜锡锌合金、 五氧化二磷和白磷的组合等。  The catalyst may further contain a cocatalyst, for example, the cocatalyst is a combination of one or at least two of an elemental substance, an oxide, a halide or a copper alloy of an element, and the element is one of zinc, tin or phosphorus. Or at least two combinations, such as: zinc, tin, white phosphorus, red phosphorus, zinc oxide, tin dioxide, phosphorus pentoxide, zinc halide, tin halide, phosphorus halide, zinc copper alloy, copper tin alloy, copper tin a combination of one or at least two of a zinc alloy, a phosphor bronze alloy, or a phosphorus copper tin alloy, and the halide may be one or at least two of a fluoride, a chloride, a bromide or an iodide. In combination, typical but non-limiting examples of the cocatalyst include: a mixture of zinc and tin, a zinc-tin alloy, a phosphorus-tin alloy, a combination of tin, white phosphorus, and red phosphorus, zinc fluoride, tin chloride, and phosphorus pentoxide. Combination, combination of zinc oxide, tin dioxide and tin tetrabromide, tin, white phosphorus, red phosphorus, a combination of zinc oxide and tin dioxide, zinc-copper alloy, copper-tin alloy, copper-tin-zinc alloy, phosphorus pentoxide and White phosphorus Combination, etc.
本发明的目的之一还在于提供一种所述三元铜基催化剂的用途。  It is also an object of the present invention to provide a use of the ternary copper-based catalyst.
所述三元铜基催化剂可用作二甲基二氯硅垸合成反应的催化剂， 具有较高 的催化活性和二甲基二氯硅垸的选择性， 可大幅提高二甲基二氯硅垸的产率。  The ternary copper-based catalyst can be used as a catalyst for the synthesis reaction of dimethyldichlorosilane, has high catalytic activity and selectivity of dimethyldichlorosilane, and can greatly improve dimethyldichlorosilane. Yield.
与现有技术相比， 本发明的优势在于： ( 1 ) 本发明采用液相球磨部分还原法制备出含有铜、 氧化亚铜和氧化铜的 三元铜基催化剂， 该方法不引入任何杂质离子， 催化剂组成和粒度大小同时得 到控制。 The advantages of the present invention over the prior art are: (1) The present invention uses a liquid phase ball milling partial reduction method to prepare a ternary copper-based catalyst containing copper, cuprous oxide and copper oxide. This method does not introduce any impurity ions, and the catalyst composition and particle size are simultaneously controlled.
(2) 本发明所涉及的铜基催化剂的制备方法工艺简单、 条件温和、 操作简 便， 易于实现规模化生产。  (2) The preparation method of the copper-based catalyst according to the present invention is simple in process, mild in condition, simple in operation, and easy to realize large-scale production.
(3 )本发明制备的铜基催化剂表现出较高的二甲基二氯硅垸的选择性及硅 粉原料的转化率。  (3) The copper-based catalyst prepared by the present invention exhibits a high selectivity for dimethyldichlorosilane and a conversion ratio of the silicon powder raw material.
附图说明 DRAWINGS
图 1是实施例 1制备的铜基催化剂的 XRD图。  BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an XRD chart of a copper-based catalyst prepared in Example 1.
图 2是实施例 1制备的铜基催化剂的粒径分析。  Figure 2 is a particle size analysis of the copper-based catalyst prepared in Example 1.
图 3是实施例 1制备的铜基催化剂的 SEM图。  Figure 3 is an SEM image of the copper-based catalyst prepared in Example 1.
图 4是实施例 2制备的铜基催化剂的 XRD图。  Figure 4 is an XRD pattern of the copper-based catalyst prepared in Example 2.
图 5是实施例 2制备的铜基催化剂的粒径分析。  Figure 5 is a particle size analysis of the copper-based catalyst prepared in Example 2.
图 6是实施例 2制备的铜基催化剂的 SEM图。  Figure 6 is an SEM image of the copper-based catalyst prepared in Example 2.
具体实施方式 detailed description
为便于理解本发明， 本发明列举实施例如下。 本领域技术人员应该明了， 所述实施例仅仅是帮助理解本发明， 不应视为对本发明的具体限制。  In order to facilitate the understanding of the present invention, the present invention is exemplified by the following. It should be understood by those skilled in the art that the present invention is not to be construed as limited.
实施例 1  Example 1
将 5.0g分析纯氧化铜粉末和 25g研磨珠放入不锈钢球磨罐中，依次加入 5.0g 水和 0.5g水合肼； 在行星式球磨机上研磨 6h， 将所得产物抽滤、干燥并分散后， 即可得到三元铜催化剂； 经化学法分析后组成为： 10.1%Cu、 51.5%Cu20 和 38.4%CuO。 5.0 g of analytically pure copper oxide powder and 25 g of grinding beads were placed in a stainless steel ball mill jar, and 5.0 g of water and 0.5 g of hydrazine hydrate were sequentially added; after grinding for 6 h on a planetary ball mill, the obtained product was suction filtered, dried and dispersed, that is, A ternary copper catalyst can be obtained; after chemical analysis, the composition is: 10.1% Cu, 51.5% Cu 2 0 and 38.4% CuO.
