CN112142551B - Device and method for synthesizing chloroethylene by catalyzing hydrochlorination of acetylene by copper-based catalyst - Google Patents
Device and method for synthesizing chloroethylene by catalyzing hydrochlorination of acetylene by copper-based catalyst Download PDFInfo
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- CN112142551B CN112142551B CN202010935651.5A CN202010935651A CN112142551B CN 112142551 B CN112142551 B CN 112142551B CN 202010935651 A CN202010935651 A CN 202010935651A CN 112142551 B CN112142551 B CN 112142551B
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Abstract
The invention relates to a device and a method for synthesizing chloroethylene by catalyzing acetylene hydrochlorination through a copper-based catalyst. The device comprises a forward converter or two forward converters connected in series, wherein the forward converter comprises a forward converter body and a jacket arranged outside the forward converter body, the forward converter body is provided with a gas phase inlet and a gas phase outlet, and the jacket is provided with a cooling medium inlet and a cooling medium outlet; the gas phase inlet and the cooling medium inlet are arranged on the same side of the gas phase outlet and the cooling medium outlet and are used for forming forward flow with the raw material mixed gas and the cooling medium. Under the catalysis of copper-based catalyst and the cooling effect of cooling medium, the method carries out primary reaction or two-stage reaction on the raw material mixed gas comprising acetylene and hydrogen chloride, and the heat exchange flow of the raw material mixed gas comprising acetylene and hydrogen chloride and the cooling medium is downstream. The mixed gas of raw materials and the cooling medium form concurrent flow, and the reaction heat is fully utilized, so that the catalyst bed layer maintains higher temperature, and the materials are completely reacted.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a device and a method for synthesizing vinyl chloride by catalyzing hydrochlorination of acetylene by using a copper-based catalyst, which efficiently utilize the copper-based catalyst.
Background
The main production process of PVC production in China is calcium carbide method, namely acetylene hydrochlorination to synthesize vinyl chloride, and further polymerization to obtain PVC. In the calcium carbide process, hgCl is adopted for PVC 2 As a catalyst, due to HgCl 2 The boiling point is low, the reaction hot spot is concentrated, and mercury is easy to volatilize and lose, so that the existing calcium carbide method vinyl chloride synthesis unit adopts a converter with two stages connected in series and with countercurrent heat exchange of raw gas and cooling medium. The most main purpose of countercurrent contact heat exchangeThe method aims to ensure that the bed temperature at the outlet end of the material is low enough to enrich mercury vapor at the tail end of the converter and prevent mercury sublimation loss. The series-connected secondary converters are used for further enriching the primary volatile mercury, and on the other hand, the fresh mercury catalyst is not easy to generate the phenomenon of temperature runaway when running at low temperature and low strength because of low production strength of the secondary, and meanwhile, the novel mercury catalyst plays a role in inducing and activating.
The main active component of the copper-based catalyst is CuCl 2 ，CuCl 2 And HgCl 2 With great differences, especially CuCl 2 The boiling point of the copper-based catalyst is high, so that the copper-based catalyst cannot volatilize and run off at the reaction temperature. In the prior converter, the raw material gas enters from the upper part and exits from the lower part, and the cooling medium enters from the lower part and enters from the upper part in a countercurrent heat exchange mode, but the copper-based catalyst can be used, so that the heat exchange mode is unfavorable for the full utilization of heat. Particularly, the catalyst bed end is difficult to start catalytic reaction due to lower material concentration and bed temperature, so that the production efficiency of the copper-based catalyst is reduced, and the performance of the catalyst cannot be fully exerted.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a device and a method for synthesizing chloroethylene by catalyzing acetylene hydrochlorination by using a copper-based catalyst, wherein a mixed gas of raw materials and a cooling medium form concurrent flow, and reaction heat is fully utilized, so that a catalyst bed layer maintains higher temperature, and materials are completely reacted.
The technical solution of the invention is realized by the following technical scheme:
the invention provides a device for synthesizing chloroethylene by hydrochlorination of acetylene under the catalysis of a copper-based catalyst, which comprises a forward converter or two forward converters connected in series, wherein the forward converter comprises a forward converter body and a jacket arranged outside the forward converter body, the forward converter body is provided with a gas phase inlet and a gas phase outlet, and the jacket is provided with a cooling medium inlet and a cooling medium outlet; the gas phase inlet and the cooling medium inlet are arranged on the same side of the gas phase outlet and the cooling medium outlet and are used for forming forward flow between the raw material mixed gas and the cooling medium.
