CN102773102B - Catalyst for low-temperature synthesis of methanol and preparation method - Google Patents

Abstract

The invention relates to the field of low-temperature synthetic methanol production, in particular, the invention relates to a catalyst and a preparation method for low-temperature synthetic methanol. The method comprises the steps of crushing and sieving waste contacts produced by the direct method of producing methyl chlorosilane, and then cleaning with an organic solvent. The method may further include the following step: performing one or more of oxidation treatment, reduction treatment and heat treatment on the cleaned waste contact body to obtain a catalyst for producing methanol at low temperature from synthesis gas. The invention has the advantages of: solving the problem of high-value comprehensive utilization of solid residue waste contacts in the organosilicon synthesis industry; low raw material cost, simple operation method, and easy large-scale production; the prepared catalyst exhibits higher methanol synthesis activity and thermal stability.

Description

Catalyst and preparation method for synthesizing methanol at low temperature

technical field

The invention relates to the field of low-temperature synthetic methanol production, in particular, the invention relates to a catalyst and a preparation method for low-temperature synthetic methanol.

Background technique

Silicone materials have dual properties of inorganic materials and organic materials, high and low temperature resistance, electrical insulation, weather resistance, corrosion resistance, non-toxic and tasteless and other excellent properties, widely used in electronics, automobiles, petroleum, chemicals, construction, aerospace, etc. field. Methylchlorosilane is the most important organosilicon monomer used in the preparation of organosilicon materials, and is the foundation and pillar of the entire organosilicon industry.

Among the various methods for synthesizing methylchlorosilane, the direct method has become the only industrialized production method because of its simple process, high yield, no solvent, low risk and convenience for continuous large-scale production. In the fluidized bed reactor, silicon powder, main catalyst copper powder, and cocatalyst zinc powder are mixed to form an active contact body. As the reaction continues, more and more deposits are deposited on the contact body surface, which reduces the activity of the contact body. The conversion rate and selectivity are greatly reduced. At this time, this part needs to be discharged from the reactor. At the same time, a new contact body is added to facilitate the stable reaction. In addition, the gas-solid separation system of the fluidized bed continuously discharges fine powder with serious surface pollution. Two parts of waste residue become waste contacts. These waste contacts are mainly composed of silicon, copper, and carbon, and contain a small amount of tin, zinc and other components. The average particle size of the waste contacts is relatively small, and they contain highly active copper. Exposure to the air can cause oxidation or even Burning, serious environmental pollution, but also a hidden danger in safe production. With the continuous expansion of the production scale of organosilicon monomers, the amount of waste contacts continues to increase. The rational treatment and utilization of waste contacts has always been an urgent problem to be solved for the sustainable development of my country's organosilicon industry.

At present, a lot of research has been done on the treatment of waste contacts at home and abroad. The patent US4758352 has studied the recovery of silicon and copper from waste contacts, adding hydrochloric acid at 70°C-80°C to the waste contacts to form a suspension; Raise the temperature to 69°C; adjust the pH value to 6 with a strong base, continuously feed SO ₂ , add 15% sodium hydroxide solution to adjust the pH value to 9, and dry the precipitate at 120°C to obtain copper oxide; The contact body is deeply converted into white plus black, SiCl ₄ , HSiCl ₃ , phenylchlorosilane and other products. In US2811853, 120g of waste contact body with a particle size of less than 50μm is put into a fluidized bed and heated at 120-140°C for 70h. Then react with 460g of monochloromethane at 320°C to obtain 232g of mixed monomers with a composition of 82% M ₂ , 13.3% M ₁ , 3.5% M ₃ , and 1.2% CH ₃ HSiCl ₂ . In order to facilitate transportation and handling, the waste contact body is deactivated, such as patent US4892694, to process it into stable granules or pellets.

Although a lot of research has been done on the treatment of waste contacts, the treatment process is complicated, the secondary pollution is serious, and the added value of the product is relatively low. Therefore, it is necessary to find a simple, clean and high-value product. very necessary and realistic.

