CN106588559B - Ethylene chlorinating agent for preparing 1, 2-dichloroethane, application thereof and preparation method of 1, 2-dichloroethane - Google Patents
Ethylene chlorinating agent for preparing 1, 2-dichloroethane, application thereof and preparation method of 1, 2-dichloroethane Download PDFInfo
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Abstract
The invention relates to an ethylene chlorinating agent for preparing 1, 2-dichloroethane, application thereof and a preparation method of 1, 2-dichloroethane, wherein the ethylene chlorinating agent comprises CuCl2And KCl, CuCl2: the KCl molar ratio is 2.5-0.5: 1, and the ethylene chlorinating agent is a mixed salt solution and is used for preparing 1, 2-dichloroethane; the preparation method comprises the following steps: step 1) containing C2H4The gas reacts with the ethylene chlorinating agent to obtain the gas containing 1, 2-dichloroethane and the mixed salt solution containing CuCl, the mixed salt solution is used as the ethylene chlorinating agent for preparing the 1, 2-dichloroethane, the transportation and the separation are easy, the operation is simple and convenient, the product quality can reach the ethylene direct chlorination method, the problem of the stability of the ethylene oxychlorination catalyst is solved, the direct mixing of organic gases such as ethylene and the like with oxygen to generate aldehydes and alcohols byproducts is avoided, the product purity is higher, the product is safer, and the cost is low.
Description
Technical Field
The invention belongs to the field of chemical production, and relates to an ethylene chlorinating agent for preparing 1, 2-dichloroethane, application thereof and a preparation method of the 1, 2-dichloroethane.
Background
1, 2-dichloroethane, commonly known as Ethylene Dichloride (EDC), is used globally at about 95% in the production of vinyl chloride monomer and then in the synthesis of polyvinyl chloride. Dichloroethane is also an organic solvent widely used in industry, as a solvent for trichloroethylene, ethylamine, vinylidene chloride and trichloroethane, and also used as an intermediate for producing tetrachloroethylene and a catalyst for producing hexachlorophenolmethane.
The industrial production of dichloroethane mainly comprises the direct chlorination of ethylene with chlorine and the oxychlorination of ethylene, hydrogen chloride, oxygen or air in the presence of a catalyst. Ethylene direct chlorination is the direct chlorination of ferric chloride (FeCl) dissolved in dichloroethane with chlorine gas and ethylene gas entering a direct chlorination reactor3) As a catalyst, the addition reaction is carried out under certain conditions to generate 1, 2-dichloroethane. However, in addition to the direct chlorination process, ethylene is also used industrially for the production of dichloroethane because of the consumption of large amounts of hydrogen chloride produced by the chlor-alkali industry. The technology is that ethylene, oxygen or air and hydrogen chloride are mixed and then subjected to oxychlorination reaction,the technology for preparing dichloroethane by oxychlorination of ethylene comprises a catalyst system, a raw material preheating system, an oxychlorination reaction system, a quenching separation system, a coarse EDC separation system, an EDC drying system and a wastewater stripping system.
The ethylene is used as a raw material whether the ethylene is directly chlorinated or oxychlorinated, and the current industrial main production methods of ethylene comprise an ethane thermal cracking method, a naphtha cracking method and an MTO method. Because of the many byproducts of the methods, ethylene can be directly chloridized or oxychlorinated to prepare dichloroethane after being separated and purified.
Such as steam cracking, is a conventional process for producing ethylene from ethane. The reaction temperature of the method is above 800 ℃, the thermal cracking temperature is high, the energy consumption is large, and the requirements on equipment materials are strict, so the production cost is high. Meanwhile, other heavy olefins such as propylene, butadiene, aromatic hydrocarbons and the like are also generated in the product, and the ethylene yield is reduced.
Patent application No. 201110324801.X discloses a method for preparing olefin by catalytic cracking naphtha, wherein a composite molecular sieve is used as a catalyst, the catalyst mainly comprises kaolin, a binder, a phosphorus oxide and a rare earth element oxide, the yield of ethylene obtained by reaction is very low and is only about 20%, and the product contains a large amount of byproducts such as propylene, butadiene and the like.