将上述制备的三元铜催化剂材料在荷兰 Panalytical 公司 （帕纳科） 生产的 X'Pert PRO MPD型多功能 X射线衍射仪上进行 XRD测试。 The ternary copper catalyst material prepared above was produced at Panalytical (Panaco), the Netherlands. XRD testing was performed on a X'Pert PRO MPD multi-function X-ray diffractometer.
将上述制备的三元铜催化剂材料在丹东百特 BT-9300Z激光粒度分布仪进行 粒径分析。  The ternary copper catalyst material prepared above was subjected to particle size analysis on a Dandong Baxter BT-9300Z laser particle size distribution analyzer.
将上述制备的三元铜催化剂材料在日本电子公司生产的 JSM7100F 型场发 射扫描电镜观测表面形貌。  The surface morphology of the ternary copper catalyst material prepared above was observed by a JSM7100F field emission scanning electron microscope manufactured by JEOL.
图 1为实施例 1得到的铜催化剂的 XRD图，其中 2 = 36.4°为 Cu20的特征 峰， 由 2 = 35.5°和 2 = 38.7°组成的肩峰是 CuO的特征峰， 2 = 43.3°是 Cu的特 征峰， 由此可见， 用此方法制备的催化剂为由 Cu、 Cu20和 CuO组成的三元铜 催化剂。 1 is an XRD pattern of the copper catalyst obtained in Example 1, wherein 2 = 36.4° is a characteristic peak of Cu 2 0, and a shoulder peak composed of 2 = 35.5° and 2 = 38.7° is a characteristic peak of CuO, 2 = 43.3. ° is a characteristic peak of Cu, and it can be seen that the catalyst prepared by this method is a ternary copper catalyst composed of Cu, Cu 2 O and CuO.
图 2为实施例 1得到的铜基催化剂的粒径分析， 由图可知， 该铜基催化剂 的粒径全部小于 30微米， 其中大部分粒径为 3微米。  Fig. 2 is a particle size analysis of the copper-based catalyst obtained in Example 1. As is apparent from the figure, the particle diameter of the copper-based catalyst was all less than 30 μm, and most of the particle diameter was 3 μm.
图 3为实施例 1得到的铜催化剂的 SEM图， 由图可知， 该铜基催化剂的颗 粒呈无定形， 大部分小于 10微米。  Fig. 3 is a SEM image of the copper catalyst obtained in Example 1. As is apparent from the figure, the particles of the copper-based catalyst were amorphous, and most of them were less than 10 μm.
实施例 2  Example 2
将 lO.Og由草酸铜煅烧而成的氧化铜粉末、 0.25g氧化锌粉末和 25g研磨珠 放入研磨罐中， 依次加入 20.0g水和 5.0g甲醛； 在搅拌磨上研磨 8h， 将所得产 物抽滤、 干燥并分散后， 即可得到三元铜催化剂； 经化学法分析后组成为： 20.2%Cu、 33.3%Cu20和 46.5%CuO。 The copper oxide powder obtained by calcining lO.Og from copper oxalate, 0.25 g of zinc oxide powder and 25 g of grinding beads were placed in a grinding jar, and 20.0 g of water and 5.0 g of formaldehyde were sequentially added; the mixture was ground for 8 h on a stirring mill to obtain the obtained product. After suction filtration, drying and dispersion, a ternary copper catalyst can be obtained; after chemical analysis, the composition is: 20.2% Cu, 33.3% Cu 2 0 and 46.5% CuO.
图 4为实施例 2得到的铜基催化剂的 XRD图，其中 2 = 36.4°为 Cu20的特 征峰， 由 26> = 35.5°和 26> = 38.7°组成的肩峰是 CuO的特征峰， 26> = 43.3°是 Cu的 特征峰， 由此可见， 用此方法制备的催化剂为由 Cu、 Cu20和 CuO组成的三元 铜催化剂。 4 is an XRD pattern of the copper-based catalyst obtained in Example 2, wherein 2 = 36.4° is a characteristic peak of Cu 2 0, and a shoulder peak composed of 26>=35.5° and 26>=38.7° is a characteristic peak of CuO. 26> = 43.3° is a characteristic peak of Cu, and it can be seen that the catalyst prepared by this method is a ternary copper catalyst composed of Cu, Cu 2 0 and CuO.
图 5为实施例 2得到的铜基催化剂的粒径分析， 由图可知， 该铜基催化剂 的粒径全部小于 20微米， 其中大部分粒径为 2-3微米。 Figure 5 is a particle size analysis of the copper-based catalyst obtained in Example 2, which shows that the copper-based catalyst The particle size is all less than 20 microns, with most of the particle size being 2-3 microns.
