CN113634259B - Copper oxide composite catalyst and preparation method and application thereof - Google Patents
Copper oxide composite catalyst and preparation method and application thereof Download PDFInfo
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- 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
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
Abstract
The invention provides a copper oxide composite catalyst, which comprises copper oxide, tin and phosphorus. The preparation method comprises the following steps: mixing copper oxide with a tin-containing assistant and a phosphorus-containing assistant to obtain a mixed material; and ball-milling the mixed material to obtain the composite catalyst. The copper oxide composite catalyst has an excellent catalytic effect in the synthetic process of an organic silicon monomer dimethyl dichlorosilane, the preparation method effectively avoids a plurality of problems in the production process of an industrially used ternary copper catalyst, and the preparation method is simple to operate, high in efficiency, free of pollution and low in production energy consumption.
Description
Technical Field
The invention belongs to the field of catalysts, relates to a composite catalyst, and particularly relates to a copper oxide composite catalyst and a preparation method and application thereof.
Background
Methylchlorosilanes are the most important organosilicon monomers for the preparation of organosilicon materials. Wherein, dimethyl dichlorosilane [ (CH) 3 ) 2 SiCl 2 Abbreviation, M2]The required amount of (C) is the largest, and accounts for about 90% of the monomer yield of the organosilicon industry. At present, the industrial production of methyl chlorosilane mainly adopts a direct method (Rochow reaction), namely, silicon powder (Si) and methyl chloride (MeCl) directly react to synthesize the methyl chlorosilane under the action of a copper-based main catalyst and a small amount of auxiliary agent. The method has the advantages of easily available raw materials and simple process, but the side reactions are numerous, and the product components are complex. Therefore, how to improve the yield and selectivity of M2 has been a hot research focus in the silicone industry.
The copper catalyst is a classical catalyst for synthesizing methyl chlorosilane by a direct method. The catalyst used in industry is electrolytic copper powder, but the catalyst has small specific surface area and poor catalytic activity and has been replaced; the cuprous chloride developed in the later period has poor stability, and is gradually eliminated.The most used three-element copper catalyst Cu-Cu in the production is developed by Smith Corona Marchant (SCM) company in the last 70 th century 2 O-CuO, the catalyst has the advantages of high activity, good selectivity, short induction period, easy storage and the like.
In recent years, a great deal of research is carried out on the preparation of the ternary copper catalyst in China. Patents CN1072870A, CN101811057A, CN102671660A, CN1008423B, CN102441382A, CN103599782B, CN103127937A and the like disclose different methods for preparing ternary copper catalysts (Cu-Cu) 2 O-CuO).
At present, the ternary copper catalyst is mainly prepared by performing ball milling on copper powder through partial oxidation, and the preparation method has the advantages of easily available raw materials and convenience for large-scale production. However, in the actual process of preparing the ternary copper catalyst by partially oxidizing copper powder, heating part oxidizing devices such as a rotary furnace, a fluidized bed and a flat furnace are adopted, so that the problems of easy sintering and agglomeration of the copper powder, sintering and bonding on a heating wall surface (sticky wall), nonuniform oxidation, low efficiency, high energy consumption and the like exist, so that the components of the ternary copper catalyst are difficult to regulate and control, the particle size distribution is nonuniform, and the performance of the ternary copper catalyst is influenced. In recent years, the above problems have not been completely solved although various improvements have been made to the processes and apparatuses. Therefore, the development of a copper catalyst preparation method which is simple in operation, controllable in process, low in cost, high in activity and high in selectivity is of great significance.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the copper oxide composite catalyst and the preparation method and application thereof, the copper oxide composite catalyst has an excellent catalytic effect in the synthetic process of an organosilicon monomer dimethyldichlorosilane, the preparation method effectively avoids a plurality of problems in the production process of an industrially used ternary copper catalyst, and the copper oxide composite catalyst is simple to operate, high in efficiency, free of pollution and low in production energy consumption.
In order to achieve the technical effect, the invention adopts the following technical scheme:
one of the objectives of the present invention is to provide a copper oxide composite catalyst, which comprises copper oxide, tin and phosphorus.