Coal is used as a raw material, and the process of preparing ethylene by methanol is adopted, so that the content of oxygen-containing smoke impurities brought by catalyst regeneration in olefin product gas is high, and the olefin product gas also contains oxygen-containing organic compounds such as methanol, dimethyl ether and the like. For example, the method disclosed in CN1833017A has the disadvantages that products such as hydrogen, methane, ethane and propane with high purity cannot be obtained, and oxygen and carbon monoxide in dimethyl ether and flue gas impurities cannot be effectively removed.
Compared with the preparation method of the ethylene, the technology for preparing the ethylene by chlorination and dehydrogenation of the ethane is more energy-saving, convenient and economical. A process for the preparation of ethylene by chlorination dehydrogenation of ethane is provided, as in application No. 201510630923. X. The technique is to mix low boiling point metal chloride with C2H6Mixing and reacting, reducing the low-boiling point metal chloride into liquid low-melting point metalIs an intermediate medium, C2H6After chlorination dehydrogenation, the product containing HCl and C is obtained2H6、C2H4And the like. The process is if C2H6Complete reaction, then by-product C is produced2H2And C2H3Cl, which needs to be separated before it can be used to make dichloroethane. But if control C2H6The conversion rate is in a certain range, and high C can be obtained2H4Is selective and is due to C produced2H4The proportion of HCl and HCl is just the proportion of ethylene oxychlorination to dichloroethane, so the tail gas of ethane chlorination dehydrogenation is particularly suitable for oxychlorination to prepare dichloroethane. However, if the ethylene dichloride prepared by the existing ethylene oxychlorination technology has the defects of unstable catalyst, low purity, long separation and purification process flow, large equipment investment, high cost and the like because a product obtained by directly mixing organic gas and oxygen contains byproducts of chloral, chloroethanol and the like.
For example, application No. CN201210330007.0 describes impregnating a catalyst carrier with an impregnating solution, which is a solution containing an alkali metal component, an alkaline earth metal component and a rare earth metal component, and then washing and drying the catalyst carrier impregnated with the impregnating solution, which contains a copper component and alumina, and a detergent for the washing which is an aqueous solution of an alkali metal bicarbonate and/or an alkali metal carbonate. The ethylene oxychlorination catalyst prepared by the method not only has complex process, but also needs washing by alkaline solution, the generated waste alkali liquor needs to be treated, the cost is increased, and the conversion rate of the hydrogen chloride and the yield of the dichloroethane when the catalyst prepared by the method is used for preparing the dichloroethane yield by the ethylene oxychlorination do not achieve ideal effects.
U.S. patent 911020454 discloses an oxychlorination process for the production of 1, 2-dichloroethane using a fluidizable catalyst in which a mixture of cupric chloride, rare earth metal salts and alkali metal salts is supported on an alumina support. Although the problem of catalyst caking property is solved, the ethylene, oxygen and hydrogen chloride are mixed and introduced into the catalyst for reaction, so that the product easily contains aldehyde and alcohol byproducts, the separation difficulty is increased, and an air separation device is required because the ethylene and the oxygen are easy to explode, the requirement on equipment is strict, and the cost is high.
In order to solve the technical defects of the prior ethylene oxychlorination, the invention develops a new economic, simple, convenient and safe ethylene oxychlorination process for preparing dichloroethane.
Disclosure of Invention
The invention overcomes the technical defects of more byproducts, long process flow, high cost and the like in the prior preparation of 1, 2-dichloroethane by solid-phase catalytic oxychlorination of ethylene, and provides an ethylene chlorinating agent for preparing 1, 2-dichloroethane, application thereof and a preparation method of 1, 2-dichloroethane, wherein the ethylene chlorinating agent comprises CuCl2And KCl, CuCl2: the KCl molar ratio is 2.5-0.5: 1, and the ethylene chlorinating agent is a mixed salt solution and is used for preparing 1, 2-dichloroethane; the preparation method comprises the following steps: step 1) containing C2H4The gas reacts with the ethylene chlorinating agent to obtain the gas containing 1, 2-dichloroethane and the mixed salt solution containing CuCl, the mixed salt solution is used as the ethylene chlorinating agent for preparing the 1, 2-dichloroethane, the transportation and the separation are easy, the operation is simple and convenient, the product quality can reach the ethylene direct chlorination method, the problem of the stability of the ethylene oxychlorination catalyst is solved, the direct mixing of organic gases such as ethylene and the like with oxygen to generate aldehydes and alcohols byproducts is avoided, the product purity is higher, the product is safer, and the cost is low.