图 6为实施例 2得到的铜基催化剂的 SEM图， 由图可知， 该铜基催化剂的 颗粒呈薄片状， 薄片大小不一， 大部颗粒小于 10微米。  Fig. 6 is a SEM image of the copper-based catalyst obtained in Example 2. As is apparent from the figure, the particles of the copper-based catalyst were in the form of flakes having a small sheet size and a large particle size of less than 10 μm.
实施例 3  Example 3
将 5.0g由铜粉氧化而成的氧化铜粉末和 50g研磨珠放入滚筒磨中， 依次加 入 5.0g水和 lO.Og水合肼； 在滚筒磨上研磨 24h， 将所得产物抽滤、 干燥并分散 后， 即可得到铜基催化剂； 经化学法分析后组成为： 90.0%Cu、 5.0%Cu2O 和 5.0%CuO， 其粒径全部小于 50微米， 大部分粒径为 10-20微米； 该铜基催化剂 的颗粒呈片状结构， 片径较大， 约为 10-20微米， 片厚很薄， 基本小于 1微米。 5.0 g of copper oxide powder oxidized from copper powder and 50 g of grinding beads were placed in a roller mill, and 5.0 g of water and 10 g of hydrazine hydrate were sequentially added; the mixture was ground for 24 h on a roller mill, and the obtained product was suction filtered and dried. After dispersion, a copper-based catalyst can be obtained; after chemical analysis, the composition is: 90.0% Cu, 5.0% Cu 2 O and 5.0% CuO, the particle diameters are all less than 50 micrometers, and most of the particle diameter is 10-20 micrometers; The copper-based catalyst has a sheet-like structure having a large diameter of about 10 to 20 μm and a sheet thickness of substantially less than 1 μm.
实施例 4  Example 4
将 5.0g由有机硅合成工业废触体回收的氧化铜粉末和 10g研磨珠放入振动 磨中，依次加入 50.0g水和 lO.Og葡萄糖；在振动磨上研磨 2h，将所得产物抽滤、 干燥并分散后， 即可得到三元铜催化剂； 经化学法分析后组成为： 11.6%Cu、 53.1%Cu20和 35.3%CuO， 其粒径全部小于 20微米， 大部分粒径为 2-3微米， 颗粒形貌为无定形。 5.0 g of copper oxide powder recovered from the silicone synthetic industrial waste contactor and 10 g of grinding beads were placed in a vibrating mill, and 50.0 g of water and 10 g of glucose were sequentially added; the mixture was ground for 2 h on a vibration mill, and the obtained product was suction filtered. After drying and dispersing, the ternary copper catalyst can be obtained; after chemical analysis, the composition is: 11.6% Cu, 53.1% Cu 2 0 and 35.3% CuO, the particle size is less than 20 microns, and most of the particle size is 2- 3 microns, the particle morphology is amorphous.
实施例 5  Example 5
将 5.0g由水热法合成的粒径大小约为 5微米的氧化铜粉末和 25g研磨珠放 入砂磨机中， 依次加入 5.0g乙醇和 0.05g水合肼； 在砂磨机上研磨 8h， 将所得 产物抽滤、 干燥并分散后， 即可得到三元铜催化剂； 经化学法分析后组成为： 1.0%Cu、 9.0%Cu2O和 90.0%CuO， 其粒径全部小于 20微米， 大部分粒径为 3 微米， 颗粒为无定形结构。 5.0 g of copper oxide powder having a particle size of about 5 μm synthesized by hydrothermal method and 25 g of grinding beads were placed in a sand mill, and 5.0 g of ethanol and 0.05 g of hydrazine hydrate were sequentially added; and grinding was performed for 8 hours on a sand mill. After the obtained product is suction filtered, dried and dispersed, a ternary copper catalyst can be obtained; after chemical analysis, the composition is: 1.0% Cu, 9.0% Cu 2 O and 90.0% CuO, the particle diameters are all less than 20 micrometers, large The partial particle size is 3 microns and the particles are amorphous.
实施例 6  Example 6
将 5.0g颗粒大小约为 500微米的工业级氧化铜粉末和 25g研磨珠放入球磨 罐内， 先于行星磨中研磨 8h; 然后， 依次加入 5.0g水和 6.0g抗坏血酸； 在行星 磨上继续研磨 4h， 将所得产物抽滤、 干燥并分散后， 即可得到三元铜催化剂； 经化学法分析后组成为： 33.5%Cu、 48.9%Cu20和 17.6%CuO， 其粒径全部小于 20微米， 大部分粒径为 2-3微米， 颗粒为无定形结构。 Put 5.0g of industrial grade copper oxide powder with a particle size of about 500 microns and 25g of grinding beads into the ball mill In the tank, grinding in the planetary mill for 8h ; then, adding 5.0g water and 6.0g ascorbic acid in turn; continuing grinding on the planetary mill for 4h, filtering the product, drying and dispersing, then obtaining the ternary copper catalyst; After chemical analysis, the composition is: 33.5% Cu, 48.9% Cu 2 0 and 17.6% CuO, the particle size is less than 20 microns, most of the particle size is 2-3 microns, and the particles are amorphous.