Preferably, the gas-phase inlet is arranged at the bottom of the downstream converter body, the gas-phase outlet is arranged at the top of the downstream converter body, and the cooling medium inlet is closer to the gas-phase inlet than the cooling medium outlet.
The second aspect of the invention provides a method for synthesizing chloroethylene by catalyzing acetylene hydrochlorination by a copper-based catalyst, which comprises the step of carrying out a first-stage reaction or a two-stage reaction on a raw material mixed gas comprising acetylene and hydrogen chloride under the catalysis of the copper-based catalyst and the cooling effect of a cooling medium, wherein the heat exchange flow of the raw material mixed gas comprising acetylene and hydrogen chloride and the cooling medium is concurrent.
Preferably, the one-stage reaction or two-stage reaction is carried out in the above-described apparatus.
Preferably, when two-stage reaction is performed, at least one of the following technical features is further included:
1) The mole ratio of acetylene to hydrogen chloride in the first stage reaction is 1:1.02 to 1:1.1, such as 1:1.02 to 1:1.05 or 1:1.05 to 1:1.1;
2) The space velocity of acetylene in the first-stage reaction is 20h -1 ～60h -1 For example 20h -1 ～40h -1 Or 40h -1 ～60h -1 ；
3) The reaction temperature in each stage of reaction is 90-180 ℃;
4) The reaction pressure in each stage of reaction is 20 KPa-70 KPa, such as 20 KPa-50 KPa or 50 KPa-70 KPa;
5) The height of each catalyst bed is 3-3.6 m, such as 3-3.3 m or 3.3-3.6 m;
6) The volume fraction of acetylene in the crude product gas obtained after the two-stage reaction is controlled to be less than or equal to 4 percent.
Preferably, when the primary reaction is performed, at least one of the following technical features is further included:
1) Molar ratio of acetylene to hydrogen chloride 1:1.02 to 1:1.1, such as 1:1.02 to 1:1.06 or 1: 1.06-1: 1.1;
2) Acetylene space velocity of 10h -1 ～40h -1 For example for 10 hours -1 ～25h -1 Or 25h -1 ～40h -1 。
Preferably, when the primary reaction is carried out, the reaction temperature is from 90℃to 180 ℃.
Preferably, when the primary reaction is carried out, the reaction pressure is 20KPa to 70KPa, such as 20KPa to 50KPa or 50KPa to 70KPa.
Preferably, when the primary reaction is carried out, the catalyst bed height is from 3.9m to 5.4m, such as from 3.9m to 4.6m or from 4.6m to 5.4m.
Preferably, when the primary reaction is carried out, the volume fraction of acetylene in the crude product gas obtained after the reaction is controlled to be less than or equal to 4%.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the raw material mixed gas and the cooling medium are subjected to concurrent heat exchange, and the reaction heat is fully utilized. The molar concentration of the raw material mixture at the gas phase inlet end is high at first, the reaction intensity and the heat release amount are high, at the moment, the cooling medium temperature is the lowest, the cooling effect can be better achieved, the reaction temperature is prevented from being too high, and the effect of protecting the catalyst is achieved; when the reactant reaches the tail end of the catalyst bed, the molar concentration of the reactant is low, the catalytic reaction is difficult to start, and the catalyst bed can maintain a high temperature by compensating heat energy accumulated by the cooling medium, so that the residual reactant is completely reacted.
2. In the invention, dust and high-boiling-point substances in the primary concurrent converter can be reduced from being entrained into the secondary concurrent converter by feeding the raw material mixed gas; meanwhile, the temperature of the second half section of the catalyst bed layer is increased, high-boiling-point substances are discharged, the service efficiency of the catalyst is improved, and the service life of the catalyst is prolonged.
3. The primary reaction (one forward converter) of the invention can completely convert acetylene at one time, thereby not only reducing the number of forward converters and greatly reducing the equipment investment, but also simplifying the field management and control.