The invention is realized by the following technical scheme:
the invention provides in a first aspect an ethylene chlorinating agent for the preparation of 1, 2-dichloroethane, the ethylene chlorinating agent comprising CuCl2And KCl, CuCl2: the molar ratio of KCl is 2.5-0.5: 1, and the ethylene chlorinating agent is a mixed salt solution.
The mixed salt melt is a mixed liquid with the components in a molten state.
Preferably, the ethylene chlorinating agent further comprises CuCl, CuCl: the molar ratio of KCl is less than or equal to 1.25.
For example, CuCl2: the molar ratio of KCl is 2.5-2: 1, 2-1.5: 1 or 1.5-0.5: 1, CuCl: the molar ratio of KCl is 0-0.4: 1, 0.4-0.8: 1 or 0.8-1.25: 1.
Preferably, the ethylene chlorinating agent has a melting point of 200 to 300 ℃, such as 200 to 250 ℃, 250 to 280 ℃ or 280 to 300 ℃.
The second aspect of the invention provides the use of the ethylene chlorinating agent described above for the preparation of 1, 2-dichloroethane.
Preferably, it contains C2H4With said ethylene chlorinating agent, C2H4Is chlorinated to obtain 1, 2-dichloroethane, CuCl in ethylene chlorinating agent2Is reduced into CuCl to obtain gas containing 1, 2-dichloroethane and mixed salt solution containing CuCl.
In a third aspect, the present invention provides a process for producing 1, 2-dichloroethane, the process comprising: step 1) containing C2H4With the above-mentioned ethylene chlorinating agent, C2H4Is chlorinated to obtain 1, 2-dichloroethane, CuCl in ethylene chlorinating agent2Is reduced into CuCl to obtain gas containing 1, 2-dichloroethane and mixed salt solution containing CuCl.
Preferably, in the step 1), the ethylene chlorinating agent enters from a liquid phase feed inlet of a chlorination tower and is introduced into a gas inlet of the chlorination tower, wherein the gas inlet of the chlorination tower contains C2H4Is counter-currently contacted with a gas containing C2H4With said ethylene chlorinating agent, C2H4Is chlorinated to obtain 1, 2-dichloroethane, CuCl in the ethylene chlorinating agent2Is reduced into CuCl to obtain gas containing 1, 2-dichloroethane and salt solution containing CuCl, the gas containing 1, 2-dichloroethane is discharged from a gas outlet of the chlorination tower, and the salt solution containing CuCl is discharged from a liquid phase discharge port of the chlorination tower.
In step 1), contains C2H4The gas of (A) may be pure C2H4Gas or containing C2H4Mixed gases, e.g. containing C2H4The refinery dry gas or the gas generated by ethane chlorination dehydrogenation.
In step 1), when containing C2H4The gas of (A) is pure C2H4When a gas is present, chloridizing1, 2-dichloroethane steam is discharged from a tower gas outlet; when containing C2H4The gas of (A) is a gas containing C2H4Mixed gases, e.g. containing C2H4The mixed gas containing 1, 2-dichloroethane vapor is discharged from a gas outlet of the chlorination tower.
In step 1), the ethylene conversion is determined by the composition of the 1, 2-dichloroethane-containing gas, and ethylene is completely chlorinated by adjusting the feed gas flow rate when ethylene conversion is not complete. If the ethylene conversion is not complete, the C content passed to the chlorination column2H4The gas flow rate of (2) is slowed down, so that the reaction time of the gas and the salt solution is prolonged to complete conversion.
Preferably, step 1) further comprises one or more of the following technical features:
1)C2H4with CuCl2In a molar ratio of 1: 2.1 to 10, such as 1: 2.1-4, 1: 4-7 or 1: 7-10;
2) the reaction temperature is 200-300 ℃, such as 200-250 ℃, 250-280 ℃ or 280-300 ℃;
3) containing C2H4The gas is the gas obtained by chlorination and dehydrogenation of ethane, namely low-boiling point metal chloride and C2H6The mixed gas obtained by the mixing reaction is BiCl which is the low boiling point metal chloride3Or SnCl2This contains C2H4The preparation of the gas of (a) is prior art, disclosed by 201510630923. X;
4) the obtained gas containing 1, 2-dichloroethane is condensed, rectified and separated to obtain refined 1, 2-dichloroethane.
