阅读说明：本技术 铜基复合催化材料、铜基复合催化材料的制备方法及用途 (Copper-based composite catalytic material, preparation method and application thereof ) 是由 白帅 汪礼敏 贺会军 胡强 付东兴 史琦 李楠楠 王�忠 于 2020-07-20 设计创作，主要内容包括：本发明提供了一种铜基复合催化材料、铜基复合催化材料的制备方法及用途,该铜基复合催化材料的组成成分主要包括Cu、Cu<Sub>2</Sub>O和CuO,以及含氯元素的催化剂,该铜基复合催化材料氧含量介于7～18wt％之间,可以通过调整铜基复合材料氧含量来改变Cu/Cu<Sub>2</Sub>O、Cu<Sub>2</Sub>O/CuO的界面数量,进而提高有机硅单体合成产物M2选择性,降低流化床反应器内物质结块粘壁发生的概率,从而解决了现有技术中水雾化铜粉难以氧化增氧及烧结结块的问题。(The invention provides a copper-based composite catalytic material, a preparation method and application thereof, and the composition components of the copper-based composite catalytic material mainly comprise Cu and Cu 2 O, CuO and a catalyst containing chlorine, wherein the oxygen content of the copper-based composite catalytic material is between 7 and 18 weight percent, and the Cu/Cu can be changed by adjusting the oxygen content of the copper-based composite material 2 O、Cu 2 The number of O/CuO interfaces is increased, and the organosilicon monomer synthesis is further improvedThe selectivity of the finished product M2 is reduced, the probability of caking and wall sticking of substances in the fluidized bed reactor is reduced, and therefore the problems that the water atomized copper powder is difficult to oxidize, increase oxygen and sinter and agglomerate in the prior art are solved.)

1. The copper-based composite catalytic material is characterized in that the components mainly comprise Cu and Cu₂O and CuO, and a catalyst containing chlorine elements; the oxygen content of the copper-based composite catalytic material is 7-18 wt%.

2. Copper-based composite catalytic material according to claim 1, characterized in that said catalyst containing chlorine elements is at least CuCl and/or CuCl₂。

3. The process for preparing copper-based composite catalytic material according to any one of claims 1 to 2, characterized by comprising the steps of:

s1: weighing wet copper powder and CuO and/or CuCl₂Uniformly mixing the powder according to the required proportion to obtain mixed powder;

s2: carrying out low-temperature pre-oxidation treatment on the mixed powder to obtain pre-oxidized powder;

s3: carrying out first-stage high-temperature oxidation treatment on the pre-oxidized powder obtained in the step S2 to obtain copper oxide;

s4: performing acid spraying treatment on the copper oxide obtained in the step S3;

s5: performing second-stage high-temperature oxidation treatment on the powder subjected to the acid spraying treatment in the step S4, and introducing compressed air in the high-temperature oxidation treatment process;

s6: and (4) collecting the powder subjected to the second-stage high-temperature oxidation treatment in the step S5, and crushing to obtain the copper-based composite catalytic material.

4. The method for preparing a copper-based composite catalytic material according to claim 3, further comprising:

s0, preparation of wet copper powder: cathode electrolytic copper plates are used as raw materials, and a water atomization process is utilized to obtain wet copper powder; the moisture content of the wet copper powder is 6-10 wt%, and the powder granularity is less than 500 mu m.

5. The method for preparing copper-based composite catalytic material according to claim 3, wherein in step S1, said wet copper powder is mixed with said CuO and/or CuCl₂The mass percentage of the powder is 10-20: 1.

6. The preparation method of the copper-based composite catalytic material according to claim 3, wherein in the step S2, the oxidation temperature of the low-temperature pre-oxidation treatment is 60-80 ℃, and the pre-oxidation time is 0.5-1 h.

7. The preparation method of the copper-based composite catalytic material according to claim 3, wherein in step S3, the oxidation temperature of the first-stage high-temperature oxidation treatment is 300-450 ℃, and the oxidation time is 1-2 h.

8. The method for preparing the copper-based composite catalytic material according to claim 3, wherein in step S4, the acid spraying treatment is spraying an acidic solution on the surface of the copper oxide; the acidic solution is 1-5.0 mol/L HCl solution or 1.5-3.5 mol/L CuCl₂And (3) solution.