According to the invention, the composite catalyst takes copper oxide as a main body, and due to the introduction of tin and phosphorus, an auxiliary agent is easily and tightly combined with copper oxide particles, and a solid-phase reaction is generated between the copper oxide and the auxiliary agent to form an active heterojunction, so that a large number of defects are generated on the surface of the copper oxide, abundant active sites are formed, the synergistic effect of a main catalyst and a cocatalyst is promoted, and the selectivity of a reaction main product and the conversion rate of silicon powder are improved.
In a preferred embodiment of the present invention, the mass ratio of tin to copper oxide in the composite catalyst is 50 to 500ppm, such as 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm or 450ppm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the mass ratio of the copper oxide to the phosphorus in the composite catalyst is 50 to 500ppm, such as 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, and the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the composite catalyst also comprises copper.
In a preferred embodiment of the present invention, the particle size distribution of the composite catalyst is in the range of 0.4 to 4.0. Mu.m, such as 0.5. Mu.m, 1.0. Mu.m, 1.5. Mu.m, 2.0. Mu.m, 2.5. Mu.m, 3.0. Mu.m, or 3.5. Mu.m, but the particle size distribution is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, and preferably in the range of 0.6 to 3.0. Mu.m.
The second object of the present invention is to provide a method for preparing the composite catalyst, comprising:
mixing copper oxide with a tin-containing auxiliary agent and a phosphorus-containing auxiliary agent to obtain a mixed material;
and ball-milling the mixed material to obtain the composite catalyst.
In the invention, the preparation method adopts single copper oxide as a raw material, and the components are easy to control; after the tin-containing assistant and the phosphorus-containing assistant are added and ball-milled, the particle size of copper oxide particles can be greatly reduced due to the brittleness characteristic of the copper oxide, the particle size distribution is uniform, and a large number of defects are generated on the surface of the copper oxide particles to form rich active sites.
As a preferred technical solution of the present invention, the copper oxide includes any one of copper oxide obtained by oxidizing elemental copper and/or low-valent copper, commercial copper oxide powder, or copper oxide obtained by calcining copper salt, or a combination of at least two of the above, and the combination is exemplified by, typically but not limited to: the copper oxide powder is prepared by oxidizing elemental copper and/or low-valent copper to obtain a combination of the copper oxide and commercial copper oxide powder, calcining the commercial copper oxide powder and copper salt to obtain a combination of the copper oxide obtained by calcining the copper salt and the copper oxide obtained by oxidizing the elemental copper and/or the low-valent copper, or oxidizing the elemental copper and/or the low-valent copper to obtain the copper oxide, calcining the commercial copper oxide powder and the copper oxide obtained by calcining the copper salt, and the like.
As a preferable technical scheme of the invention, the tin-containing auxiliary agent comprises simple substance tin and copper-tin alloy;
preferably, the copper-tin alloy has a tin mass fraction of 3 to 20%, such as 4%, 5, 6, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%, but is not limited to the recited values, and other values not recited within the range are equally applicable.
As a preferable technical scheme of the invention, the phosphorus-containing additive comprises copper-phosphorus alloy.
Preferably, the mass fraction of phosphorus in the copper-phosphorus alloy is 8 to 12, such as 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, or 11.5%, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
In a preferred embodiment of the present invention, the ball milling is dry ball milling.
In the present invention, the ball milling is performed in a dry type agitator ball mill, and the ball milling method using the dry type agitator ball mill is well known in the art, and the specific conditions may be selected according to the actual specification of the material and the product, and are not specifically limited herein.
Preferably, the material of the grinding beads used for ball milling comprises zirconium oxide and/or stainless steel, and preferably stainless steel.
Preferably, the beads have a diameter of from 2 to 10mm, such as 3mm, 4mm, 5mm, 6mm, 7mm, 8mm or 9mm, but are not limited to the values recited, and other values not recited within this range are equally applicable, preferably from 3 to 8mm.
Preferably, the mass ratio of the mixed material to the milling beads is 1 (1-7), such as 1;
preferably, the ball milling time is 0.5 to 4 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or 3.5 hours, but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 1 to 2 hours.
