CN108993595B - Copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method and application thereof - Google Patents
Copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) dissolving copper salt and a compound shown in a formula I in water to prepare a mixed solution; 2) adding activated carbon into the mixed solution obtained in the step 1) for impregnation; 3) filtering, draining and then heating and drying the activated carbon obtained in the step 2) to obtain the copper-based catalyst. The copper-based catalyst is used for synthesizing vinyl chloride by hydrochlorinating acetylene, operates according to the current industrial strength, has the conversion per pass of the acetylene of more than 98 percent, the selectivity of the vinyl chloride of more than 99 percent and the service life of more than 8000 hours, can directly and simply replace the mercury catalyst in the existing calcium carbide process, and meets the industrial application.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene as well as a preparation method and application thereof.
Background
The vinyl chloride monomer is a basic raw material for synthesizing various chemical products, and the most important purpose of the vinyl chloride monomer is to produce polyvinyl chloride mainly by a calcium carbide acetylene method and a petroleum ethylene method. The existence of energy sources rich in coal, lean oil and little gas in China determines that the calcium carbide acetylene method will continue to be the main process for producing vinyl chloride in China in a long time in the future, namely mercury chloride catalyzes the reaction of acetylene and hydrogen chloride to generate vinyl chloride. However, highly toxic mercuric chloride catalysts severely pollute the environment and harm human health. Therefore, the development of non-mercury catalysts is necessary for the sustainable development of the industry for synthesizing vinyl chloride by the calcium carbide acetylene method.
At present, various researches are carried out by domestic and foreign people on noble metals such as gold, palladium, platinum, ruthenium and the like as active components, although the catalytic activity is higher, the cost of the catalyst is very high, the large-scale industrial production is difficult to realize, and the catalyst has the problems of inactivation and difficult regeneration. Compared with the non-noble metal catalyst, the non-noble metal catalyst has low cost and convenient regeneration, and becomes a research hotspot.
Deng Fei et alSnCl is prepared by using stannous chloride as main active component as catalyst2-BiCl3-CuCl/C composite catalyst, but its main active component SnCl2The loss is serious, and the space velocity is 30h-1At times, the catalyst life was only 120 hours.
The invention patent application No. 201510487905.0 discloses a composite metal salt catalyst for acetylene hydrochlorination. The catalyst takes copper salt loaded on a carbon-based carrier as a main active component, and the catalytic activity and the stability of the catalyst are improved by adding a synergistic metal or an anionic ligand. The anion ligand is a group with electron withdrawing, such as ammonia, phosphoric acid, sodium thiosulfate, melamine, ethylene diamine tetraacetic acid, ammonium phosphomolybdate and derivatives thereof. The catalyst prepared by the method is used for acetylene hydrochlorination, has low initial acetylene conversion rate and poor stability, and has great difference from industrial application.
Application No. 201210575484.3 discloses an acetylene hydrochlorination catalyst which is prepared by taking copper chloride as an active component and one or a mixture of any of non-noble metal elements which are difficult to volatilize chlorides in alkali metal, alkaline earth metal and transition metal elements as a cocatalyst metal element through the processes of dipping, drying and the like. The catalyst has an acetylene space velocity of 60h-1The reaction temperature is 184 ℃, and the raw material ratio n (HCl): n (C)2H2) 1: under the condition of 1.15, the conversion rate of the obtained acetylene is only 76 percent.
The application number 201711188078.0 is that the carrier is coal activated carbon, coconut shell activated carbon or pitch-based spherical activated carbon, the active component is chloride, phosphate, sulfate or acetate of bismuth or copper, and the catalytic performance of the catalyst is improved by a step impregnation method. But the prepared catalyst has the space velocity of acetylene of 50h-1，n(HCl)：n(C2H2) 1.2, the reaction temperature is 160 ℃, the acetylene conversion is 65%, and the vinyl chloride selectivity is 85%.