9. The preparation method of the copper-based composite catalytic material according to claim 3, wherein in step S5, the oxidation temperature of the second-stage high-temperature oxidation treatment is 400-450 ℃, and the oxidation time is 1-2 h; the flow rate of the compressed gas is 10-25 Nm³And h, the oxygen content in the compressed gas is more than or equal to 20 percent.

10. Use of the copper-based composite catalytic material prepared by the preparation method according to any one of claims 3 to 9, wherein the copper-based composite catalytic material is used for synthesizing dimethyldichlorosilane.

Technical Field

The invention relates to the technical field of preparation of copper catalyst materials, in particular to a copper-based composite catalytic material, a preparation method and application of the copper-based composite catalytic material.

Background

Organosilicon products are widely applied to various fields of industry, agriculture, national defense and military industry and daily life of people, and the organosilicon refers to a compound which contains Si-C bonds and at least one organic group is directly connected with silicon atoms.

Rochow reaction, also known as direct synthesis, is widely used for the industrial preparation of organosilicon monomers. The reaction process is as follows: reacting solid silicon with gaseous chloromethane under the action of a copper catalyst to generate methyl chlorosilane. During the Rochow reaction, the copper catalyst function is critical. At present, ternary copper Cu-Cu is mainly used in industry₂O-CuO is used as a catalyst for synthesizing an organic silicon monomer, and the oxygen content is generally considered to be 11-14 wt%, and the catalyst contains a small amount of Cl^-The ternary copper catalyst has better use effect. The ternary copper catalyst has the characteristics of high activity, short induction period, high selectivity, long service life, good catalytic effect, high storage and reaction stability and the like.

At present, research reports on a process method for preparing a ternary copper catalyst by using water atomized copper powder as a raw material. The copper powder prepared by the water atomization method is mainly near-spherical powder and is put into a high-temperature furnace for oxidation (static oxidation mode). In order to ensure that the oxygen content of the powder reaches a preset target, the powder needs to undergo the process of primary oxidation → primary crushing → secondary oxidation → secondary crushing. In the preparation process, a compact CuO layer is formed on the surface of the copper powder after primary oxidation. In the process, the materials are repeatedly taken out, cooled and reheated, so that not only is a large amount of energy wasted, but also the operation procedure is long and tedious.

In addition, the water atomized copper powder is screened out, the copper powder with small particle size and large specific surface area is subjected to high-temperature oxidation, and the ternary copper catalyst with the oxygen content meeting the requirement can be prepared, but the raw material utilization rate is low.

Some researchers place the water atomized copper powder in a rotary kiln type furnace for rolling oxidation (dynamic oxidation mode), but in the process, the inner wall of the furnace can be bonded with the copper powder, so that the utilization rate of raw materials is reduced, and meanwhile, the phenomenon of serious powder floating can be caused, so that air pollution is caused.

Therefore, the water atomized copper powder is used as the raw material of the ternary copper catalyst, and the process for increasing the oxygen content has the following problems: in the oxidation stage, water atomized copper powder is used as a raw material, and a production process of static oxidation, non-sieving of granularity and multiple crushing is adopted, so that the oxygen content of the oxidized copper powder is difficult to reach more than 7 wt%; the existing process for increasing the oxygen content of the water atomized copper powder has high energy consumption, long and complex flow and easy air pollution; the water atomized copper powder is nearly spherical particles, and a compact CuO layer is formed after the surface of the water atomized copper powder is oxidized, so that the copper is prevented from being further oxidized.

Disclosure of Invention

The invention mainly aims to provide a copper-based composite catalytic material, a preparation method and application thereof, wherein the copper-based composite catalytic material mainly comprises Cu and Cu₂O and CuO, and a catalyst containing chlorine elements; the oxygen content is 7-18 wt%, and Cu/Cu can be changed by adjusting the oxygen content of the copper-based composite material₂O、Cu₂The number of O/CuO interfaces is increased, the selectivity of an organosilicon monomer synthesis product M2 (dichlorodimethylsilane) is improved, and the probability of caking and wall sticking of substances in a fluidized bed reactor is reducedThe technical problems that the water atomized copper powder is difficult to oxidize, oxygenate and sinter in the prior art are solved.

In order to achieve the above object, according to a first aspect of the present invention, there is provided a copper-based composite catalytic material.

The copper-based composite catalytic material mainly comprises Cu and Cu₂O and CuO, and a catalyst containing chlorine elements; the oxygen content of the copper-based composite catalytic material is 7-18 wt%.