When the gas containing 1, 2-dichloroethane is 1, 2-dichloroethane vapor, condensing the 1, 2-dichloroethane vapor to obtain a crude liquid phase of 1, 2-dichloroethane, rectifying and separating to obtain refined 1, 2-dichloroethane, and when the gas containing 1, 2-dichloroethane contains other gases besides 1, 2-dichloroethane, separating the condensed 1, 2-dichloroethane, and recovering the residual gas.
Preferably, the preparation method further comprises: and 2) reacting the salt solution containing CuCl with oxygen, and oxidizing all or part of CuCl into copper oxychloride to obtain the salt solution containing copper oxychloride.
Copper oxychloride is a product obtained by oxidizing CuCl with oxygen and contains three elements, Cu, O and Cl.
Preferably, in step 2), the salt solution containing CuCl discharged from the liquid phase discharge port of the chlorination tower enters the oxidation tower from the liquid phase feed port of the oxidation tower, oxygen is introduced from the gas inlet of the oxidation tower and reversely contacts with the salt solution containing CuCl, the CuCl is completely or partially oxidized into copper oxychloride, so as to obtain the salt solution containing copper oxychloride, and the salt solution containing copper oxychloride is discharged from the liquid phase discharge port of the oxidation tower.
When the ethylene chlorinating agent is CuCl2And KCl, CuCl is completely oxidized into copper oxychloride or partially oxidized into copper oxychloride; when the ethylene chlorinating agent comprises CuCl2CuCl and KCl, the CuCl is partially oxidized to copper oxychloride.
More preferably, step 2) further comprises one or more of the following technical features:
1) the molar ratio of CuCl to oxygen is 2-3: 1, such as 2-2.4: 1. 2.4-2.6: 1 or 2.6-3: 1;
2) the reaction temperature is 250-400 ℃, such as 250-300 ℃, 300-350 ℃ or 350-400 ℃.
More preferably, the preparation method further comprises: step 3), reacting the salt solution containing copper oxychloride with HCl-containing gas to completely absorb HCl, and reacting the copper oxychloride with HCl to obtain CuCl2And steam to obtain the ethylene chlorinating agent and the steam-containing gas.
More preferably, in step 3), the salt solution containing copper chloride and discharged from the liquid phase discharge port of the oxidation tower enters the HCl absorption tower through the liquid phase feed port of the HCl absorption tower, and reversely contacts with the gas containing HCl and introduced from the gas inlet of the HCl absorption tower, so that the copper chloride and the HCl react to obtain CuCl2And water vapor to obtain the ethylene chlorinating agent and gas containing water vapor, wherein the gas containing water vapor is discharged from a gas outlet of the HCl absorption tower, and the ethylene chlorinating agent is discharged from a liquid-phase discharge port of the HCl absorption tower.
Even more preferably, when C is contained2H4The gas of (A) is a low boiling point metal chloride and C2H6When the mixed gas is obtained by the mixing reaction, in the step 3), the salt solution containing copper chloride and discharged from the liquid-phase discharge port of the oxidation tower enters the HCl absorption tower through the liquid-phase feed port of the HCl absorption tower, and the copper chloride and the HCl react to obtain CuCl2And water vapor to obtain the ethylene chlorinating agent and gas containing water vapor, wherein the gas containing water vapor is discharged from a gas outlet of the HCl absorption tower, the ethylene chlorinating agent is discharged from a liquid-phase discharge port of the HCl absorption tower, and the gas containing HCl can not be introduced because the gas-phase component obtained by chlorination and dehydrogenation of ethane is C2H4HCl and C2H6In which C is2H4And HCl is just the raw material for preparing 1, 2-dichloroethane by oxychlorination of ethylene and the mixture ratio.
In step 3), the HCl-containing gas may be pure HCl gas or HCl-containing mixed gas, such as one or more of HCl-containing mixed gas obtained by methane chlorination, ethane chlorination dehydrogenation, or other methods.