Application number 201710174566.X discloses a mercury-free catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene, which is prepared by dissolving base metal salt and an amide solvent in water to prepare a mixed solution, adding activated carbon into the mixed solution, filtering, draining and drying. The catalyst has high low-temperature activity and vinyl chloride selectivity, the conversion per pass of acetylene can reach 95%, the performance of the catalyst is greatly improved compared with other non-noble metal mercury-free catalysts, and the catalyst can basically meet the industrial requirement. However, because all H substituents on the amide solvent amino group adopted by the invention are alkane substituents, the prepared catalyst has the following two problems: (1) when the substituent is a micromolecular hydrocarbyl group, the obtained catalyst has high activity, but the effective component of the catalyst is easy to lose due to low boiling point and high vapor pressure, and the stability of the catalyst is poor; (2) when the substituent is macromolecular alkyl, the effective component of the catalyst has high boiling point, is not easy to run off, has good stability and low activity. Therefore, the overall performance of the mercury-free catalyst prepared by the technology of application number 201710174566.X is slightly different from that of the mercury catalyst, and a space for further improvement exists.
Disclosure of Invention
Aiming at the technical defects of the mercury-free catalyst with the application number of 201710174566.X, the invention provides an industrial catalyst with higher catalytic activity and better stability, and the industrial catalyst can directly and simply replace the existing calcium carbide mercury catalyst.
The invention is realized by the following technical scheme:
the invention provides a preparation method of a copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene, which comprises the following steps:
1) dissolving copper salt and a compound shown in a formula I in water to prepare a mixed solution;
wherein R is a small molecular polar group;
2) adding activated carbon into the mixed solution obtained in the step 1) for impregnation;
3) filtering, draining and then heating and drying the activated carbon obtained in the step 2) to obtain the copper-based catalyst.
The draining may be performed by a spin dryer.
Preferably, step 1) further comprises at least one of the following technical features:
1) the copper salt is selected from one or more of copper chloride, copper nitrate and copper phosphate;
2) r is an oxygen-containing polar group of C2-C6; introducing oxygen-containing polar groups such as alcohol groups (-OH), ether groups (-O-), ketone groups (C ═ O), ester groups (-OCO-), amide groups (-CON-), and the like into an alkyl molecular chain, wherein the carbon number is 2-6 after introduction;
3) the content of the copper salt in the mixed solution is 20-45 wt%, such as 20-27 wt%, 27-30 wt%, 30-35 wt%, 35-40 wt% or 40-45 wt%, and the content of the compound of formula I in the mixed solution is 2-12 wt%, such as 2-5 wt%, 5-8 wt%, 8-10 wt% or 10-12 wt%; if the copper salt contains water of crystallization, the mass of the water of crystallization does not account for the content of the copper salt, and the content of water is accounted for.
More preferably, in the feature 1), the copper salt is copper chloride.
More preferably, in the feature 2), the oxygen-containing polar group is an alcohol, an ether, an ester, a ketone, or an amide.
Preferably, step 2) further comprises at least one of the following technical features:
1) the volume ratio of the activated carbon to the mixed solution is 1: 1-3, such as 1: 1-1.5, 1: 1.5-2, 1: 2-3;
2) the activated carbon is acid-washed granular activated carbon, and the specific surface area of the activated carbon is 700-1500 m2The carbon tetrachloride adsorption value is 50-70%, and the ash content is less than 6%;
3) the soaking temperature is room temperature to 100 ℃, such as room temperature to 40 ℃, 40 to 50 ℃, 50 to 70 ℃ or 70 to 100 ℃;
4) the impregnation was carried out until the concentration of copper salt in the solution was constant.
Preferably, in the step 3), the drying temperature is 70-150 ℃, such as 70-100 ℃, 100-120 ℃ or 120-150 ℃.
Preferably, in step 3), drying is performed in a vacuum state.
The invention provides a copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene, which is prepared by adopting the preparation method.
The third aspect of the invention provides the use of the copper-based catalyst for the hydrochlorination of acetylene to synthesize vinyl chloride.