Further, the catalyst containing the chlorine element is at least CuCl and/or CuCl₂。

In order to achieve the above object, according to a second aspect of the present invention, there is provided a method for preparing a copper-based composite catalytic material.

The preparation method of the copper-based composite catalytic material comprises the following steps:

s1: weighing wet copper powder and CuO and/or CuCl₂Uniformly mixing the powder according to the required proportion to obtain mixed powder;

s2: carrying out low-temperature pre-oxidation treatment on the mixed powder to obtain pre-oxidized powder;

s3: carrying out first-stage high-temperature oxidation treatment on the pre-oxidized powder obtained in the step S2 to obtain copper oxide;

s4: performing acid spraying treatment on the copper oxide obtained in the step S3;

s5: performing second-stage high-temperature oxidation treatment on the powder subjected to the acid spraying treatment in the step S4, and introducing compressed air in the high-temperature oxidation treatment process;

s6: and (4) collecting the powder subjected to the second-stage high-temperature oxidation treatment in the step S5, and crushing to obtain the copper-based composite catalytic material.

Further, the method further comprises:

s0, preparation of wet copper powder: cathode electrolytic copper plates are used as raw materials, and a water atomization process is utilized to obtain wet copper powder; the moisture content of the wet copper powder is 6-10 wt%, and the powder granularity is less than 500 mu m.

Further, in step S1, the wet copper powder is mixed with the CuO and the CuO/or CuCl₂The mass percentage of the powder is 10-20: 1.

Further, in step S2, the oxidation temperature of the low-temperature pre-oxidation treatment is 60 to 80 ℃, and the pre-oxidation time is 0.5 to 1 hour.

Further, in step S3, the oxidation temperature of the first-stage high-temperature oxidation treatment is 300 to 450 ℃, and the oxidation time is 1 to 2 hours.

Further, in step S4, the acid spraying treatment is to spray an acidic solution on the surface of the copper oxide.

Further, the acidic solution is 1-5.0 mol/L HCl solution or 1.5-3.5 mol/L CuCl₂And (3) solution.

Further, in step S5, the oxidation temperature of the second high-temperature oxidation treatment is 400 to 450 ℃, and the oxidation time is 1 to 2 hours.

Further, in step S5, the flow rate of the compressed gas is 10 to 25Nm³And h, the oxygen content in the compressed gas is more than or equal to 20 percent.

Further, the CuO or CuCl₂The purity of the powder is more than 99 wt%, and the total content of impurities Fe, Al and Ca is less than 0.4 wt%.

In order to achieve the above object, according to a third aspect of the present invention, there is provided a use of a copper-based composite catalytic material.

The copper-based composite catalytic material is used for synthesizing dimethyldichlorosilane.

The copper-based composite catalytic material is used as a catalyst for synthesizing an organic silicon monomer, is particularly applied to synthesizing dimethyldichlorosilane, and has high selectivity.

The invention has the beneficial effects that:

1. the invention provides a preparation method of copper-based composite catalytic materials with different oxygen contents, and the preparation method directly carries out acid spraying treatment after the first-stage high-temperature oxidation treatment and then carries out the second-stage high-temperature oxidation treatment, so that the materials are prevented from being repeatedly taken out, cooled and reheated in the whole process, the energy consumption is reduced, no pollution is caused, and the automatic production can be realized.

2. The invention canChanging Cu/Cu by adjusting oxygen content of copper-based composite catalytic material₂O、Cu₂The interface quantity of O/CuO, so that the selectivity of an organosilicon monomer synthesis product M2 (dichlorodimethylsilane) is improved from 60-85% to 85-88%, and the probability of caking and wall adhesion of substances in a fluidized bed reactor is reduced.

3. According to the invention, the acid spraying treatment is added between the first-stage high-temperature oxidation treatment and the second-stage high-temperature oxidation treatment, so that the oxygen content of the prepared copper-based composite catalytic material is in the range of 7-18 wt%, and the problem that the water-atomized copper powder is difficult to oxidize and enrich oxygen is solved.

4. Compared with the traditional rolling oxidation mode of putting the water atomized copper powder into a rotary kiln type furnace, the invention avoids sintering and caking, improves the utilization rate of raw materials and lightens air pollution.