Methanol is an important basic organic chemical raw material, but also a vehicle fuel and fuel cell fuel with great potential. The research and exploration of synthesizing methanol has always been paid attention to internationally. There are two main types of methanol synthesis catalysts used in industrialization, zinc-chromium-based catalysts and copper-based catalysts. Zinc-chromium-based (ZnO/Cr ₂ O ₃ ) catalysts are high-pressure solid catalysts. Due to their low activity and low selectivity, Distillation is difficult, and chromium is poisonous to the human body. At present, this type of catalyst has been phased out. Copper-based catalyst is a low-temperature and low-pressure methanol synthesis catalyst. Its main component is CuO/ZnO/Al ₂ O ₃ (Cu/Zn/Al). ℃, the pressure is 5MPa～10MPa, which is much lower than the traditional synthesis process temperature, which is beneficial to the methanol reaction balance. It has high activity and high selectivity, but it has poor high temperature resistance and is sensitive to sulfur. It is currently the main catalyst used in methanol synthesis in industry.

At present, the existing industrial methods for synthesizing methanol have reached a fairly high level, but there are still three major shortcomings to be overcome and breakthroughs: (1) due to the restriction of the thermodynamic equilibrium at the reaction temperature, the single-pass conversion rate is low, and at the outlet of the synthesis tower The methanol concentration in the product can rarely exceed 7%, so multiple cycles have to be used, which greatly increases the investment in the synthesis gas manufacturing process and the cost of the synthesis gas. (2) ICI and other methods require that the feed gas must contain 5% CO ₂ , thus producing a harmful impurity - water. In order to make the methanol product meet the requirements of fuel and downstream chemical products, the methanol- water separation. (3) The cost of syngas purification by traditional methods such as ICI is very high.

In order to overcome the above three major shortcomings, a large number of improvement studies have been carried out abroad since the 1970s. The long-term research results show that the catalyst system must be fundamentally changed to develop a catalyst system with low temperature (90-180 ° C), high activity, high selectivity, The catalyst system with no overheating problem enables the production process to operate at a high conversion rate of more than 90% and a high selectivity state, which is low temperature liquid phase synthesis of methanol.

Low-temperature synthesis of methanol overcomes the shortcomings of traditional methods, and has a series of advantages, such as: high conversion rate per pass, no need for recycling, good crude product composition, no water, higher alcohols and carbonyl compounds, so it is particularly easy to obtain pure grade anhydrous ethanol , and greatly reduce the energy consumption of separation. The method of liquid phase synthesis of methanol at low temperature is being paid more and more attention.

At present, a large number of researches have been carried out on catalysts for low-temperature synthesis of methanol at home and abroad. Represented by American Amoco Company and Brookhaven National Laboratory, they have developed nickel-based catalysts. The research results show that the active center of the system is composed of a homogeneous catalyst, the reaction system is very active, and the selectivity of methanol can be greater than 95%, with only a small amount of Methyl formate and dimethyl ether by-products. Machionna of SNAM Company has done a lot of research work on copper-based catalysts, and the research results show that its activity and selectivity can reach the same level as that of nickel-based catalysts. Cu/SiO ₂ and Cu/Al ₂ O ₃ catalysts are very active, but are easily poisoned by CO. When Cu/Al ₂ O ₃ is modified, catalysts with higher activity and less poisoning can be obtained. Tsubaki et al. prepared a Cu/ZnO catalyst, using an alcohol solvent as a solvent, to synthesize methanol at low temperature and low pressure (Catalysis Communications 2001, 2, 213-217), and the reaction process is as follows:

CO+H ₂ O=CO ₂ +H ₂

CO ₂ +1/2H ₂ +Cu=HCOOCu

HCOOCu+ROH=HCOOR+CuOH

HCOOR+2H ₂ ＝ROH+CH ₃ OH

CuOH+1/2H ₂ ＝H ₂ O+Cu

The overall reaction is: CO+2H ₂ =CH ₃ OH

When the reaction proceeds, CO and H ₂ O first react to generate CO ₂ and H ₂ , and then CO ₂ and H ₂ react to form copper formate on the surface of the copper catalyst, and then copper formate and alcohol solvent undergo nucleophilic addition and elimination reaction, Formate is generated, and finally the formate is reduced to methanol by the active hydrogen on the copper, and the ROH used in the process is a liquid phase alcohol solvent.

The catalyst prepared by the above method has a high cost, and because the composite catalyst system is used, there are certain interactions and optimal synergistic effects among the components. When some components are dissimilated or poisoned, the activity of the entire system can be caused. decline, the catalyst is easily deactivated.

The invention intends to use silicon-containing waste contacts as catalysts in the synthesis gas methanol production process after simple physical and chemical treatment.

Contents of the invention

The object of the present invention is to provide a catalyst for synthesizing methanol at low temperature.