实施例 7  Example 7
将 lO.Og分析纯氧化铜粉末、 0.9635g金属锌粉、 0.0015g金属锡粉和 0.0350g 铜磷合金粉放入烧杯中， 依次加入 lO.Og水和 5.0g水合肼； 在磁力搅拌器上反 应 2h， 在振动磨上研磨 0.5h， 将所得产物抽滤、 干燥并分散后， 即可得到三元 铜催化剂； 经化学法分析后组成为： 20.6%Cu、 28.2%Cu20和 51.2%CuO， 其粒 径全部小于 30微米， 大部分粒径为 10微米， 颗粒呈无定形结构。 The lO.Og analytical pure copper oxide powder, 0.9635 g metal zinc powder, 0.0015 g metal tin powder and 0.0350 g copper phosphorus alloy powder were placed in a beaker, and 10 g of water and 5.0 g of hydrazine hydrate were sequentially added; on a magnetic stirrer After reacting for 2 h, grinding on a vibration mill for 0.5 h, the obtained product was suction filtered, dried and dispersed to obtain a ternary copper catalyst; after chemical analysis, the composition was: 20.6% Cu, 28.2% Cu 2 0 and 51.2% CuO has a particle size of less than 30 microns, most of which has a particle size of 10 microns, and the particles have an amorphous structure.
实施例 8  Example 8
将 5.0g由单质铜和氧化亚铜混合物氧化而成的氧化铜粉末以及 25g研磨珠 放入研磨罐内，依次加入 20.0g乙醇水溶液和 50.0g葡萄糖；在振动磨上研磨 6h， 将所得产物抽滤、 干燥并分散后， 即可得到三元铜催化剂； 经化学法分析后组 成为： 24.9%Cu、 54.3%Cu20和 20.8%CuO， 其粒径全部小于 20微米， 大部分 粒径为 2-3微米， 颗粒形貌为无定形。 5.0 g of copper oxide powder obtained by oxidizing a mixture of elemental copper and cuprous oxide and 25 g of grinding beads were placed in a grinding tank, and 20.0 g of an aqueous ethanol solution and 50.0 g of glucose were sequentially added; the mixture was ground for 6 h on a vibration mill, and the obtained product was pumped. After filtering, drying and dispersing, the ternary copper catalyst can be obtained; after chemical analysis, the composition is: 24.9% Cu, 54.3% Cu 2 0 and 20.8% CuO, the particle size is less than 20 microns, most of the particle size is 2-3 microns, the particle morphology is amorphous.
实施例 9  Example 9
将 lO.Og工业级氧化铜粉末、 0.0030g二氯化锡粉和 0.0050g磷粉以及 25g 研磨珠放入砂磨机内，依次加入 50.0g水和 2.0g硼氢化钠；在砂磨机上研磨 10h， 将所得产物抽滤、 干燥并分散后， 即可得到三元铜催化剂； 经化学法分析后组 成为： 1.4%Cu、 90.0%Cu2O和 8.6%CuO， 其粒径全部小于 20微米， 大部分粒 径为 2-3微米， 颗粒呈无定形结构。 Put lO.Og industrial grade copper oxide powder, 0.0030g of tin dichloride powder and 0.0050g of phosphorus powder and 25g of grinding beads into the sand mill, and sequentially add 50.0g water and 2.0g sodium borohydride; on the sand mill After grinding for 10 h, the obtained product was suction filtered, dried and dispersed to obtain a ternary copper catalyst; after chemical analysis, the composition was: 1.4% Cu, 90.0% Cu 2 O and 8.6% CuO, and the particle diameters were all less than 20 Micron, most of the particle size is 2-3 microns, and the particles have an amorphous structure.
实施例 10 将 5.0g由氧化亚铜氧化而成的氧化铜粉末和 25g研磨珠放入滚筒磨中， 依 次加入 lO.Og水和 6.0g葡萄糖； 在滚筒磨上研磨 8h， 将所得产物抽滤、 干燥并 分散后， 即可得到铜基催化剂； 经化学法分析后组成为： 10.5%Cu、 47.8%Cu20 禾口 41.7%CuO， 其粒径大小约为 0.2微米， 颗粒呈无定形结构。 Example 10 5.0 g of copper oxide powder oxidized by cuprous oxide and 25 g of grinding beads were placed in a roller mill, and 10 g of water and 6.0 g of glucose were sequentially added; the mixture was ground for 8 h on a roller mill, and the obtained product was suction filtered and dried. After dispersion, a copper-based catalyst can be obtained; after chemical analysis, the composition is: 10.5% Cu, 47.8% Cu 2 0 and 41.7% CuO, the particle size is about 0.2 μm, and the particles have an amorphous structure.