The invention also aims to provide application of the composite catalyst, and the composite catalyst is applied to selective synthesis of dimethyldichlorosilane in organosilicon monomer synthesis reaction.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The invention provides a composite copper oxide catalyst, which has excellent catalytic performance, can regulate and control the tin content and the phosphorus content in a certain range, is applied to methyl chlorosilane synthesis reaction, and shows higher selectivity of dimethyl dichlorosilane and conversion rate of raw material silicon powder compared with the traditional ternary copper catalyst;
(2) The invention provides a preparation method of a composite copper oxide catalyst, which adopts single copper oxide as a raw material, and is easy to control components; after ball milling, a large number of defects can be generated on the surface of the copper oxide, and abundant active sites are formed; simple operation, high efficiency and low production energy consumption.
Drawings
FIG. 1 is an XRD pattern of a copper oxide composite catalyst prepared in example 1 of the present invention;
FIG. 2 is a particle size distribution diagram of the copper oxide composite catalyst prepared in example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 150kg of stainless steel grinding balls with the diameter of 5mm, wherein the copper oxide composite catalyst is obtained after ball milling for 2 hours, the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.6-3.0 microns.
XRD test analysis and particle size analysis are carried out on the prepared copper oxide composite catalyst, and the method specifically comprises the following steps:
(1) XRD test analysis: XRD measurement was carried out on the copper oxide composite catalyst obtained as described above by using X' pertro MPD type multifunctional X-ray diffractometer manufactured by Panalytical corporation (panacaceae) in the netherlands, and the XRD spectrum is as shown in fig. 1, and it can be seen from fig. 1 that shoulder peaks consisting of 2 θ =35.5 ° and 2 θ =38.7 ° are characteristic peaks of CuO;
(2) And (3) particle size analysis: particle size analysis was performed using a Dandongbertt BT-9300Z laser particle size distribution analyzer, as can be seen from FIG. 2, the particle size range of the prepared copper oxide composite catalyst was 0.6-3.0. Mu.m.
Example 2
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 25g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 150kg of stainless steel grinding balls with the diameter of 5mm, wherein the copper oxide composite catalyst is obtained after ball milling for 2 hours, the mass ratio of tin to copper oxide is 0.005% (50 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.5-2.6 mu m.
Example 3
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 250g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 150kg of stainless steel grinding balls with the diameter of 5mm, wherein the copper oxide composite catalyst is obtained after ball milling for 2 hours, the mass ratio of tin to copper oxide is 0.050% (500 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.8-2.9 mu m.
Example 4
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
50kg of commercial copper oxide powder, 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 31.3g of commercial copper-phosphorus alloy (CuP 8, containing 8% of P) are simply mixed, and then dry-ball milled together with 350kg of stainless steel milling balls with the diameter of 5mm, and the copper oxide composite catalyst is obtained after ball milling for 2 hours, wherein the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.005% (50 ppm), and the particle size distribution range of the catalyst is 0.9-4.0 mu m.
Example 5
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
after mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 312.5g of commercial copper-phosphorus alloy (CuP 8, containing 8% of P), dry ball milling is carried out together with 350kg of stainless steel grinding balls with the diameter of 5mm, and the copper oxide composite catalyst is obtained after ball milling for 2h, wherein the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.050% (500 ppm), and the particle size distribution range of the catalyst is 0.7-4.0 μm.
Example 6
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
after mixing 50kg of commercial copper oxide powder, 7.5g of commercial copper-tin powder and 50g of commercial copper-phosphorus alloy (CuP 8, the content of P is 8%), carrying out dry ball milling on the mixture and 150kg of stainless steel grinding balls with the diameter of 5mm together, and carrying out ball milling for 2 hours to obtain the copper oxide composite catalyst, wherein the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.1-2.6 mu m.
Example 7
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 150kg of zirconia grinding balls with the diameter of 5mm, wherein the copper oxide composite catalyst is obtained after ball milling for 2 hours, the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.4-4.0 mu m.
Example 8
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 150kg of stainless steel grinding balls with the diameter of 2mm, wherein the copper oxide composite catalyst is obtained after ball milling for 0.5h, the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 1.0-4.0 mu m.
Example 9
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8% of P), and carrying out dry ball milling on the mixture and 150kg of stainless steel grinding balls with the diameter of 8mm, wherein the copper oxide composite catalyst is obtained after ball milling for 4 hours, the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 1.0-4.0 mu m.