Another object of the present invention is to provide a method for preparing a catalyst for synthesizing methanol at low temperature.

According to the preparation method of the catalyst for synthesizing methanol at low temperature of the present invention, the method comprises the steps of crushing and screening waste catalysts produced by the direct method of producing methyl chlorosilane, and then cleaning with an organic solvent.

According to the method for preparing a catalyst for synthesizing methanol at low temperature of the present invention, the waste contact body is a waste contact body produced during the preparation of organosilicon monomer methylchlorosilane by a "direct method" fluidized bed process, and mainly contains silicon, One or more of copper and/or carbon, and one or more of traces of zinc, iron, aluminum and tin. The particle size of the waste contact body is 0.5 microns to 100 microns, and its pore structure size is 2 nanometers to 10 microns, wherein the silicon content is 10 to 95 wt%, the copper content is 2 to 50 wt%, and the carbon content is 5 to 20 wt%. The waste contacts in the method are applicable to the present invention, and have good effect when used as a methanol catalyst for synthesis gas at low temperature.

According to the preparation method of the catalyst for synthesizing methanol at low temperature of the present invention, in said step 1), the solid residue waste contact body produced in the organic silicon synthesis industry is cleaned once or more times with an organic solvent, and dried in a drying oven after filtering , obtain silicon/carbon/copper porous composite body, it can be used as the silicon/carbon/copper porous composite body catalyst used in syngas to methanol, described organic solvent can be: ethanol, benzene, toluene, chloroform, acetone, tetrahydrofuran , One or more of ether.

According to the preparation method of the catalyst for synthesizing methanol at low temperature of the present invention, in said step 2), the waste contact body in step 1) can be modified and modified by simple methods such as oxidation, reduction, pyrolysis, etc., to obtain a catalyst containing copper, Silicon-based porous composite materials made of one or more elements such as carbon, zinc, iron, aluminum, and tin. These modification methods can change the pore structure, components, and content of the complex. The catalytic properties of the porous composites are improved to varying degrees.

According to the preparation method of the catalyst for low-temperature synthesis of methanol of the present invention, the specific operation of the oxidation treatment in the step 2) is: placing the waste contact body of solid residue in the organic silicon synthesis industry in a high-temperature furnace for calcination in air, and the calcination temperature is at 100 ~900°C, the calcination time is 0.5-10h, and naturally cool to room temperature after calcination to obtain a silicon/copper oxide porous composite, which can be used as a catalyst in methanol production from syngas.

According to the preparation method of the catalyst for synthesizing methanol at low temperature of the present invention, wherein, the reduction treatment in the step 2) can treat the waste contact body alone, and can also be combined with the oxidation treatment to modify the waste contact body, specifically: Reduct the silicon/copper oxide porous composite obtained above in a hydrogen-containing high-purity inert gas at 300-900°C for a reduction time of 2-10 hours, and cool to room temperature under the atmosphere, or use a reducing agent in the liquid phase Reduction, the silicon/copper porous composite is finally obtained, which can be used as a catalyst in methanol production from synthesis gas. The high-purity inert gas includes nitrogen, helium, argon, etc., and the reducing agent is one or more of solution reducing agents such as formaldehyde, glucose, and sodium biborate.

According to the method for preparing a catalyst for low-temperature synthesis of methanol of the present invention, the specific operation of the heat treatment in the step 2) is: heat-treat the waste contact body of the solid residue in the organic silicon synthesis industry at 800-2500°C in a high-purity inert gas , the treatment time is 0.5-10h, and cooled to room temperature under the atmosphere to obtain a silicon/graphitized carbon/copper porous composite that can be used as a catalyst for methanol production from synthesis gas, and the high-purity inert gas includes nitrogen and helium , argon, etc.

The purpose of the above-mentioned cleaning, oxidation, reduction and heat treatment is to remove the organosilicon monomer on the surface of the waste contact body, which is beneficial to increase the number of active centers, and further adjust the content of each active component, thereby improving the catalyst produced by the waste contact body. activity.