The fourth aspect of the invention provides a method for synthesizing vinyl chloride by hydrochlorinating acetylene by using the copper-based catalyst, and C is2H2And HCl mixed gas are subjected to hydrochlorination reaction in the presence of the copper-based catalyst.
Preferably, at least one of the following technical features is also included:
1)C2H2and HCl in a molar ratio of 1: 0.95-1.05, such as 1: 0.95-0.97, 1: 0.97 to 1 or 1: 1 to 1.05;
2) the reaction temperature is 80-160 ℃, such as 80-100 ℃, 100-110 ℃, 110-120 ℃, 120-130 ℃, 130-150 ℃ or 150-160 ℃;
3) the reaction gauge pressure is 0-0.1 MPa, such as 0-0.03 MPa, 0.03-0.05 MPa, 0.05-0.07 MPa or 0.07-0.1 MPa;
4) the space velocity of acetylene is 20-60 h-1，20～30h-1、30～40h-1、40～50h-1Or 50 to 60 hours-1。
In the method, the acetylene conversion rate is more than 98 percent. The acetylene conversion was adjusted by the following method: collecting gas-phase products obtained by hydrochlorination in unit time, measuring the content of unreacted acetylene, and calculating the acetylene conversion rate according to the following formula; if the conversion rate of acetylene in the mixed gas is less than 98%, the conversion rate of acetylene can be increased to more than 98% by reducing the flow rate of the mixed gas of acetylene and hydrogen chloride, or increasing the reaction temperature or the reaction pressure.
Conversion of acetylene is 100% -molar concentration of acetylene in the gas phase product obtained by the reaction.
On the basis of the patent application number 201710174566.X, a micromolecule polar group is introduced on the amino group of a pyrrolidone compound, so that on one hand, the polarity of an effective component of the copper-based catalyst is further enhanced, the adsorption capacity and the activation capacity of the copper-based catalyst on raw materials, namely hydrogen chloride and acetylene, are further improved, and the activity of the copper-based catalyst is further improved; on the other hand, the boiling point of the effective component of the copper-based catalyst is increased by introducing the micromolecule polar group, and the loss rate of the effective component is greatly reduced, so that the prepared copper-based catalyst has good stability. The copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene is operated under the industrial operation conditions of the existing mercury catalyst, the conversion per pass of acetylene is more than 98%, the selectivity of vinyl chloride is more than 99%, the service life of the catalyst can reach more than 8000 hours, the catalyst can directly and simply replace the mercury catalyst in the existing calcium carbide process, the industrial application is met, and the following beneficial effects can be obtained:
(1) the copper-based catalyst can directly and simply replace a mercury catalyst under the existing calcium carbide method operation condition, and thoroughly solves the problem of mercury pollution in the calcium carbide method PVC industry.
(2) The catalyst has wide temperature application range, has good catalytic activity and stability within the range of 80-160 ℃, can operate on the existing hot water circulating cooling device, can also operate at high jacket water temperature, and can produce steam as a byproduct, thereby saving more energy.
(3) The copper-based catalyst can stably operate under the condition of not excessive HCl, the waste acid amount can be reduced by more than 60% under the condition, the content of heavy components is greatly reduced, and the discharge of hazardous waste is reduced.
In conclusion, the comprehensive performance of the copper-based catalyst is superior to that of the mercury catalyst.
Drawings
FIG. 1 is a graph of the stability of catalyst A1 for 8000h of operation.
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination step or that other method steps may be inserted between the explicitly mentioned steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The reaction pressures in the following examples are both gauge pressures.
