CN113209978B - Organosilicon high-activity ternary copper catalyst and preparation method thereof - Google Patents
Organosilicon high-activity ternary copper catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of an organosilicon high-activity multielement copper catalyst, which comprises the following steps: s1, preparing rare earth-dispersed copper powder: adding 0-10wt% of rare earth oxide into copper liquid of a melting electrolytic copper plate, and spraying the copper liquid into copper powder by adopting a high-pressure water atomization process, wherein the particle size of the obtained atomized copper powder is 20-100 mu m; s2, partially oxidizing and dispersing rare earth copper powder: carrying out annealing oxidation on the atomized copper powder obtained in the step S1 by using an atmosphere furnace, and controlling the partial pressure of nitrogen-oxygen mixture gas to be 0-200mbar so that the contents of copper, cuprous oxide and cupric oxide in the product respectively reach 0-20%,50-80% and 5-35%; s3, ball milling: and (3) ball milling the dispersed rare earth copper powder obtained in the step (S2) after partial oxidation. The invention improves the yield of the generated dimethyl dichlorosilane to be higher than 90% and improves the Si conversion rate to be higher than 75% by adopting the organosilicon high-activity multi-element copper catalyst.
Description
Technical Field
The invention relates to the field of organosilicon synthesis, in particular to an organosilicon high-activity ternary copper catalyst and a preparation method thereof.
Background
The organic silicon has unique structure, combines the performances of inorganic materials and organic materials, has the basic properties of low surface tension, small viscosity-temperature coefficient, high compressibility, high gas permeability and the like, has the excellent characteristics of high and low temperature resistance, electric insulation, oxidation stability resistance, weather resistance, flame resistance, hydrophobicity, corrosion resistance, innocuity, tastelessness, physiological inertia and the like, and is widely applied to the industries of aerospace, electronics, electric, construction, transportation, chemical industry, textile, food, light industry, medical treatment and the like. As the number and variety of silicones increases, their range of application is expanding. Because the production of the domestic organic silicon monomer is started later, the production technology of the most advanced organic silicon monomer is mastered by developed countries such as Europe and America at present. The main factors affecting the synthesis of silicone monomers are three: firstly, the quality of a silicon metal raw material; second, catalyst capacity; and thirdly, synthesizing equipment and parameter control. At present, the synthesis of industrial organosilicon silane monomers mainly adopts a direct method, and a certain proportion of copper-based powder is required to be added as a reaction catalyst in the synthesis reaction process, so that the performance characteristics of the copper-based powder catalyst can greatly influence the selectivity and conversion rate of a synthesized product.
In the synthesis reaction of the organic silicon monomer by taking copper-based powder as a catalyst, the components of the reaction products are diversified due to the complex reaction mechanism and the simultaneous occurrence of a plurality of side reactions. Among the numerous reaction products, dimethyldichlorosilane is the most fundamental important monomer raw material in the silicone industry, namely the most important target reaction product of the silicone synthesis reaction. In the direct method for synthesizing methyl chlorosilane monomer products which is commonly adopted at home and abroad at present, the target product dimethyl dichlorosilane can generate more than 10 percent of high-boiling products and low-boiling products. The invention provides a high-activity multielement copper catalyst, which can improve the selectivity of generating dimethyl dichlorosilane in the direct method synthesis of organosilicon and increase the reaction speed.
Copper powder catalyst is an indispensable important raw material in the process of synthesizing organic silicon by a direct method. At present, copper chloride series catalysts, copper tin zinc phosphorus series catalysts and copper oxide ternary copper powder catalysts are widely used in the industry. The yield of the dimethyl dichlorosilane generated by adopting the reactions of the catalysts is about 85 percent, and the silicon conversion rate is lower than 70 percent.