Example 10
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 150kg of stainless steel grinding balls with the diameter of 10mm, wherein the copper oxide composite catalyst is obtained after ball milling for 4 hours, the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.9-3.5 microns.
Example 11
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 50kg of stainless steel grinding balls with the diameter of 5mm, wherein the copper oxide composite catalyst is obtained after ball milling for 2 hours, the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.5-4.0 mu m.
Example 12
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
mixing 50kg of commercial copper oxide powder with 75g of commercial copper-tin alloy (CuSn 10, containing 10% of Sn) and 50g of commercial copper-phosphorus alloy (CuP 8, containing 8%) and carrying out dry ball milling on the mixture and 350kg of stainless steel grinding balls with the diameter of 5mm, wherein the copper oxide composite catalyst is obtained after ball milling for 2 hours, the mass ratio of tin to copper oxide is 0.015% (150 ppm), the mass ratio of phosphorus to copper oxide is 0.008% (80 ppm), and the particle size distribution range of the catalyst is 0.5-4.1 mu m.
Comparative example 1
The comparative example provides a preparation method of a copper oxide catalyst, 200g of commercial copper oxide powder is weighed, then the commercial copper oxide powder and 2000g of stainless steel balls with the diameter of 5mm are added into a vertical stirring mill, and the copper oxide catalyst is obtained after ball milling for 2 hours, does not contain Sn and P auxiliaries, and has the particle size distribution range of 0.5-3.1 mu m.
Comparative example 2
This comparative example was conducted under the same conditions as example 1 except that the commercial copper-tin alloy (CuSn 10, with Sn of 10%) was added in an amount of 115g (keeping the total mass of the assistants the same as that of example 1) and no commercial copper-phosphorus alloy was added.
Comparative example 3
This comparative example was conducted under the same conditions as example 1 except that the commercial copper-phosphorus alloy (CuP 8, containing 8% of P) was added in an amount of 143.75g (keeping the total mass of the assistants the same as that of example 1) and no commercial copper-tin alloy was added.
Comparative example 4
This comparative example was the same as example 1 except that a commercial copper-tin alloy (CuSn 10, with Sn of 10%) was replaced with an equal mass of a commercial copper-zinc alloy (CuZn 10, with Zn of 10%).
Comparative example 5
This comparative example was identical to example 1 except that a commercial copper-phosphorus alloy (CuP 8, containing 8% of P) was replaced with an equivalent mass of a commercial copper-boron alloy (CuB 8, containing 8% of B).
In order to examine the catalytic performance of the copper oxide composite catalyst provided by the invention in the selective synthesis process of dimethyldichlorosilane, the copper oxide catalysts prepared in examples 1-12 and comparative examples 1-5 and commercial ternary copper catalysts (A, B and C) produced by different manufacturers are subjected to catalytic performance tests, and the test specifically comprises the following steps: a miniature fixed bed device is adopted for carrying out catalytic performance test, and 10g of silicon powder, 0.5g of catalyst and 0.015g of zinc auxiliary agent are uniformly mixed and then are loaded into a fixed bed reactor (phi 20 multiplied by 50) to form a mixed contact body; purging the reaction system for 10 minutes by adopting nitrogen before heating, then starting heating, switching to chloromethane gas with the flow rate of 25mL/min, preheating, contacting with a mixed contact body, controlling the reaction temperature at 325 ℃, and stopping after reacting for 48 hours; the product after reaction flows out from the lower end of the reactor, is condensed by a condenser pipe and then is collected by toluene, and the redundant tail gas is absorbed by alkaline liquor and then is exhausted; and carrying out chromatographic analysis after the collected mixed liquid is subjected to constant volume, and calculating the conversion rate of the silicon powder and the product distribution, wherein the results are shown in table 1.
TABLE 1
Description of Table 1:
(1) M1 represents methyltrichlorosilane; m2 refers to dimethyldichlorosilane, M3 refers to trimethylchlorosilane; M1H represents a methyl hydrosilane; M2H denotes dimethyl hydrosilane; LBR denotes low boiler; HBR denotes high boilers;
(2) The silicon conversion was calculated using the following formula:
wherein W is the weight of the contact.