In the step 3), when the HCl-containing gas is pure HCl gas, water vapor is discharged from a gas outlet of the HCl absorption tower; when the HCl-containing gas is a mixed gas containing HCl, the mixed gas containing water vapor is discharged from the gas outlet of the HCl absorption tower.
Even more preferably, in step 3), when the gas containing water vapor is pure water vapor, water is obtained after condensation; when the gas containing water vapor is a mixed gas containing water vapor, water after condensation is separated and the remaining gas is recovered.
Even more preferably, step 3) further comprises one or more of the following technical features:
1) the molar ratio of copper oxychloride to HCl is 1: 2-2.1, preferably 1: 2;
2) the reaction temperature is 180-230 ℃, such as 180-190 ℃, 190-210 ℃ or 210-230 ℃;
3) recycling the ethylene chlorinating agent obtained in the step 3) to the step 1) to react with C2H4The gas of (2) reacts.
The invention has at least one of the following beneficial effects:
1) the invention adopts liquid-phase salt solution as an oxychlorination circulating reagent, is easy to convey and separate, is simple and convenient to operate, has the product quality reaching that of an ethylene direct chlorination method, and solves the problem of catalyst stability compared with the prior oxychlorination technology.
2) Compared with the existing ethylene oxychlorination method, the method avoids the generation of aldehyde and alcohol byproducts by directly mixing organic gases such as ethylene and the like with oxygen, has higher product purity, is safer, does not need an air separation device, and has low cost.
3) Invention C2H4The chlorination and the HCl absorption are carried out in different towers without mutual interference, thereby omitting the processes of purification and separation of the raw material gas in the prior ethylene oxychlorination method and leading C to be2H4The source of HCl and HCl is wider, and reaction and one-by-one purification and separation of products are realized at the same time; the three reaction towers can be used in series or independently according to different raw materials, and are more flexible.
4) Due to the above-mentioned features of the ethylene oxychlorination process of the present invention, the oxychlorination technology is particularly suitable for the preparation of 1, 2-dichloroethane from the gas obtained from the chlorination dehydrogenation of ethane disclosed in patent application No. 201510630923. Because the gas phase component obtained by chlorination and dehydrogenation of ethane is C2H4HCl and C2H6In which C is2H4And HCl is just the raw material for preparing 1, 2-dichloroethane by oxychlorination of ethylene and the mixture ratio. C2H4HCl and C2H6After the mixed gas passes through a chlorination tower and an HCl absorption tower in sequence, C2H4And HCl are reacted one by one to realize the separation and purification of the mixed gas, simultaneously obtain single products of each unit in sequence, and finally only C is left in the mixed gas2H6Continuously circulating to an ethane chlorination dehydrogenation area for reaction, and achieving the purpose of preparing the 1, 2-dichloroethane by using ethane as a raw material in a more economical, simple and efficient way.
Drawings
FIG. 1 is a schematic diagram of the process for the preparation of 1, 2-dichloroethane according to the invention.
Reference numerals:
1-a chlorination column gas inlet;
2-a chlorination column gas outlet;
3-chlorination tower liquid phase discharge port;
4-liquid phase feeding of an oxidation tower;
5-an oxidation tower gas inlet;
6-a liquid phase discharge hole of the oxidation tower;
a liquid phase feed inlet of the 7-HCl absorption tower;
a gas inlet of the 8-HCl absorption tower;
a gas outlet of the 9-HCl absorption tower;
a liquid phase discharge port of the 10-HCl absorption tower;
11-a liquid phase feed inlet of the chlorination tower.
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.
Example 1
(1) As shown in FIG. 1, the molar ratio of CuCl is adjusted2: KCl is 2.5: 1 of CuCl2A KCl mixed salt solution with the melting point of 300 ℃, enters from a liquid phase feed inlet 11 of the chlorination tower and is introduced into a pure C inlet 1 of the chlorination tower2H4Reverse contact of gas, control C2H4And CuCl2In a molar ratio of 1: 2.1, at 300 ℃ C2H4And CuCl2Reacting to make all C2H4The 1, 2-dichloroethane vapor obtained by chlorination is discharged from a gas outlet 2 of the chlorination tower and condensed to obtain liquid phase 1, 2-dichloroethane, and the detection resultSee table 1.