The copper is subjected to hot melting, heat preservation and water atomization and other process treatments by application number CN201910116090.3 of patent 'a production process of ternary copper powder catalyst' filed by Anhui Xudi crystal powder new material technology Co., ltd., which belongs to a branch of the existing ternary copper powder catalyst process and is different from the multi-element copper powder catalyst with the molten rare earth oxide; patent 'a double single-atom auxiliary agent supported copper oxide catalyst' reported by the process engineering institute of the Chinese family 'Jihengfang' discloses No. CN109663596A, a preparation method and application thereof, which is a copper-based catalyst added with Sn, zn and other elements, the preparation mode is different from the traditional ball milling mode, and the yield and the silicon conversion rate of the target product are not obviously improved; patent publication No. CN109908924A of Lanzhou Star cleaning Co., ltd. Preparation method for high activity cuprous chloride catalyst for organosilicon monomer synthesis score is a preparation method for cupric chloride series catalyst.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides an organosilicon high-activity ternary copper catalyst and a preparation method thereof, wherein the yield of the generated dimethyl dichlorosilane is increased to be higher than 90%, and the Si conversion rate is increased to be higher than 75%.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of an organosilicon high-activity multi-element copper catalyst comprises the following steps:
s1, preparing rare earth-dispersed copper powder: adding 0-10wt% of rare earth oxide into copper liquid of a melting electrolytic copper plate, and spraying the copper liquid into copper powder by adopting a high-pressure water atomization process, wherein the particle size of the obtained atomized copper powder is 0-200 mu m, and the particle size is preferably 20-100 mu m;
s2, partially oxidizing and dispersing rare earth copper powder: carrying out annealing oxidation on the atomized copper powder obtained in the step S1 by using an atmosphere furnace, and controlling the partial pressure of nitrogen-oxygen mixture gas to be 0-200mbar so that the contents of copper, cuprous oxide and cupric oxide in the product respectively reach 0-20%,50-80% and 5-35%;
s3, ball milling: and (3) ball milling the dispersed rare earth copper powder obtained in the step (S2) after partial oxidation.
Further, the electrolytic copper plate is melted in the step S1, and the superheat degree of the molten copper is kept to be 100-600 ℃.
Further, the annealing oxidation temperature in the S2 is 600-700 ℃, the oxygen partial pressure of the nitrogen-oxygen mixture is 50-100mbar, and the contents of copper, cuprous oxide and cupric oxide in the product respectively reach 0-12%,50-75% and 10-30%.
Further, the ball milling time in the step S3 is 80-100min.
Further, the Cu content of the electrolytic copper plate adopted in the S1 is more than 99.995 percent, and the particle size of the rare earth oxide powder is 0.05-20 mu m.
Further, the organic silicon high-activity multi-element copper catalyst sequentially comprises a copper oxide outer layer, a cuprous oxide middle layer, a cuprous oxide layer and a copper core from inside to outside, wherein the copper oxide outer layer, the cuprous oxide middle layer, the cuprous oxide layer and the copper core all have dispersed rare earth oxides.
Further, the organosilicon high-activity polybasic elementThe copper catalyst is gray or black powder, and has bulk density of 0.5-2.0g/cm 3 The grain diameter is 1-80 mu m, and the microcosmic appearance is porous spheroid particles.
Compared with the prior art, the invention has the beneficial effects that: by adopting the organosilicon high-activity multi-element copper catalyst, the yield of the generated dimethyl dichlorosilane is increased to be higher than 90%, and the Si conversion rate is increased to be higher than 75%.
Drawings
The disclosure of the present invention is described with reference to the accompanying drawings. It is to be understood that the drawings are designed solely for the purposes of illustration and not as a definition of the limits of the invention. In the drawings, like reference numerals are used to refer to like parts. Wherein:
figure 1 schematically shows a block diagram of a multi-component copper powder catalyst particle.
Fig. 2 shows the variation of the particle size of the powder with increasing ball milling time.
Reference numerals in the drawings: 1-copper core, 2-cuprous oxide layer, 3-copper oxide layer, 4-rare earth oxide particles.
Detailed Description
It is to be understood that, according to the technical solution of the present invention, those skilled in the art may propose various alternative structural modes and implementation modes without changing the true spirit of the present invention. Accordingly, the following detailed description and drawings are merely illustrative of the invention and are not intended to be exhaustive or to limit the invention to the precise form disclosed.
An embodiment according to the invention is shown in connection with fig. 1. The organic silicon high-activity multi-element copper catalyst sequentially comprises a copper oxide outer layer, a cuprous oxide middle layer, a cuprous oxide layer and a copper inner core from inside to outside, wherein the copper oxide outer layer, the cuprous oxide middle layer, the cuprous oxide layer and the copper inner core all have dispersed rare earth oxides.
The preparation method of the organosilicon high-activity multi-element copper catalyst specifically comprises the following steps:
(1) Production of rare earth-dispersed copper powder
An electrolytic copper plate with Cu content more than 99.995% is used as a raw material for smelting, and the superheat degree of molten copper is kept at 100-600 ℃. The rare earth oxide powder is added while stirring the copper liquid, and the particle size of the rare earth oxide powder used in the invention is 0.05um-20um. And (3) carrying out water atomization on the copper liquid with the uniformly dispersed rare earth oxide, wherein in the water atomization process, copper liquid drops containing the rare earth oxide are rapidly cooled, and the rare earth oxide is dispersed in copper powder particles.