Example 1
(1) 68.6g of CuCl are weighed out2·2H2O and 18.6g
R is CH2CH2OH (the oxygen-containing polar group is an alcohol group) is dissolved in 67.5g of deionized water to obtain a steeping liquor containing copper chloride and pyrrolidone compounds;
(2) the specific surface area is 700-1500 m2And g, soaking the pickled granular activated carbon with the carbon tetrachloride adsorption value of 50-70% and the ash content of less than 6% in the prepared solution at room temperature, controlling the soaking temperature to be room temperature, and controlling the volume ratio of the solution to the activated carbon to be 1.5: 1, soaking until the concentration of copper chloride in the solution is constant;
(3) filtering the soaked activated carbon, drying the activated carbon by spin-drying the activated carbon, and drying the activated carbon at 120 ℃ to obtain the required catalyst A1;
(4) c is to be2H2And HCl gas mixture (C)2H2And HCl in a molar ratio of 1: 1.05) is introduced into a tubular reactor filled with a catalyst A1 to carry out hydrochlorination, the reaction temperature is controlled to be 80 ℃, and the acetylene space velocity is controlled to be 20h-1The reaction pressure is 0.03MPa, the conversion rate of the obtained acetylene is 98.5 percent of the initial conversion rate of the acetylene, and the selectivity of the chloroethylene is 99.5 percent;
example 2
(1) 152.2g of CuCl are weighed out2·2H2O and 40g
R is CH2COCH3(the oxygen-containing polar group is ketone group) is dissolved in 207.8g of deionized water to obtain impregnation liquid containing copper chloride and pyrrolidone compounds;
(2) the specific surface area is 700-1500 m2And g, soaking the pickled granular activated carbon with the carbon tetrachloride adsorption value of 50-70% and the ash content of less than 6% in the prepared solution at room temperature, controlling the soaking temperature to be 70 ℃, and controlling the volume ratio of the solution to the activated carbon to be 2: 1, soaking until the concentration of copper chloride in the solution is constant;
(3) filtering the soaked activated carbon, drying the activated carbon by spin-drying the activated carbon, and drying the activated carbon at 120 ℃ to obtain the required catalyst A2;
(4) c is to be2H2And HCl gas mixture (C)2H2And HCl in a molar ratio of 1: 1) introducing into a tubular reactor filled with a catalyst A2 to perform hydrochlorination, controlling the reaction temperature at 100 ℃ and the acetylene space velocity at 30h-1The reaction pressure is 0MPa, the initial conversion rate of the obtained acetylene is 99.0 percent, and the selectivity of the chloroethylene is 99.6 percent;
example 3
(1) 101.5g of CuCl are weighed out2·2H2O and 4g
R is CH2CH2OCOCH3(the oxygen-containing polar group is an ester group) is dissolved in 94.5g of deionized water to obtain impregnation liquid containing copper chloride and pyrrolidone compounds;
(2) the specific surface area is 700-1500 m2And g, soaking the pickled granular activated carbon with the carbon tetrachloride adsorption value of 50-70% and the ash content of less than 6% in the prepared solution at room temperature, controlling the soaking temperature to be 50 ℃, and controlling the volume ratio of the solution to the activated carbon to be 1: 1, soaking until the concentration of copper chloride in the solution is constant;
(3) filtering the soaked activated carbon, drying the activated carbon by spin-drying the activated carbon, and drying the activated carbon at 150 ℃ to obtain the required catalyst A3;
(4) c is to be2H2And HCl gas mixture (C)2H2And HCl in a molar ratio of 1: 1) introducing into a tubular reactor filled with a catalyst A3 to carry out hydrochlorination, controlling the reaction temperature at 120 ℃ and the acetylene space velocity at 40h-1The reaction pressure is 0.05MPa, and the obtained acetylene has the conversion rate of acetyleneThe initial conversion was 98.6% and the vinyl chloride selectivity was 99.3%;
example 4
(1) 152.2g of CuCl are weighed out2·2H2O and 30g