Drawings

Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:

FIG. 1 is a schematic view of the addition of external medium powder and the structure of a steel strip furnace in an embodiment of the present invention;

FIG. 2 is a microscopic morphology of the copper-based composite catalytic material prepared in comparative example 1 (no CuO powder is added and no acid spraying treatment is performed);

FIG. 3 is a surface morphology of the copper-based composite catalytic material prepared in example 1 (adding 4mol/l HCl solution for acid spraying treatment) of the present invention;

FIG. 4 is a flow chart of a process for preparing a copper-based composite material in an embodiment of the present invention.

Detailed Description

Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.

The invention discloses a copper-based composite catalytic material, which mainly comprises Cu and Cu₂O and CuO, and a catalyst containing chlorine elements; the oxygen content of the copper-based composite catalytic material is 7-18 wt%.

In the above examples, the main components of the copper-based composite catalytic material were Cu and Cu₂O and CuO, and a catalyst containing a small amount of chlorine elements. Moreover, the oxygen content of the copper-based composite catalytic material is controlled within the range of 7-18 wt%, and the Cu/Cu can be changed by adjusting the oxygen content of the copper-based composite catalytic material₂O、Cu₂The number of O/CuO interfaces further improves the selectivity of an organosilicon monomer synthesis product M2 (dichlorodimethylsilane), and reduces the probability of caking and wall adhesion of substances in a fluidized bed reactor.

In some embodiments, the elemental chlorine containing catalyst is CuCl.

In some embodiments, the elemental chlorine-containing catalyst is CuCl₂。

In some embodiments, the elemental chlorine-containing catalyst is CuCl and CuCl₂. In the invention, the catalyst containing chlorine elements is CuCl and CuCl₂Namely the copper-based composite catalytic material comprises the components of Cu and Cu₂O, CuO, CuCl and CuCl₂。

The invention also discloses a preparation method of the copper-based composite catalytic material, which comprises the following steps:

s0, preparation of wet copper powder: cathode electrolytic copper plate (99.99 wt%) is used as raw material, and water atomization process is used to prepare copper powder, and the particle size of the powder is less than 500 μm; then, putting the pure copper powder containing water into a centrifuge, and separating the copper powder from the water according to the process of rotating speed of 300r/min and centrifugation time of 10-20 min to obtain wet copper powder with the water content of 6-10 wt%; or mixing the added water with the water atomized copper powder to obtain wet copper powder with the water content of 6-10 wt%.

S1: according to the ratio of wet copper powder to CuO or CuCl₂Weighing wet copper powder and CuO or CuCl with the mass percentage of the powder being 10-20: 1₂And putting the powder into a V-shaped mixer with a certain vibration function, and uniformly mixing to obtain mixed powder. And then placing the mixed powder on a steel belt of a steel belt type oxidation furnace, and entering the oxidation furnace along with the steel belt for oxidation treatment. Wherein: CuO or CuCl₂The purity of the powder is more than 99 wt%, and the total content of impurities Fe, Al and Ca is less than 0.4 wt%.

S2: and carrying out low-temperature pre-oxidation treatment on the mixed powder at an oxidation temperature of 60-80 ℃ for 0.5-1 h to obtain pre-oxidized powder.

S3: and carrying out first-stage high-temperature oxidation treatment on the pre-oxidized powder at the oxidation temperature of 300-450 ℃ for 1-2 h to obtain the copper oxide. In the first-stage high-temperature oxidation treatment process, an air compressor can be used for 10-25 Nm according to actual needs³The flow velocity of the compressed air is changed in the reverse direction (opposite to the feeding direction of the steel strip) to the high-temperature oxidation furnace; moreover, the oxygen content in the compressed air is more than or equal to 20 percent.

S4: spraying acid on the obtained copper oxide, specifically spraying an acid solution on the surface of the copper oxide; the acidic solution is 1-5.0 mol/L HCl solution or 1.5-3.5 mol/L CuCl₂And (3) solution.

S5: carrying out second-stage high-temperature oxidation treatment on the powder subjected to the acid spraying treatment, wherein the oxidation temperature is 400-450 ℃, and the oxidation time is 1-2 h; and an air compressor is used for 10-25 Nm³The flow velocity of the compressed air is changed in the reverse direction (opposite to the feeding direction of the steel strip) to the high-temperature oxidation furnace; moreover, the oxygen content in the compressed air is more than or equal to 20 percent.

S6: and collecting the powder subjected to the second-stage high-temperature oxidation treatment, and crushing the powder by using a pendulum crusher to obtain the copper-based composite catalytic material with the oxygen content of 7-18 wt%.

The copper-based composite catalytic material and the preparation method thereof according to the present invention will be described in detail with reference to specific examples.