Drawings
FIG. 1 is a schematic diagram of an apparatus for synthesizing vinyl chloride by hydrochlorination of acetylene under the catalysis of a copper-based catalyst comprising a forward converter.
FIG. 2 is a schematic diagram of an apparatus for synthesizing vinyl chloride by hydrochlorination of acetylene catalyzed by a copper-based catalyst comprising two downstream converters in series.
FIG. 3 is a schematic diagram of a device for synthesizing vinyl chloride by hydrochlorination of acetylene under the catalysis of a copper-based catalyst in the prior art.
Reference numerals
1. Concurrent flow converter body
2. Gas phase inlet
3. Gas phase outlet
4. Cooling medium inlet
5. Cooling medium outlet
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
The device for synthesizing chloroethylene by hydrochlorination of acetylene catalyzed by a copper-based catalyst comprises a forward converter or two serial forward converters, wherein the forward converter comprises a forward converter body 1 and a jacket arranged outside the forward converter body, the forward converter body 1 is provided with a gas phase inlet 2 and a gas phase outlet 3, and the jacket is provided with a cooling medium inlet 4 and a cooling medium outlet 5; the gas phase inlet 2 and the cooling medium inlet 4 are arranged on the same side of the gas phase outlet 3 and the cooling medium outlet 5 and are used for forming forward flow of the raw material mixed gas and the cooling medium.
In a preferred embodiment, as shown in fig. 1, the gas phase inlet 2 is disposed at the bottom of the downstream converter body 1, the gas phase outlet 3 is disposed at the top of the downstream converter body 1, and the cooling medium inlet 4 is closer to the gas phase inlet 2 than the cooling medium outlet 5.
Example 1
The device for synthesizing chloroethylene by hydrochlorination of acetylene catalyzed by a copper-based catalyst comprises two parallel flow converters (a first-stage parallel flow converter and a second-stage parallel flow converter) which are connected in series, wherein the parallel flow converters comprise a parallel flow converter body 1 and a jacket arranged outside the parallel flow converter body, the parallel flow converter body 1 is provided with a gas phase inlet 2 and a gas phase outlet 3, and the jacket is provided with a cooling medium inlet 4 and a cooling medium outlet 5; the gas phase inlet 2 and the cooling medium inlet 4 are arranged on the same side of the gas phase outlet 3 and the cooling medium outlet 5 and are used for forming forward flow between the raw material mixed gas and the cooling medium; the gas-phase inlet 2 is arranged at the bottom of the downstream converter body 1, the gas-phase outlet 3 is arranged at the top of the downstream converter body 1, and the cooling medium inlet 4 is closer to the gas-phase inlet 2 than the cooling medium outlet 5.
The molar ratio after preheating is 1:1.02 of acetylene and hydrogen chloride mixed gas enters the first-stage concurrent converter from a gas phase inlet 2 of the first-stage concurrent converter, and the airspeed of the acetylene is controlled to be 20h -1 The height of the catalyst bed layer is 3m, the reaction temperature is 90-180 ℃, and the pressure is 20KPa. Under the action of a copper-based catalyst, a gas phase component obtained by the primary reaction is extracted from a gas phase outlet 3 of a primary concurrent converter, then enters the secondary concurrent converter from a gas phase inlet 2 of the secondary concurrent converter, the height of a catalyst bed layer is 3m, the reaction temperature is 90-180 ℃, the pressure is 20KPa, the materials in the secondary concurrent converter undergo secondary reaction, and the obtained crude chloroethylene product gas is extracted from the gas phase outlet 3 of the secondary concurrent converter.
The shell side cooling medium of the primary concurrent converter enters the jacket from the cooling medium inlet 4 and leaves the primary concurrent converter from the cooling medium outlet 5. The shell side cooling medium of the secondary concurrent converter enters the jacket from the cooling medium inlet 4 and leaves the secondary concurrent converter from the cooling medium outlet 5.
The operating conditions are as follows:
operational condition of primary concurrent converter
Operation condition of two-stage concurrent converter
Example 2
The apparatus used was the same as in example 1.