实施例 11  Example 11
称取 lO.Og工业级氧化铜粉末、 0.6g金属锌粉、 0.0015g金属锡粉和 0.0360g 铜磷合金粉以及 25g研磨珠和 10g水， 在行星磨上研磨 2h; 然后， 在上述溶液 中继续添加 lO.Og水和 5.0g水合肼， 再继续研磨 6h; 最后， 将所得产物抽滤、 干燥并分散， 即可得到三元铜催化剂； 经化学法分析后组成为： 23.0%Cu、 43.4%Cu20和 28.7%CuO， 其粒径全部小于 20微米， 大部分粒径为 10微米， 颗 粒呈无定形结构。 Weigh lO.Og industrial grade copper oxide powder, 0.6g metal zinc powder, 0.0015g metal tin powder and 0.0360g copper phosphorus alloy powder and 25g grinding beads and 10g water, grind on the planetary mill for 2h; then, in the above solution Continue to add lO.Og water and 5.0g hydrazine hydrate, and continue grinding for 6h ; finally, the obtained product is suction filtered, dried and dispersed to obtain a ternary copper catalyst; after chemical analysis, the composition is: 23.0% Cu, 43.4 %Cu 2 0 and 28.7% CuO, all of which have a particle size of less than 20 μm, most of which have a particle size of 10 μm, and the particles have an amorphous structure.
实施例 12  Example 12
称取 lO.Og分析纯氧化铜粉末、 1.5g氧化锌粉末以及 25g研磨珠和 5g丙酮， 在行星磨上研磨 4h， 然后， 在上述溶液中继续添加 3.1g丙酮和 O.lg甲醛， 再继 续研磨 20h， 最后， 将所得产物抽滤、 干燥并分散， 即可得到三元铜催化剂； 经 化学法分析后组成为： 2.4%Cu、 12.4%Cu20和 80.2%CuO， 其粒径全部小于 15 微米， 大部分粒径为 8微米， 颗粒呈无定形结构。 Weigh lO.Og analysis of pure copper oxide powder, 1.5g of zinc oxide powder and 25g of grinding beads and 5g of acetone, grind on the planetary mill for 4h, then continue to add 3.1g of acetone and O.lg formaldehyde in the above solution, and then continue Grinding for 20h, finally, the obtained product is suction filtered, dried and dispersed to obtain a ternary copper catalyst; after chemical analysis, the composition is: 2.4% Cu, 12.4% Cu 2 0 and 80.2% CuO, the particle size is all less than At 15 microns, most of the particle size is 8 microns and the particles are amorphous.
实施例 13  Example 13
称取 lO.Og分析纯氧化铜粉末、 0.6g五氧化二磷， 以及 25g研磨珠和 50g乙 醚， 在上述溶液中继续添加 250g***和 150g葡萄糖， 在行星磨上研磨 0.1h， 然后静置反应 10小时， 最后， 将所得产物抽滤、 干燥并分散， 即可得到三元铜 催化剂； 经化学法分析后组成为： 72.1%Cu、 12.4%Cu20和 2.1%CuO， 其粒径 全部小于 65微米， 大部分粒径为 50微米， 颗粒呈无定形结构。 催化活性评价： 催化剂性能评价采用微型固定床装置进行： 将 Si粉和铜基 催化剂以 10:1的比例均匀混合后，填入固定床反应器（Φ20χ50)形成混合触体； 反应时， 首先采用 N2吹扫反应***， 然后， 切换为 MeCl气体， 经过预热后与 混合触体发生接触， 反应温度 325°C ; 反应后的产物从反应器下端流出， 经冷凝 管冷凝后采用甲苯收集， 多余尾气用碱液吸收后排空； 收集的混合液定容后进 行色谱分析， 计算 Si粉转化率和产物中各组分的分布情况 （其中， 二甲基二氯 硅垸的计算结果统称为二甲基二氯硅垸的选择性）。 所述实施例得到的催化剂以及对比例中的某商业铜基催化剂的性能评价结 果如表 1 所示。 可以看出， 本发明中催化剂性能评价所涉及的固定床装置上， 某商业铜催化剂进行该催化反应时，二甲基二氯硅垸的选择性仅为 65.1%,其中， 一甲基三氯硅垸为 14.0%， 一甲基二氯氢硅垸为 13.2%， Si粉转化率为 20.2%; 因此， 该商业催化剂由于大量副产一甲基三氯硅垸和一甲基二氯氢硅垸， 使目 标产物二甲基二氯硅垸的选择性较低。 而当使用该法制备的铜基催化剂时， 由 于该铜催化剂中三元组分的含量不同， 催化性能也不同， 最重要的指标二甲基 二氯硅垸的含量从 69.0%到 86.8%不等， 硅粉转化率从 26.4%到 65.7%不等； 该 铜基催化剂的催化性能有较大幅度提升， 二甲基二氯硅垸的选择性最高可达 86.8%, 同时 Si粉转化率也有 42.1%。 Weigh 10% Og of pure copper oxide powder, 0.6 g of phosphorus pentoxide, and 25 g of grinding beads and 50 g of diethyl ether. Continue to add 250 g of diethyl ether and 150 g of glucose to the above solution, grind on a planetary mill for 0.1 h, and then let stand. After 10 hours, finally, the obtained product was suction filtered, dried and dispersed to obtain a ternary copper catalyst; after chemical analysis, the composition was: 72.1% Cu, 12.4% Cu 2 0 and 2.1% CuO, and the particle diameters were all smaller than At 65 microns, most of the particles are 50 microns in size and the particles are amorphous. Evaluation