R is CH2CH2OCH2CH2CH3(the oxygen-containing polar group is an ether group) is dissolved in 415g of deionized water to obtain a steeping liquor containing copper chloride and a pyrrolidone compound;
(2) the specific surface area is 700-1500 m2And g, soaking the pickled granular activated carbon with the carbon tetrachloride adsorption value of 50-70% and the ash content of less than 6% in the prepared solution at room temperature, controlling the soaking temperature to be room temperature, and controlling the volume ratio of the solution to the activated carbon to be 3: 1, soaking until the concentration of copper chloride in the solution is constant;
(3) filtering the soaked activated carbon, drying the activated carbon by spin-drying the activated carbon, and drying the activated carbon at 100 ℃ to obtain the required catalyst A4;
(4) c is to be2H2And HCl gas mixture (C)2H2And HCl in a molar ratio of 1: 0.97) is introduced into a tubular reactor filled with a catalyst A4 to carry out hydrochlorination, the reaction temperature is controlled to be 150 ℃, and the acetylene space velocity is controlled to be 50h-1The reaction pressure is 0.07MPa, the conversion rate of the obtained acetylene is 99.3 percent of the initial conversion rate of the acetylene, and the selectivity of the chloroethylene is 99.4 percent;
example 5
(1) 228g of CuCl were weighed2·2H2O and 32g
R is CH2CON(CH2CH3)2(the oxygen-containing polar group is an amide group) is dissolved in 140g of deionized water to obtain a dipping solution containing copper chloride and pyrrolidone compounds;
(2) the specific surface area is 700-1500 m2Soaking the pickled granular activated carbon with carbon tetrachloride adsorption value of 50-70% and ash content of less than 6% in the prepared solution at room temperatureControlling the soaking temperature to be 40 ℃, and controlling the volume ratio of the solution to the active carbon to be 2: 1, soaking until the concentration of copper chloride in the solution is constant;
(3) filtering the soaked activated carbon, drying the activated carbon by spin-drying the activated carbon, and drying the activated carbon at 150 ℃ to obtain the required catalyst A5;
(4) will be coated with C2H2And HCl gas mixture (C)2H2And HCl in a molar ratio of 1: 0.95) is introduced into a tubular reactor filled with a catalyst A5 to carry out hydrochlorination, the reaction temperature of a bed layer is controlled at 160 ℃, and the space velocity of acetylene is controlled for 60h-1The reaction pressure is 0.1MPa, the conversion rate of the obtained acetylene is 99.7 percent of the initial conversion rate of the acetylene, and the selectivity of the chloroethylene is 99.2 percent;
example 6
(1) 68.5g of CuCl are weighed out2·2H2O and 10g
R is CH2COOCH2CH3(the oxygen-containing polar group is an ester group) is dissolved in 121.5g of deionized water to obtain impregnation liquid containing copper chloride and pyrrolidone compounds;
(2) the specific surface area is 700-1500 m2And g, soaking the pickled granular activated carbon with the carbon tetrachloride adsorption value of 50-70% and the ash content of less than 6% in the prepared solution at room temperature, controlling the soaking temperature to be 100 ℃, and controlling the volume ratio of the solution to the activated carbon to be 1: 1, soaking until the concentration of copper chloride in the solution is constant;
(3) filtering the soaked activated carbon, drying the activated carbon by spin-drying the activated carbon, and drying the activated carbon at 70 ℃ to obtain the required catalyst A6;
(4) c is to be2H2And HCl gas mixture (C)2H2And HCl in a molar ratio of 1: 1) introducing into a tubular reactor filled with a catalyst A6 to carry out hydrochlorination, controlling the reaction temperature at 130 ℃ and the acetylene space velocity at 50h-1The reaction pressure is 0.05MPa, the conversion rate of the obtained acetylene is 98.9 percent of the initial conversion rate of the acetylene, and the selectivity of the chloroethylene is 99.2 percent;
the catalysts A1-A6 obtained in examples 1-6 showed acetylene conversion and vinyl chloride selectivity in hydrochlorination as shown in Table 1.