The granularity of the finished product finally prepared by the overlarge grain size of the copper powder is coarser, and the catalytic activity is lower; the particle size of the finished product finally prepared is smaller, and the catalytic activity is better, but because the powder is too small, the powder can be carried away by the air flow in the reaction bed, the residence time is too short, and the good catalytic effect can not be achieved.
In examples 1 to 6, the electrolytic copper plate was melted and then adjusted to different superheating degrees, and rare earth oxide powder was added to the copper liquid to observe the dispersion of the rare earth oxide powder.
| Degree of superheat of copper liquid | Rare earth oxide dispersion | |
| Example 1 | 20 | Not disperse |
| Example 2 | 100 | Dispersing with micronucleus of more than 1mm |
| Example 3 | 200 | Dispersing, and has a small amount of micronuclei above 0.5mm |
| Example 4 | 300 | Uniformly dispersed |
| Example 5 | 400 | Uniformly dispersed |
| Example 6 | 500 | Uniformly dispersed |
The results of examples 1-6 show that a high degree of superheat of the copper liquid is advantageous for dispersion of the rare earth oxide powder particles, and that the combined cost and refractory life should be at least 300 ℃ greater than the degree of superheat.
(2) Partial oxidation of rare earth-dispersed copper powder
The atomized dispersed rare earth copper powder is annealed by using an atmosphere furnace, and the content of copper, cuprous oxide and cupric oxide in the final product is regulated and controlled by controlling the partial pressure of nitrogen-oxygen mixed gas to be 0mbar-200mbar, so that the content of copper oxide and cuprous oxide in the final product is respectively 0% -20%,50% -80% and 5% -35%. The microstructure of the finally obtained copper powder particles is respectively as follows from outside to inside: the copper oxide composite material comprises a copper oxide outer layer, a cuprous oxide middle layer, a copper layer with dispersed cuprous oxide and a copper inner core, wherein dispersed rare earth oxide exists in each layer.
In examples 7 to 14, the oxygen partial pressure of the nitrogen-oxygen mixture was controlled to 50mbar, the oxidation temperature was controlled to increase from 200℃to 100℃and the content of copper oxide and cuprous oxide finally produced was measured.
Note that: rare earth oxide content is not taken into account
Example 7-example 14 shows that at an oxygen partial pressure of 50mbar, the copper oxide and cuprous oxide contents increase with increasing temperature, and that the oxidation efficiency increases significantly above 500 ℃.
In examples 15 to 22, the oxygen partial pressure of the nitrogen-oxygen mixture was controlled to 100mbar, the oxidation temperature was controlled to increase from 200℃to 100℃and the content of copper oxide and cuprous oxide finally produced was measured.
Note that: rare earth oxide content is not taken into account
Example 15-example 22 the accuracy of the copper oxide, cuprous oxide, copper content to reach target value range is higher at 100mbar oxygen partial pressure. The preferred partial oxidation conditions are 600℃to 700℃and an oxygen partial pressure of 100 mbar.
(3) Ball milling
The ball milling process is shown in fig. 2, powder particles are continuously impacted by steel balls, the broken particle size is gradually reduced, and the specific surface area of the powder is increased, so that the activity is increased. On the other hand, in the ball milling process, the microscopic crystal lattice of the powder has the defects of distortion, dislocation and the like, so that a large amount of crystal lattice energy is stored, and the activity of the powder is increased. In example 23, the partially oxidized rare earth oxide copper powder dispersion was subjected to a ball milling treatment, and the particle size of the powder was gradually reduced with increasing ball milling time, preferably 80 minutes to 100 minutes.
(4) Synthetic reaction test
On an organosilicon synthesis pilot plant, organosilicon monomers are synthesized by a direct method, and the catalytic effect of the copper powder of the invention is evaluated by analyzing the monomer products. Example 23-example 29 the results of the test are shown in the following table with rare earth oxide additions of 6% -8% optimum, dimethyldichlorosilane yields of greater than 90% and silicon conversions of greater than 75%.
The invention will be further described with respect to an exemplary embodiment.