The molar ratio after preheating is 1:1.05 of acetylene and hydrogen chloride mixed gas enters the first-stage concurrent converter from a gas phase inlet 2 of the first-stage concurrent converter, and the airspeed of the acetylene is controlled to be 40h -1 The height of the catalyst bed is 3.3m, the reaction temperature is 90-180 ℃, and the pressure is 50KPa. Under the action of a copper-based catalyst, a gas phase component obtained by the primary reaction is extracted from a gas phase outlet 3 of a primary concurrent converter, then enters the secondary concurrent converter from a gas phase inlet 2 of the secondary concurrent converter, the height of a catalyst bed layer is 3.3m, the reaction temperature is 90-180 ℃, the pressure is 50KPa, the materials in the secondary concurrent converter undergo secondary reaction, and the obtained crude chloroethylene product gas is extracted from the gas phase outlet 3 of the secondary concurrent converter.
The shell side cooling medium of the primary concurrent converter enters the jacket from the cooling medium inlet 4 and leaves the primary concurrent converter from the cooling medium outlet 5. The shell side cooling medium of the secondary concurrent converter enters the jacket from the cooling medium inlet 4 and leaves the secondary concurrent converter from the cooling medium outlet 5.
The operating conditions are as follows:
operational condition of primary concurrent converter
Operation condition of two-stage concurrent converter
Example 3
The apparatus used was the same as in example 1.
The molar ratio after preheating is 1:1.1, the mixed gas of acetylene and hydrogen chloride enters the first-stage concurrent converter from a gas phase inlet 2 of the first-stage concurrent converter, and the airspeed of the acetylene is controlled to be 60h -1 The height of the catalyst bed is 3.6m, the reaction temperature is 90-180 ℃, and the pressure is 70KPa. Under the action of a copper-based catalyst, a gas phase component obtained by the primary reaction is extracted from a gas phase outlet 3 of a primary concurrent converter, then enters the secondary concurrent converter from a gas phase inlet 2 of the secondary concurrent converter, the height of a catalyst bed layer is 3.6m, the reaction temperature is 90-180 ℃, the pressure is 70KPa, the materials in the secondary concurrent converter undergo secondary reaction, and the obtained crude chloroethylene product gas is extracted from the gas phase outlet 3 of the secondary concurrent converter.
The shell side cooling medium of the primary concurrent converter enters the jacket from the cooling medium inlet 4 and leaves the primary concurrent converter from the cooling medium outlet 5. The shell side cooling medium of the secondary concurrent converter enters the jacket from the cooling medium inlet 4 and leaves the secondary concurrent converter from the cooling medium outlet 5.
The operating conditions are as follows:
operational condition of primary concurrent converter
Operation condition of two-stage concurrent converter
Example 4
The device for synthesizing chloroethylene by hydrochlorination of acetylene catalyzed by a copper-based catalyst comprises a forward converter, as shown in fig. 1, wherein the forward converter comprises a forward converter body 1 and a jacket arranged outside the forward converter body, the forward converter body 1 is provided with a gas phase inlet 2 and a gas phase outlet 3, and the jacket is provided with a cooling medium inlet 4 and a cooling medium outlet 5; the gas phase inlet 2 and the cooling medium inlet 4 are arranged on the same side of the gas phase outlet 3 and the cooling medium outlet 5 and are used for forming forward flow between the raw material mixed gas and the cooling medium; the gas-phase inlet 2 is arranged at the bottom of the downstream converter body 1, the gas-phase outlet 3 is arranged at the top of the downstream converter body 1, and the cooling medium inlet 4 is closer to the gas-phase inlet 2 than the cooling medium outlet 5.
The molar ratio after preheating is 1:1.02 of acetylene and hydrogen chloride raw material mixed gas enters the concurrent converter from a gas phase inlet 2 of the concurrent converter, and the airspeed of the acetylene is controlled to be 10h -1 The height of the catalyst bed is 3.9m, the reaction temperature is 90-180 ℃, and the pressure is 20KPa. The crude chloroethylene product gas is obtained by the reaction under the catalysis of a copper-based catalyst and is extracted from a gas phase outlet 3 of the concurrent converter.
The shell side cooling medium of the forward flow converter enters the jacket from the cooling medium inlet 4 and leaves the forward flow converter from the cooling medium outlet 5.
The operating conditions are as follows:
single stage forward converter operation
Example 5
The apparatus used was the same as in example 4.