TABLE 1 catalysts A1-A6 hydrochlorination acetylene conversion and vinyl chloride selectivity
| Catalyst and process for preparing same | Conversion (%) | Vinyl chloride selectivity (%) |
| A1 | 98.5 | 99.5 |
| A2 | 99.0 | 99.6 |
| A3 | 98.6 | 99.3 |
| A4 | 99.3 | 99.4 |
| A5 | 99.7 | 99.2 |
| A6 | 98.9 | 99.2 |
To further investigate the reactivity of the catalyst of the present invention, catalyst A1 prepared as described in example 1 above was placed in a tubular reactor and C was passed through2H2And HCl gas mixture (C)2H2And HCl in a molar ratio of 1: 1.05) carrying out hydrochlorination, controlling the reaction temperature at 110 ℃ and the acetylene space velocity at 40h-1The catalyst was evaluated for stability at a reaction gauge pressure of 0.05MPa, and the evaluation results are shown in Table 2 and FIG. 1.
TABLE 2 evaluation table of hydrochlorination reaction performance of catalyst A1
It can be seen from table 2 and fig. 1 that the copper-based catalyst prepared by the method of the present invention has the same reactivity and vinyl chloride selectivity as the mercury catalyst in the hydrochlorination of acetylene, and has good stability, and can directly and simply replace the mercury catalyst of the existing calcium carbide method to realize the industrial mercury-free PVC production.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene is characterized by comprising the following steps:
1) dissolving copper salt and a compound shown in a formula I in water to prepare a mixed solution;
I
wherein R is an oxygen-containing polar group of C2-C6;
2) adding activated carbon into the mixed solution obtained in the step 1) for impregnation;
3) filtering, draining and then heating and drying the activated carbon obtained in the step 2) to obtain the copper-based catalyst.
2. The method according to claim 1, wherein the step 1) further comprises at least one of the following technical features:
1) the copper salt is selected from one or more of copper chloride, copper nitrate and copper phosphate;
2) the content of copper salt in the mixed solution is 20-45 wt%, and the content of the compound in the formula I in the mixed solution is 2-12 wt%.
3. The method according to claim 2, wherein in the step 1), the copper salt is copper chloride.
4. The method of claim 1, wherein the oxygen-containing polar group is an alcohol, an ether, an ester, a ketone, or an amide.
5. The method according to claim 1, wherein the step 2) further comprises at least one of the following technical features:
1) the volume ratio of the activated carbon to the mixed solution is 1: 1-3;
2) the activated carbon is acid-washed granular activated carbon, and the specific surface area of the activated carbon is 700-1500 m2The carbon tetrachloride adsorption value is 50-70%, and the ash content is less than 6%;
3) the dipping temperature is between room temperature and 100 ℃;
4) the impregnation was carried out until the concentration of copper salt in the solution was constant.
6. The method according to claim 1, wherein the drying temperature in step 3) is 70 to 150 ℃.
7. A copper-based catalyst for the hydrochlorination of acetylene to vinyl chloride, which is prepared by the preparation method of any one of claims 1 to 6.
8. The copper-based catalyst of claim 7 for the hydrochlorination of acetylene to vinyl chloride.
9. A process for the hydrochlorination of acetylene to vinyl chloride using a copper-based catalyst as claimed in claim 7, wherein C is added2H2And HCl in the presence of the copper-based catalyst according to claim 7.
10. The method of claim 9, further comprising at least one of the following technical features:
1）C2H2and HCl in a molar ratio of 1: 0.95 to 1.05;
2) the reaction temperature is 80-160 ℃;
3) the reaction gauge pressure is 0-0.1 MPa;
4) the space velocity of acetylene is 20-60 h-1。
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| CN111389423A (en) * | 2020-04-30 | 2020-07-10 | 鄂尔多斯市瀚博科技有限公司 | Modified copper-based catalyst for acetylene hydrochlorination and preparation method thereof |
| CN112121840A (en) * | 2020-09-30 | 2020-12-25 | 李通 | Activated carbon of catalyst for preparing chloroethylene by calcium carbide method and preparation method thereof |
| CN112121809B (en) * | 2020-09-30 | 2023-06-23 | 宁夏新龙蓝天科技股份有限公司 | Catalyst for preparing chloroethylene by calcium carbide method and preparation method thereof |
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