of catalytic activity: Catalyst performance evaluation was carried out using a micro-fixed bed apparatus: Si powder and copper-based catalyst were uniformly mixed at a ratio of 10:1, and then filled into a fixed bed reactor (Φ20χ50) to form a mixed contact; The reaction system is purged with N 2 , and then switched to MeCl gas. After preheating, it is contacted with the mixed contact body at a reaction temperature of 325 ° C. The reacted product flows out from the lower end of the reactor, is condensed through a condenser, and is collected by using toluene. Excess exhaust gas is absorbed by lye and then emptied; the collected mixture is subjected to chromatographic analysis after constant volume calculation, and the conversion rate of Si powder and the distribution of each component in the product are calculated (wherein the calculation results of dimethyldichlorosilane are collectively referred to as Selectivity of dimethyldichlorosilane. The performance evaluation results of the catalyst obtained in the above examples and a commercial copper-based catalyst in the comparative examples are shown in Table 1. It can be seen that, in the fixed bed apparatus involved in the performance evaluation of the catalyst of the present invention, when a commercial copper catalyst performs the catalytic reaction, the selectivity of dimethyldichlorosilane is only 65.1%, wherein monomethyltrichloro The silicon germanium is 14.0%, the monomethyldichlorosilane is 13.2%, and the Si powder conversion is 20.2%; therefore, the commercial catalyst has a large amount of by-produced monomethyltrichlorosilane and monomethyldichlorosilane.垸, the selectivity of the target product dimethyldichlorosilane is low. When the copper-based catalyst prepared by the method is used, the catalytic performance is different due to the different content of the ternary component in the copper catalyst, and the most important index of dimethyldichlorosilane is from 69.0% to 86.8%. Etc., the conversion rate of silicon powder varies from 26.4% to 65.7%; the catalytic performance of the copper-based catalyst is greatly improved, the selectivity of dimethyldichlorosilane is up to 86.8%, and the conversion rate of Si powder is also 42.1%.
表 1 各种催化剂的催化活性评价结果 Table 1 Evaluation results of catalytic activity of various catalysts
Mi M2 M3 MiH M2 H LBR HBR Si 转化 催化剂 Mi M 2 M 3 MiH M 2 H LBR HBR Si Conversion Catalyst
(%) (%) (%) (%) (%) (%) (%) 率 (％) 实施例 1 9.8 81.5 4.0 2.0 1.5 0.7 0.5 34.8 实施例 2 16.3 69.0 1.4 11.7 0.4 0.9 0.3 26.4 实施例 3 14.4 76.5 2.5 2.5 2.3 0.5 1.3 53.6 实施例 4 6.6 86.8 1.6 1.9 0.9 1.5 0.7 42.1 实施例 5 12.5 76.7 1.4 6.1 1.4 1.0 0.9 45.6 实施例 6 9.2 81.0 2.3 3.7 0.9 0.1 2.8 60.0 实施例 7 15.8 72.1 2.2 4.4 1.3 1.5 2.7 26.5 实施例 8 8.8 83.8 1.3 4.2 0.7 0.4 0.8 42.5 实施例 9 11.4 70.3 1.4 13.1 3.1 0.2 0.5 34.5 实施例 10 8.5 80.3 1.5 5.6 0.9 0.6 2.6 30.1 实施例 11 8.4 79.1 1.8 5.8 0.7 1.0 3.2 65.7 实施例 12 11.6 73.5 2.0 9.1 1.3 0.4 2.1 41.2 实施例 13 11.0 76.2 1.8 6.8 1.5 0.8 1.9 39.4 某商业 (%) (%) (%) (%) (%) (%) (%) Rate (%) Example 1 9.8 81.5 4.0 2.0 1.5 0.7 0.5 34.8 Example 2 16.3 69.0 1.4 11.7 0.4 0.9 0.3 26.4 Example 3 14.4 76.5 2.5 2.5 2.3 0.5 1.3 53.6 Example 4 6.6 86.8 1.6 1.9 0.9 1.5 0.7 42.1 Example 5 12.5 76.7 1.4 6.1 1.4 1.0 0.9 45.6 Example 6 9.2 81.0 2.3 3.7 0.9 0.1 2.8 60.0 Example 7 15.8 72.1 2.2 4.4 1.3 1.5 2.7 26.5 Example 8 8.8 83.8 1.3 4.2 0.7 0.4 0.8 42.5 Example 9 11.4 70.3 1.4 13.1 3.1 0.2 0.5 34.5 Example 10 8.5 80.3 1.5 5.6 0.9 0.6 2.6 30.1 Implementation Example 11 8.4 79.1 1.8 5.8 0.7 1.0 3.2 65.7 Example 12 11.6 73.5 2.0 9.1 1.3 0.4 2.1 41.2 Example 13 11.0 76.2 1.8 6.8 1.5 0.8 1.9 39.4 A business