The molar ratio after preheating is 1:1.06 the mixed gas of acetylene and hydrogen chloride raw material enters the concurrent converter from the gas phase inlet 2 of the concurrent converter, and the space velocity of the acetylene is controlled to be 25h -1 The height of the catalyst bed layer is 4.6m, the reaction temperature is 90-180 ℃ and the pressure is 50KPa. The crude chloroethylene product gas is obtained by the reaction under the catalysis of a copper-based catalyst and is extracted from a gas phase outlet 3 of the concurrent converter.
The shell side cooling medium of the forward flow converter enters the jacket from the cooling medium inlet 4 and leaves the forward flow converter from the cooling medium outlet 5.
The operating conditions are as follows:
single stage forward converter operation
Example 6
The apparatus used was the same as in example 4.
The molar ratio after preheating is 1:1.1, the mixed gas of acetylene and hydrogen chloride raw material enters the concurrent converter from a gas phase inlet 2 of the concurrent converter, and the space velocity of the acetylene is controlled to be 40h -1 The height of the catalyst bed is 5.4m, the reaction temperature is 90-180 ℃, and the pressure is 70KPa. The crude chloroethylene product gas is obtained by the reaction under the catalysis of a copper-based catalyst and is extracted from a gas phase outlet 3 of the concurrent converter.
The shell side cooling medium of the forward flow converter enters the jacket from the cooling medium inlet 4 and leaves the forward flow converter from the cooling medium outlet 5.
The operating conditions are as follows:
single stage forward converter operation
Comparative example
The device used is shown in fig. 3, and comprises two countercurrent converters (a first countercurrent converter and a second countercurrent converter) connected in series, wherein the countercurrent converter comprises a countercurrent converter body 1 and a jacket arranged outside the countercurrent converter body, the countercurrent converter body 1 is provided with a gas phase inlet 2 and a gas phase outlet 3, and the jacket is provided with a cooling medium inlet 4 and a cooling medium outlet 5; the gas phase inlet 2 is arranged at the top of the countercurrent converter body 1, the gas phase outlet 3 is arranged at the bottom of the countercurrent converter body 1, and the cooling medium inlet 4 is closer to the gas phase outlet 3 than the cooling medium outlet 5.
The molar ratio after preheating is 1:1.05 of acetylene and hydrogen chloride mixed gas enters the first-stage countercurrent converter from a gas phase inlet 2 of the first-stage countercurrent converter, and the airspeed of the acetylene is controlled to be 40h -1 The height of the catalyst bed is 3.3m, the reaction temperature is 100-160 ℃, and the pressure is 50KPa. Under the action of a copper-based catalyst, the gas phase component obtained by the primary reaction is extracted from a gas phase outlet 3 of a primary countercurrent converter, then enters the secondary countercurrent converter from a gas phase inlet of the secondary countercurrent converter, the height of a catalyst bed is 3m, the reaction temperature is 100-160 ℃, the pressure is 50KPa, the materials in the secondary countercurrent converter undergo the secondary reaction, and the obtained crude chloroethylene product gas is extracted from the gas phase outlet of the secondary countercurrent converter.
The shell side cooling medium of the primary countercurrent converter enters the jacket from the cooling medium inlet 4 and leaves the primary countercurrent converter from the cooling medium outlet 5. The shell side cooling medium of the secondary countercurrent converter enters the jacket from the cooling medium inlet 4 and leaves the secondary countercurrent converter from the cooling medium outlet 5.