As can be seen from the performance evaluation results in table 1, in the methylchlorosilane synthesis reaction of the copper oxide composite catalysts (examples 1 to 12) prepared by the present invention, the selectivity of the target product dimethyldichlorosilane and the conversion rate of the reaction raw material silicon powder are significantly higher than those of comparative example 1 (containing no tin and phosphorus promoter), comparative example 2 (containing only tin promoter), comparative example 3 (containing only phosphorus promoter), comparative example 4 (replacing tin promoter with zinc promoter), comparative example 5 (replacing phosphorus promoter with boron promoter), pure commercial copper oxide and commercial ternary copper catalysts a, B and C produced by 3 different manufacturers. Because the preparation method of the invention adds proper tin-containing and phosphorus-containing additives, the prepared copper oxide composite catalyst has better performance. Therefore, the method disclosed by the invention is outstanding in innovation and easy to industrialize and apply.
The applicant states that the present invention is described by the above embodiments to explain the detailed structural features of the present invention, but the present invention is not limited to the above detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications, equivalent substitutions of selected elements of the present invention, additions of auxiliary elements, selection of specific forms, etc., are intended to fall within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (14)
1. The copper oxide composite catalyst is characterized by consisting of copper oxide, tin, phosphorus and copper;
the mass ratio of tin to the copper oxide in the composite catalyst is 50-500 ppm;
the mass ratio of phosphorus in the composite catalyst to the copper oxide is 50-500 ppm;
the particle size distribution range of the composite catalyst is 0.4-4.0 mu m;
the composite catalyst is prepared by the following preparation method: mixing copper oxide with a tin-containing auxiliary agent and a phosphorus-containing auxiliary agent to obtain a mixed material; ball-milling the mixed material to obtain the composite catalyst;
the copper oxide comprises any one or combination of at least two of copper oxide obtained by oxidizing simple substance copper and/or low-valence copper, commercial copper oxide powder or copper salt calcined copper oxide;
the tin-containing auxiliary agent comprises simple substance tin and copper-tin alloy;
the phosphorus-containing additive comprises a copper-phosphorus alloy;
the ball milling mode is dry ball milling.
2. The composite catalyst according to claim 1, wherein the particle size distribution of the composite catalyst is in the range of 0.6 to 3.0 μm.
3. A method for preparing the composite catalyst according to claim 1 or 2, comprising:
mixing copper oxide with a tin-containing auxiliary agent and a phosphorus-containing auxiliary agent to obtain a mixed material;
ball-milling the mixed material to obtain the composite catalyst;
the copper oxide comprises any one or the combination of at least two of copper oxide obtained by oxidizing simple substance copper and/or low-valence copper, commercial copper oxide powder or copper oxide obtained by calcining copper salt;
the tin-containing auxiliary agent comprises simple substance tin and copper-tin alloy;
the phosphorus-containing additive comprises a copper-phosphorus alloy;
the ball milling mode is dry ball milling.
4. A preparation method according to claim 3, wherein the mass fraction of tin in the copper-tin alloy is 3-20%.
5. A preparation method according to claim 3, wherein the mass fraction of phosphorus in the copper-phosphorus alloy is 8-12%.
6. The preparation method of claim 3, wherein the material of the milling beads used for the ball milling comprises zirconia and/or stainless steel.
7. The preparation method of claim 6, wherein the material of the grinding beads used for the ball milling is stainless steel.
8. The method of claim 6, wherein the beads have a diameter of 2 to 10mm.
9. The method of claim 8, wherein the beads have a diameter of 3 to 8mm.
10. The preparation method according to claim 6, wherein the mass ratio of the mixed material to the milling beads is 1 (1-7).
11. The preparation method of claim 10, wherein the mass ratio of the mixed material to the milling beads is 1 (3-5).
12. The preparation method according to claim 3, wherein the time for ball milling is 0.5 to 4 hours.
13. The preparation method according to claim 12, wherein the time for ball milling is 1 to 2 hours.
14. Use of the composite catalyst according to claim 1 or 2, wherein the composite catalyst is used for selective synthesis of dimethyldichlorosilane in the synthesis reaction of organosilicon monomers.
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| CN202110935288.1A CN113634259B (en) | 2021-08-16 | 2021-08-16 | Copper oxide composite catalyst and preparation method and application thereof |
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