(2) Discharging the salt solution obtained after chlorination in the step 1) from a liquid-phase discharge port 3 of a chlorination tower, feeding the salt solution into an oxidation tower from a liquid-phase feed port 4 of the oxidation tower, introducing oxygen from a gas inlet 5 of the oxidation tower, reversely contacting with the salt solution, and controlling the molar ratio of CuCl to the introduced oxygen to be 2: oxidizing CuCl into copper oxychloride at the oxidation temperature of 400 ℃.
(3) Discharging the oxygen-containing copper chloride salt solution obtained after oxidation in the step 2) from a liquid phase discharge port 6 of the oxidation tower, feeding the oxygen-containing copper chloride salt solution into an HCl absorption tower through a liquid phase feed port 7 of the HCl absorption tower, reversely contacting with pure HCl gas introduced from a gas inlet 8 of the HCl absorption tower, and controlling the molar ratio of copper oxychloride to HCl to be 1: 2.10 at 230 ℃ and reacting copper oxychloride with HCl to obtain CuCl2And HCl-containing water vapor discharged from a gas outlet 9 of the HCl absorption tower, and condensed to obtain dilute acid, and the salt solution absorbs HCl to obtain CuCl2Discharging KCl salt solution through a liquid phase discharge port 10 of the HCl absorption tower, circulating to the step 1) and continuing to react with C2H4And (4) reacting.
Example 2
(1) The molar ratio of CuCl2: CuCl: KCl is 2: 0.4:1 of CuCl2A melting point of the-CuCl-KCl mixed salt solution is 280 ℃, and the solution enters from a liquid phase feed inlet of the chlorination tower and is introduced into a gas inlet of the chlorination tower and contains C2H4HCl and C2H6Ethane chlorination dehydrogenation of (i) BiCl3And C2H6The mixed gas obtained by the reaction is in reverse contact, and C is controlled2H4And CuCl2In a molar ratio of 1: 4, C in the mixed gas at 280 ℃2H4And CuCl2Reacting to make all C2H4Is chlorinated to obtain 1, 2-dichloroethane vapor, HCl and C2H6Discharging the mixed gas together from the gas outlet of the chlorination tower, wherein 1, 2-dichloroethane is condensed to obtain liquid phase 1, 2-dichloroethane, the detection results are shown in Table 1, and the residual unreacted HCl and C2H6And (6) recovering.
(2) Discharging the salt solution obtained after chlorination in the step 1) from a liquid-phase discharge port of a chlorination tower, feeding the salt solution into an oxidation tower from a liquid-phase feed port of the oxidation tower, introducing oxygen from a gas inlet of the oxidation tower, reversely contacting with the salt solution, and controlling the molar ratio of CuCl to the introduced oxygen to be 2.4: 1, oxidizing at 350 ℃ to oxidize part of CuCl into copper oxychloride.
(3) Discharging the oxygen-containing copper chloride salt solution obtained after oxidation in the step 2) from a liquid phase discharge port of the oxidation tower, feeding the oxygen-containing copper chloride salt solution into an HCl absorption tower through a liquid phase feed port of the HCl absorption tower, and reversely introducing HCl and C from a gas inlet of the HCl absorption tower2H6And (3) contacting the mixed gas, and controlling the molar ratio of copper oxychloride to HCl to be 1: 2, the reaction temperature is 210 ℃, so that copper oxychloride and HCl react to obtain CuCl2And steam, steam and unreacted C2H6Discharging from gas outlet of HCl absorption tower, condensing to obtain liquid phase water and gas phase C2H6The recovery is continuously returned to the chlorination and dehydrogenation zone for reaction. CuCl obtained again after HCl absorption of salt solution2Discharging the-CuCl-KCl salt solution through a liquid phase discharge port of the HCl absorption tower, circulating to the step 1) and continuing to react with C2H4And (4) reacting.