To sum up, organosilicon synthesis and synthesis gas to methanol are two fields with different research directions. At present, the research on catalysts for synthesis gas to methanol is limited to the use of impregnation method, precipitation method, flame combustion method, and mechanical grinding method. , Skeleton synthesis and other methods, the cost of this specific catalyst preparation process is high, and the waste generated at the same time will cause environmental pollution and other problems. The inventors of the present invention broke through the limitations of existing research ideas, macroscopically considered the development status and needs of the two research fields, and combined the characteristics of organic silicon synthesis solid residues and the performance requirements of catalysts in syngas to methanol, first found that, And it has been verified by experiments that the waste contact body produced in the process of preparing organosilicon monomer methylchlorosilane can be used as a catalyst in the synthesis gas methanol process, and the technical scheme of the present invention has utilized the solid residue of the organosilicon synthesis industry, greatly The cost is reduced, economic benefits are produced, and at the same time, the waste utilization of the organosilicon synthesis industry and the high performance and low cost requirements of synthesis gas to methanol are solved, which will have a profound impact on the development of the two industries. Therefore, the present invention belongs to a brand new groundbreaking invention.

The advantages of the present invention are:

1. The present invention solves the problem of high-value comprehensive utilization of solid residue waste contacts in the organic silicon synthesis industry;

2. The catalyst prepared by the present invention is used as a catalyst for producing methanol from syngas, with low raw material cost, simple operation method, and easy large-scale production;

3. The catalyst prepared by the present invention exhibits higher methanol synthesis activity and thermal stability;

4. The catalyst prepared by the invention has good reproducibility, which is beneficial to control product quality.

Description of drawings

Fig. 1 is the XRD figure that the embodiment 1 of the present invention prepares the catalyst;

Fig. 2 is the XRD figure that the embodiment 2 in the present invention prepares catalyst;

Fig. 3 is the SEM figure of the catalyst prepared by Example 1 of the present invention;

Fig. 4 obtains SEM figure for the catalyst prepared in embodiment 2 of the present invention;

Fig. 5 obtains TG figure for the catalyst prepared in embodiment 1 of the present invention;

Fig. 6 is a TG diagram obtained from the catalyst prepared in Example 2 of the present invention.

Detailed ways

The following examples further illustrate the method of the present invention, but the present invention is not limited to the following examples.

The waste contacts used in the following examples are unreacted silicon and copper particle catalyst powders in the process of producing chlorosilane monomers under the action of copper as the main catalyst and zinc as the co-catalyst for elemental silicon and methyl chloride, and due to the A porous composite composed of carbon deposits produced by the pyrolysis of carbon-containing organic matter. Examples 1-5 are catalysts for synthesis gas to methanol prepared by modifying waste contacts synthesized by organosilicon monomers, and comparative example 1 is a commercial catalyst for synthesis gas to methanol. Comparative Example 2 is a catalyst for producing methanol from synthesis gas prepared according to the patent CN101327431.

Example 1

The "direct method" fluidized bed process commonly used in the silicone industry is used to prepare 5g of waste contacts produced in the process of preparing organosilicon monomer methylchlorosilane. 2 nanometers to 10 microns, wherein the silicon content is 84wt%, the copper content is 6wt%, and the carbon content is 10wt%. .

The catalyst material prepared above was tested by XRD on the X'Pert PROMPD multifunctional X-ray diffractometer produced by Panalytical Company of the Netherlands (Panalytical).

The surface morphology of the catalyst material prepared above was observed with a JSM6700 field emission scanning electron microscope produced by JEOL Ltd.

The catalyst material prepared above was subjected to a TG test on a model TG/DTA6300 enthusiasm analyzer produced by Japan SEICO.

The catalyst materials prepared above were tested by ICP on the Pekin-Elmer Inductively Coupled Plasma Atomic Emission Spectrometer in the United States, and the results are shown in Table 1.

Fig. 1 is the XRD figure of the catalyst that embodiment 1 obtains, wherein 2θ=28.6 ° is the characteristic peak of Si, the peak that is made up of 2θ=43.3 ° is the characteristic peak of Cu, 2θ=26.6 ° is the characteristic peak of C, thus It can be seen that the catalyst synthesized by this method is a silicon/carbon/copper catalyst.

Fig. 3 is the SEM figure of the catalyst that embodiment 1 obtains, and as can be seen from the figure, this catalyst synthesized is a porous structure.

Figure 5 is a TG diagram of the catalyst obtained in Example 1, from which it can be seen that the synthesized catalyst contains about 8% carbon.

