WO2014117464A1 - Procédé de préparation d'un catalyseur par broyage à boulet et réduction partielle en phase liquide et catalyseur à base de cuivre ternaire - Google Patents

Procédé de préparation d'un catalyseur par broyage à boulet et réduction partielle en phase liquide et catalyseur à base de cuivre ternaire 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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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.

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Abstract

La présente invention concerne un catalyseur à base de cuivre ternaire, un procédé de préparation associé et une application associée. Le procédé de préparation du catalyseur consiste à : ajouter de l'oxyde de cuivre et un matériau réducteur dans un solvant, broyer, faire réagir, extraire les impuretés et concasser pour obtenir un catalyseur à base de cuivre, comprenant des composants ternaires de cuivre, de l'oxyde cuivreux et de l'oxyde de cuivre. Lorsque le catalyseur est utilisé pour synthétiser un monomère d'organo-silicium, son activité catalytique et sa sélectivité supérieures permettent d'augmenter la capacité de traitement de l'équipement à base de monomère d'organo-silicium de la présente invention, de réduire les coûts de production et d'améliorer le rendement des produits cibles. Le procédé de préparation est simple, peut être effectué facilement dans des conditions modérées et peut être utilisé en production à grande échelle.
PCT/CN2013/076874 2013-02-04 2013-06-06 Procédé de préparation d'un catalyseur par broyage à boulet et réduction partielle en phase liquide et catalyseur à base de cuivre ternaire WO2014117464A1 (fr)

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