14.0 65.1 1.1 13.2 1.2 0.6 4.8 20.2 催化剂 注： （1 ) M1 : —甲基三氯硅垸， M2 : 二甲基二氯硅垸， M3 : 三甲基一氯硅 垸， Μ^: 甲基二氯含氢硅垸， M2H: 二甲基一氯含氢硅垸， LBR: 低沸点物 质总称， HBR: 高沸点物质总称； 14.0 65.1 1.1 13.2 1.2 0.6 4.8 20.2 Catalyst Note: (1) M 1 : -methyltrichlorosilane, M 2 : dimethyldichlorosilane, M 3 : trimethylsilyl phosphonium, Μ^: Methyl dichlorohydrosilane, M 2 H: dimethyl-chlorohydrosilane, LBR: low-boiling substance, HBR: high-boiling substance;
(2) 各产物分布情况计算公式为：
Figure imgf000016_0001
(2) The calculation formula for each product distribution is:
Figure imgf000016_0001
S S
■xl00%  ■xl00%
Q _L Q _L Q _L Q _L Q _L Q _L Q  Q _L Q _L Q _L Q _L Q _L Q _L Q
^M^ T ^> 2 T ^M3 T T ^M2H ^LBR ^HBR
Figure imgf000017_0001
^M^ T ^> 2 T ^M 3 TT ^M 2 H ^LBR ^HBR
Figure imgf000017_0001
w -w  w -w
Si(转化率 ) = -^1 ~~ ^xl00% Si (conversion rate) = -^ 1 ~~ ^xl00%
^^应前  ^^ should be before
其中， s为物质的色谱峰面积， 为物质的重量。  Where s is the chromatographic peak area of the substance and is the weight of the substance.
申请人声明， 本发明通过上述实施例来说明本发明的详细工艺设备和工艺 流程， 但本发明并不局限于上述详细工艺设备和工艺流程， 即不意味着本发明 必须依赖上述详细工艺设备和工艺流程才能实施。 所属技术领域的技术人员应 该明了， 对本发明的任何改进， 对本发明产品各原料的等效替换及辅助成分的 添加、 具体方式的选择等， 均落在本发明的保护范围和公开范围之内。  The Applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims

WO 2014/117464 权 利 要 求 书 PCT/CN2013/076874 WO 2014/117464 Claims PCT/CN2013/076874
1、 一种三元铜基催化剂的制备方法， 包括： 将氧化铜与还原性物质加入至 溶剂中， 研磨反应， 除杂， 粉碎， 得到三元铜基催化剂。 1. A method for preparing a ternary copper-based catalyst, including: adding copper oxide and reducing substances to a solvent, grinding and reacting, removing impurities, and pulverizing to obtain a ternary copper-based catalyst.
2、 如权利要求 1所述的方法， 其特征在于， 所述氧化铜为分析纯氧化铜粉 末或工业级氧化铜粉末； 2. The method of claim 1, wherein the copper oxide is analytically pure copper oxide powder or industrial grade copper oxide powder;
优选地， 所述氧化铜的粒度为 600微米以下， 进一歩优选为 1~550微米， 特别优选为 5~500微米。 Preferably, the particle size of the copper oxide is 600 microns or less, further preferably 1 to 550 microns, particularly preferably 5 to 500 microns.
3、 如权利要求 1或 2所述的方法， 其特征在于， 在反应体系中加入助催化 剂； 3. The method according to claim 1 or 2, characterized in that a cocatalyst is added to the reaction system;
优选地， 所述助催化剂为元素的单质、 氧化物、 卤化物或铜合金中的 1 种 或至少 2种的组合， 所述元素为锌、 锡或磷中的 1种或至少 2种的组合； Preferably, the cocatalyst is one or a combination of at least two of the elements, oxides, halides or copper alloys, and the element is one or a combination of at least two of zinc, tin or phosphorus. ;
优选地， 所述助催化剂的粒度为 600微米以下， 进一歩优选为 1~550微米， 特别优选为 5~500微米； Preferably, the particle size of the cocatalyst is 600 microns or less, further preferably 1 to 550 microns, particularly preferably 5 to 500 microns;
优选地， 所述助催化剂与所述氧化铜的质量比为 15: 100以下， 进一歩优选 为 12: 100以下， 特别优选为 10:100以下。 Preferably, the mass ratio of the cocatalyst to the copper oxide is 15:100 or less, further preferably 12:100 or less, particularly preferably 10:100 or less.