Example 2

The "direct method" fluidized bed process commonly used in the silicone industry is used to prepare 5g of waste contacts produced in the process of preparing organosilicon monomer methylchlorosilane. 2 nanometers to 10 microns, where the silicon content is 84wt%, the copper content is 6wt%, and the carbon content is 10wt%. After washing twice with 100mL of benzene and chloroform, filter and dry in a vacuum oven at 100°C for 2 hours. , placed in a muffle furnace, heated at 100°C for 10h, and cooled to room temperature. The catalyst materials prepared above were tested by ICP on the Pekin-Elmer Inductively Coupled Plasma Atomic Emission Spectrometer in the United States, and the results are shown in Table 1.

Fig. 2 is the XRD figure of the catalyst that embodiment 2 obtains, wherein 2θ=28.6 ° is the characteristic peak of Si, the shoulder peak that is made up of 2θ=35.5 ° and 2θ=38.7 ° is the characteristic peak of CuO, 2θ=26.6 ° is C The characteristic peak, thus it can be seen that the catalyst synthesized by this method is a silicon/carbon/copper oxide catalyst.

Fig. 4 is the SEM figure of the copper catalyst that embodiment 2 obtains, as can be seen from the figure, this catalyst synthesized is a porous structure.

Fig. 6 is the TG diagram of the catalyst obtained in Example 2. It can be seen from the figure that the synthesized catalyst contains about 5% carbon.

Example 3

The "direct method" fluidized bed process commonly used in the silicone industry is used to prepare 5g of waste contacts produced in the process of preparing organosilicon monomer methylchlorosilane. 2 nanometers to 10 microns, where the silicon content is 84wt%, the copper content is 6wt%, and the carbon content is 10wt%. After washing twice with 100mL of toluene and acetone, filter and dry in a vacuum oven at 100°C for 2 hours. , placed in a muffle furnace, heated at 900°C for 0.5h, then passed through an inert gas, heated at 800°C for 10h, and cooled to room temperature to obtain a silicon/copper oxide porous composite catalyst for synthesis gas to methanol. The catalyst materials prepared above were tested by ICP on the Pekin-Elmer Inductively Coupled Plasma Atomic Emission Spectrometer in the United States, and the results are shown in Table 1.

Example 4

The "direct method" fluidized bed process commonly used in the silicone industry is used to prepare 5g of waste contacts produced in the process of preparing organosilicon monomer methylchlorosilane. 2 nanometers to 10 microns, wherein the silicon content is 84wt%, the copper content is 6wt%, and the carbon content is 10wt%. , while N ₂ and H ₂ were introduced for reduction, the reduction temperature was 900°C, the reduction time was 2 h, and the gas flow rate was 50 SCCM, respectively, to obtain a silicon/carbon/copper porous composite catalyst for syngas to methanol. The catalyst materials prepared above were tested by ICP on the Pekin-Elmer Inductively Coupled Plasma Atomic Emission Spectrometer in the United States, and the results are shown in Table 1.

Example 5

The "direct method" fluidized bed process commonly used in the silicone industry is used to prepare 5g of waste contacts produced in the process of preparing organosilicon monomer methylchlorosilane. 2 nanometers to 10 microns, wherein the silicon content is 84wt%, the copper content is 6wt%, and the carbon content is 10wt%. After washing twice with 100mL of toluene and tetrahydrofuran, filter and dry in a vacuum oven at 100°C for 2 hours. , put it into a muffle furnace, heat at 600°C for 2h, then pass in an inert gas, heat at 2500°C for 0.5h, cool to room temperature, and at the same time pass through _N2 and _H2 for reduction, the reduction temperature is 300°C, and the reduction time is 10h , and the gas flow rate is 50 SCCM, respectively, to obtain a silicon/copper porous composite catalyst for methanol production from synthesis gas. The catalyst materials prepared above were tested by ICP on the Pekin-Elmer Inductively Coupled Plasma Atomic Emission Spectrometer in the United States, and the results are shown in Table 1.

Comparative Example 1

Weighed 0.15g of the C306 type catalyst for industrial synthesis gas to methanol for catalytic evaluation. The above catalyst materials were tested by ICP on the Pekin-Elmer Inductively Coupled Plasma Atomic Emission Spectrometer in the United States, and the results are shown in Table 1.

Comparative Example 2

According to the patent CN101327431, a catalyst for producing methanol from synthesis gas was prepared, and 0.15 g was weighed for catalytic evaluation. The catalyst materials prepared above were tested by ICP on the Pekin-Elmer Inductively Coupled Plasma Atomic Emission Spectrometer in the United States, and the results are shown in Table 1.