1. Production of rare earth-dispersed copper powder
Melting a raw material electrolytic copper plate by using an induction furnace, keeping the superheat degree at 350-400 ℃, starting a stirring system, adding rare earth oxide powder into the middle part of the copper liquid by using a special feeding system, wherein the addition amount of the rare earth oxide is 5.0wt%, and uniformly dispersing the rare earth oxide powder particles in the copper liquid under the stirring effect. And then high-pressure water atomization spray granulation is adopted, and after the granulation is finished, powder is collected, the detection granularity D50 is 36um, and the D90 is 67um.
2. Partial oxidation of rare earth-dispersed copper powder
Annealing the atomized dispersed rare earth copper powder by using an atmosphere furnace, controlling the partial pressure of nitrogen-oxygen mixture gas and oxygen to be 100mbar, maintaining the temperature at 700 ℃ for 8 hours, detecting the partially oxidized product, and detecting Cu of 6.6 percent and Cu of 2 O 68.5％，CuO 24.9％。
3. Ball milling treatment
Ball milling is carried out on powder by using a high-energy ball mill for 90 minutes, and the powder after ball milling is detected: bulk density 0.97g/cm 3 The average particle diameter was 3.6. Mu.m.
4. Organosilicon synthetic reaction test
100g of industrial silicon powder and 3g of multi-element copper powder catalyst are weighed, stirred and mixed uniformly, then added into a test fluidized bed device, nitrogen is introduced and the temperature is raised to 300 ℃, and when the temperature is higher than 280 ℃, methyl chloride gas is opened and the flow rate is kept at 120mg/h. The reaction products are connected to a gas chromatograph for analysis, and the results are shown in the following table, the yield of the dimethyldichlorosilane is improved to be higher than 90%, and the Si conversion rate is improved to be higher than 75%.
| First yield of | Yield of dimethyl | Trimethyl yield | High boiling yields | Hydride yield | Others | Silicon conversion |
| 3.4％ | 90.5％ | 1.6％ | 1.3％ | 1.7％ | 1.5％ | 79.5％ |
The technical scope of the present invention is not limited to the above description, and those skilled in the art may make various changes and modifications to the above-described embodiments without departing from the technical spirit of the present invention, and these changes and modifications should be included in the scope of the present invention.
Claims (5)
1. The preparation method of the organic silicon high-activity multi-element copper catalyst is characterized by comprising the following steps of:
s1, preparing rare earth-dispersed copper powder: adding 2-10wt% of rare earth oxide into copper liquid of a melting electrolytic copper plate, and spraying the copper liquid into copper powder by adopting a high-pressure water atomization process, wherein the particle size of the obtained atomized copper powder is 0-200 mu m; wherein, the electrolytic copper plate is melted, and the superheat degree of the molten copper liquid is kept to be 300-600 ℃; the Cu content of the adopted electrolytic copper plate is more than 99.995 percent, and the particle size of the rare earth oxide powder is 0.05-20 mu m;
s2, partially oxidizing and dispersing rare earth copper powder: carrying out annealing oxidation on the atomized copper powder obtained in the step S1 by using an atmosphere furnace, wherein the annealing oxidation temperature is 600-700 ℃, and the oxygen partial pressure of the nitrogen-oxygen mixture is controlled to be 50-100mbar, so that the copper, cuprous oxide and copper oxide content in the product respectively reach 0-20%,50-80%,5-35%, and the copper content in the product is not 0;
s3, ball milling: and (3) ball milling the dispersed rare earth copper powder obtained in the step (S2) after partial oxidation.
2. The method for preparing the organosilicon high-activity multi-element copper catalyst according to claim 1, wherein in the S2, the copper, cuprous oxide and cupric oxide content in the product respectively reach 0-12%,50-75% and 10-30%, and the copper content is not 0.
3. The method for preparing the organosilicon high-activity multi-element copper catalyst according to claim 1, wherein the ball milling time in the step S3 is 80-100min.
4. The organic silicon high-activity multi-element copper catalyst prepared by the preparation method of the organic silicon high-activity multi-element copper catalyst according to any one of claims 1 to 3, which is characterized by sequentially comprising a copper oxide outer layer, a cuprous oxide intermediate layer, a cuprous oxide layer and a copper core from inside to outside, wherein the copper oxide outer layer, the cuprous oxide intermediate layer, the cuprous oxide layer and the copper core all have dispersed rare earth oxides.
5. The organosilicon high-activity multi-element copper catalyst according to claim 4, wherein the organosilicon high-activity multi-element copper catalyst is gray or black powder, the loose density is 0.5-2.0g/cm < 3 >, the particle size is 1-80 μm, and the micro morphology is porous spheroid particles.
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