4、 如权利要求 1-3任一项所述的方法， 其特征在于， 所述还原性物质为水 合肼、 葡萄糖、 甲醛、 抗坏血酸或硼氢化钠中的 1种或至少 2种的组合； 4. The method according to any one of claims 1 to 3, wherein the reducing substance is one or a combination of at least two of hydrazine hydrate, glucose, formaldehyde, ascorbic acid or sodium borohydride;
优选地， 所述还原性物质与所述氧化铜的质量比为 0.01 :1~15:1， 进一歩优 选为 0.01 :1~10:1， 特别优选 0.1 :1~2:1。 Preferably, the mass ratio of the reducing substance to the copper oxide is 0.01:1~15:1, further preferably 0.01:1~10:1, particularly preferably 0.1:1~2:1.
5、 如权利要求 1-4任一项所述的方法， 其特征在于， 所述溶剂为水和 /或有 机溶剂， 更优选为水、 d~C5醇类、 C广 C5酮类中的 1种或至少 2种的组合， 特 别优选为水和 /或乙醇； 5. The method according to any one of claims 1 to 4, characterized in that the solvent is water and/or an organic solvent, more preferably water, d~ C5 alcohols, C~ C5 ketones. One or a combination of at least two, particularly preferably water and/or ethanol;
优选地， 所述溶剂与原料氧化铜的质量比为 0.8:1~15:1， 进一歩优选为 1 : 1-10: 1 , 特别优选 1 : 1~5: 1。 Preferably, the mass ratio of the solvent to the raw material copper oxide is 0.8:1~15:1, further preferably 1:1-10:1, particularly preferably 1:1~5:1.
6、 如权利要求 1-5任一项所述的方法， 其特征在于， 所述研磨所采用设备 为行星球磨机、 滚筒研磨机、 搅拌研磨机、 振动磨或砂磨机中的任意 1种； 优选地， 所述研磨时间为大于 0小时， 进一歩优选为 0.5~24小时， 特别优 选为 2~10小时； 6. The method according to any one of claims 1 to 5, characterized in that the equipment used for grinding is any one of a planetary ball mill, a drum grinder, a stirrer grinder, a vibration mill or a sand mill; Preferably, the grinding time is greater than 0 hours, further preferably 0.5 to 24 hours, particularly preferably 2 to 10 hours;
优选地， 所述除杂包括依次过滤和干燥； Preferably, the impurity removal includes filtering and drying in sequence;
优选地， 所述过滤为抽滤。 Preferably, the filtration is suction filtration.
7、一种三元铜基催化剂，其特征在于，所述三元铜基催化剂由权利要求 1-6 任一项所述的方法制备， 其含有单质铜、 氧化亚铜和氧化铜。 7. A ternary copper-based catalyst, characterized in that the ternary copper-based catalyst is prepared by the method described in any one of claims 1 to 6, and contains elemental copper, cuprous oxide and copper oxide.
8、 如权利要求 7所述的三元铜基催化剂， 其特征在于， 所述铜基三元催化 剂粒径为 0.1-70微米， 优选为 0.2-50微米， 特别优选 0.5-10微米； 8. The three-way copper-based catalyst according to claim 7, wherein the particle size of the copper-based three-way catalyst is 0.1-70 microns, preferably 0.2-50 microns, particularly preferably 0.5-10 microns;
优选地，所述三元铜基催化剂中单质铜的含量为 0.5~95wt%，进一歩优选为 0.8~93wt%, 特别优选为 l~90wt%； Preferably, the content of elemental copper in the ternary copper-based catalyst is 0.5~95wt%, further preferably 0.8~93wt%, and particularly preferably 1~90wt%;
优选地，所述三元铜基催化剂中氧化亚铜的含量为 2-95wt%，进一歩优选为 3-93 wt%, 特别优选为 5-90wt%； Preferably, the content of cuprous oxide in the ternary copper-based catalyst is 2-95wt%, further preferably 3-93wt%, particularly preferably 5-90wt%;
优选地， 所述三元铜基催化剂中氧化铜的含量为 2-95wt%， 进一歩优选为 3-93 wt%, 特别优选为 5-90wt%。 Preferably, the content of copper oxide in the ternary copper-based catalyst is 2-95 wt%, further preferably 3-93 wt%, particularly preferably 5-90 wt%.
9、 如权利要求 7或 8所述的三元铜基催化剂， 其特征在于， 所述催化剂还 含有助催化剂； 9. The ternary copper-based catalyst according to claim 7 or 8, characterized in that the catalyst further contains a cocatalyst;
优选地， 所述助催化剂为元素的单质、 氧化物、 卤化物或铜合金中的 1 种 或至少 2种的组合， 所述元素为锌、 锡或磷中的 1种或至少 2种的组合。 Preferably, the cocatalyst is one or a combination of at least two of the elements, oxides, halides or copper alloys, and the element is one or a combination of at least two of zinc, tin or phosphorus. .
10、一种如权利要求 7-9任一项所述的三元铜基催化剂的用途，其特征在于， 所述三元铜基催化剂用作二甲基二氯硅垸合成反应的催化剂。 10. The use of the ternary copper-based catalyst according to any one of claims 7 to 9, characterized in that the ternary copper-based catalyst is used as a catalyst for the synthesis reaction of dimethyldichlorosilane.
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