Catalyst evaluation

Take this catalyzer of 0.15g by weighing, place in autoclave, add 40ml 2-butanol as solvent, use feed gas V _(CO) : V _{(CO )} : V _{(H )} : V _(Ar) =33: 5.27: balance: 3.02 Replace the air in the kettle for 3 times, and the inflation pressure is 1.0MPa. After removing the air in the kettle, inflate the reactor to 3.0MPa at room temperature, then start stirring at a stirring rate of 2000rpm, and raise the temperature to 170°C. After the reaction is carried out for 6 hours, stop stirring, cool down, and collect the gas in the reactor To the air bag for detection, the methanol catalyst activity test results are shown in Table 2.

Table 1. Metal element composition ICP test results in the catalysts of each embodiment

serial number Example Cu(%) Zn(%) Fe(%) Al(%) 1 Example 1 2.97 0.144 0.23 0.15 2 Example 2 3.29 0.43 0.6 0.45 3 Example 3 2.27 0.39 0.43 0.39 4 Example 4 3.5 0.27 0.35 0.29 5 Example 5 3.6 0.33 0.41 0.35 6 Comparative Example 1 39 twenty two 0.5 10 7 Comparative Example 2 32 twenty three - 13

Table 2. Catalyst activity results

It can be seen from Table 1 that the copper content of catalysts prepared from waste contacts is relatively low, less than 5%, while the copper content of commercial catalysts is relatively high, generally above 30%. It can be seen from Table 2 that although the catalyst prepared from the waste contact body has a low content of active components, it shows better methanol activity than the commercial catalyst, and the selectivity and yield are relatively high. Therefore, the catalyst for producing methanol from syngas with better performance can be obtained by using the waste contact body as raw material after simple physical or chemical treatment.

Claims (8)

1. A preparation method of a catalyst for low-temperature synthesis of methanol, characterized in that, said method comprises the step of crushing and sieving the waste contact body produced by direct method production of methyl chlorosilane, and then cleaning with an organic solvent; Reducing the waste contact body obtained by washing with an organic solvent to obtain a catalyst for methanol synthesis at low temperature; The catalyst for synthesizing methanol at low temperature is a silicon/copper porous composite. 2. according to the preparation method of the described low-temperature synthetic methanol catalyst of claim 1, it is characterized in that, described waste contact body is produced by direct method fluidized bed technique and produces methyl chloride silane, and its particle diameter after crushing and sieving 0.5 to 100 microns. 3. according to the preparation method of the described low-temperature synthetic methanol catalyst of claim 1, it is characterized in that, described organic solvent is one or more in ethanol, benzene, toluene, chloroform, acetone, THF and ether. 4. according to the preparation method of the described low-temperature synthetic methanol catalyst of claim 1, it is characterized in that, The reduction treatment is to reduce the cleaned waste contact body in a hydrogen-containing high-purity inert gas at 300-900°C for a reduction time of 2-10 hours, and cool it to room temperature under this atmosphere. The high-purity The inert gas is nitrogen, helium or argon; or, using a reducing agent to reduce the cleaned waste contacts in the liquid phase, and the reducing agent is one or more of formaldehyde, glucose and sodium biborate. 5. A catalyst for synthesizing methanol at low temperature, characterized in that, the preparation method of the catalyst comprises the steps of crushing and screening the waste contacts produced by direct method production of methyl chlorosilane, and then cleaning with an organic solvent; Reducing the waste contact body obtained by washing with an organic solvent to obtain a catalyst for methanol synthesis at low temperature; The catalyst for synthesizing methanol at low temperature is a silicon/copper porous composite. 6. according to the described low-temperature synthetic methanol catalyst of claim 5, it is characterized in that, described waste contact body is the waste contact body that direct method fluidized bed process prepares the waste contact body that methyl chlorosilane produces, and its broken, sieved particle diameter 0.5 to 100 microns. 7. The catalyst for synthesizing methanol at low temperature according to claim 5, wherein the organic solvent is one or more of ethanol, benzene, toluene, chloroform, acetone, tetrahydrofuran and ether. 8. the catalyst of low-temperature synthetic methanol according to claim 5, is characterized in that, The reduction treatment is to reduce the cleaned waste contact body in a hydrogen-containing high-purity inert gas at 300-900°C for a reduction time of 2-10 hours, and cool it to room temperature under this atmosphere. The high-purity The inert gas is nitrogen, helium or argon; or, using a reducing agent to reduce the cleaned waste contacts in the liquid phase, and the reducing agent is one or more of formaldehyde, glucose and sodium biborate.