The operating conditions are as follows:
operation of the primary countercurrent converter
Operation of the two-stage countercurrent converter
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. A method for synthesizing chloroethylene by hydrochlorination of acetylene under the catalysis of a copper-based catalyst is characterized in that under the catalysis of the copper-based catalyst and the cooling effect of a cooling medium, raw material mixed gas comprising acetylene and hydrogen chloride is subjected to one-stage reaction or two-stage reaction, wherein the heat exchange flow of the raw material mixed gas comprising acetylene and hydrogen chloride and the cooling medium is concurrent;
the primary reaction or the two-stage reaction is carried out in a device for synthesizing chloroethylene by catalyzing acetylene hydrochlorination by a copper-based catalyst, the device comprises a downstream converter or two downstream converters connected in series, the downstream converter comprises a downstream converter body (1) and a jacket arranged outside the downstream converter body, the downstream converter body (1) is provided with a gas phase inlet (2) and a gas phase outlet (3), and the jacket is provided with a cooling medium inlet (4) and a cooling medium outlet (5); the gas phase inlet (2) and the cooling medium inlet (4) are arranged on the same side of the gas phase outlet (3) and the cooling medium outlet (5) and are used for forming forward flow between the raw material mixed gas and the cooling medium; the gas-phase inlet (2) is arranged at the bottom of the concurrent converter body (1), the gas-phase outlet (3) is arranged at the top of the concurrent converter body (1), and the cooling medium inlet (4) is closer to the gas-phase inlet (2) than the cooling medium outlet (5);
when the primary reaction is carried out, the space velocity of acetylene is 10h -1 ～40h -1 The method comprises the steps of carrying out a first treatment on the surface of the The height of the catalyst bed layer is 3.9 m-5.4 m;
when two-stage reaction is carried out, the space velocity of acetylene in the first-stage reaction is 20h -1 ～60h -1 The method comprises the steps of carrying out a first treatment on the surface of the The height of each catalyst bed is 3 m-3.6 m.
2. The method for synthesizing vinyl chloride by hydrochlorination of acetylene catalyzed by a copper based catalyst according to claim 1, wherein when the two-stage reaction is carried out, the mole ratio of acetylene to hydrogen chloride in the first stage reaction is 1:1.02 to 1:1.1.
3. the method for synthesizing vinyl chloride by hydrochlorination of acetylene catalyzed by a copper based catalyst according to claim 1, wherein when two-stage reaction is carried out, the reaction temperature in each stage reaction is 90 ℃ to 180 ℃.
4. The method for synthesizing vinyl chloride by hydrochlorination of acetylene catalyzed by a copper based catalyst according to claim 1, wherein when two-stage reaction is carried out, the reaction pressure in each stage reaction is 20KPa to 70KPa.
5. The method for synthesizing chloroethylene by hydrochlorination of acetylene by using a copper-based catalyst according to claim 1, wherein when two-stage reaction is performed, the volume fraction of acetylene in the crude product gas obtained after the two-stage reaction is controlled to be less than or equal to 4%.
6. The method for synthesizing vinyl chloride by hydrochlorination of acetylene catalyzed by a copper based catalyst according to claim 1, wherein when the primary reaction is carried out, the mole ratio of acetylene to hydrogen chloride is 1:1.02 to 1:1.1.
7. the method for synthesizing vinyl chloride by hydrochlorination of acetylene under the catalysis of a copper-based catalyst according to claim 1, wherein when the primary reaction is carried out, the reaction temperature is 90-180 ℃.
8. The method for synthesizing vinyl chloride by hydrochlorination of acetylene catalyzed by a copper based catalyst according to claim 1, wherein when the primary reaction is carried out, the reaction pressure is 20KPa to 70KPa.
9. The method for synthesizing chloroethylene by hydrochlorination of acetylene under the catalysis of a copper-based catalyst according to claim 1, wherein when the primary reaction is carried out, the volume fraction of acetylene in the crude product gas obtained after the reaction is controlled to be less than or equal to 4%.
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| CN106478383A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The method of preparing dimethyl ether from methanol and the method and system of consersion unit and methanol-to-olefins |
| CN105330512A (en) * | 2015-12-04 | 2016-02-17 | 厦门中科易工化学科技有限公司 | Method for preparing chloroethylene from acetylene and hydrogen chloride in mercuration-free mode |
| CN109539837A (en) * | 2017-09-21 | 2019-03-29 | 程长春 | Parallel flow heat exchanger |
| CN108358744A (en) * | 2018-02-05 | 2018-08-03 | 陕西北元化工集团股份有限公司 | A kind of non-mercury catalyst acetylene method VCM synthesis technique |
| CN110052222A (en) * | 2019-05-20 | 2019-07-26 | 陕西金泰氯碱化工有限公司 | A kind of process of cold shock formula mercury-free catalysis VCM synthesis |
| CN211216594U (en) * | 2019-09-30 | 2020-08-11 | 河北美邦工程科技股份有限公司 | Chloroethylene production device |
| CN110743470A (en) * | 2019-10-31 | 2020-02-04 | 河北美邦工程科技股份有限公司 | Gas-liquid phase chloroethylene production device and process |
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