Example 3
(1) The molar ratio of CuCl2: CuCl: KCl is 1.5: 0.8:1 of CuCl2A melting point of the-CuCl-KCl mixed salt solution is 250 ℃, and the solution enters from a liquid phase feed inlet of the chlorination tower and is introduced into a gas inlet of the chlorination tower and contains C2H4HCl and C2H6Ethane chlorination dehydrogenation of (i) BiCl3And C2H6The mixed gas obtained by the reaction is in reverse contact, and C is controlled2H4And CuCl2In a molar ratio of 1: 7, C in mixed gas at 250 ℃2H4And CuCl2Reacting to make all C2H4Is chlorinated to obtain 1, 2-dichloroethane vapor, HCl and C2H6Discharging the mixed gas together from the gas outlet of the chlorination tower, wherein 1, 2-dichloroethane is condensed to obtain liquid phase 1, 2-dichloroethane, the detection results are shown in Table 1, and the residual unreacted HCl and C2H6And (6) recovering.
(2) Discharging the salt solution obtained after chlorination in the step 1) from a liquid-phase discharge port of a chlorination tower, feeding the salt solution into an oxidation tower from a liquid-phase feed port of the oxidation tower, introducing oxygen from a gas inlet of the oxidation tower, reversely contacting with the salt solution, and controlling the molar ratio of CuCl to the introduced oxygen to be 2.6: oxidizing part of CuCl into copper oxychloride at the oxidation temperature of 300 ℃.
(3) Discharging the oxygen-containing copper chloride salt solution obtained after oxidation in the step 2) from a liquid phase discharge port of the oxidation tower, feeding the oxygen-containing copper chloride salt solution into an HCl absorption tower through a liquid phase feed port of the HCl absorption tower, and reversely introducing HCl and C from a gas inlet of the HCl absorption tower2H6And (3) contacting the mixed gas, and controlling the molar ratio of copper oxychloride to HCl to be 1: 2, the reaction temperature is 190 ℃, so that copper oxychloride and HCl react to obtain CuCl2And steam, steam and unreacted C2H6Discharging from gas outlet of HCl absorption tower, condensing to obtain liquid phase water and gas phase C2H6The recovery is continuously returned to the chlorination and dehydrogenation zone for reaction. CuCl obtained again after HCl absorption of salt solution2Discharging the-CuCl-KCl salt solution through a liquid phase discharge port of the HCl absorption tower, circulating to the step 1) and continuing to react with C2H4And (4) reacting.
Example 4
(1) The molar ratio of CuCl2: CuCl: KCl 0.5: 1.25:1 of CuCl2A melting point of the-CuCl-KCl mixed salt solution is 200 ℃, and the solution enters from a liquid phase feed inlet of the chlorination tower and is introduced into a gas inlet of the chlorination tower and contains C2H4The reverse contact of the refinery dry gas and the control C2H4And CuCl2In a molar ratio of 1: c in refinery dry gas at 200 ℃2H4And CuCl2Reacting to make all C2H4The 1, 2-dichloroethane vapor obtained by chlorination and the 1, 2-dichloroethane vapor and the residual unreacted gas are discharged from a gas outlet of the chlorination tower, wherein the 1, 2-dichloroethane is condensed to obtain the liquid phase 1, 2-dichloroethane, the detection results are shown in Table 1, and the residual unreacted dry gas is recovered.
(2) Discharging the salt solution obtained after chlorination in the step 1) from a liquid-phase discharge port of a chlorination tower, feeding the salt solution into an oxidation tower from a liquid-phase feed port of the oxidation tower, introducing oxygen from a gas inlet of the oxidation tower, reversely contacting with the salt solution, and controlling the molar ratio of CuCl to the introduced oxygen to be 3: 1, oxidizing part of CuCl into copper oxychloride at the oxidation temperature of 250 ℃.
(3) Discharging the oxygen-containing copper chloride salt solution obtained after oxidation in the step 2) from a liquid-phase discharge port of an oxidation tower, feeding the oxygen-containing copper chloride salt solution into an HCl absorption tower through a liquid-phase feed port of the HCl absorption tower, reversely contacting with a mixed gas obtained by chlorination of HCl-containing methane introduced from a gas inlet of the HCl absorption tower, and controlling the molar ratio of copper chloride oxide to HCl to be 1: 2, the reaction temperature is 180 ℃, so that copper oxychloride and HCl react to obtain CuCl2And discharging mixed gas obtained by chlorination of the water vapor and the unreacted methane from a gas outlet of the HCl absorption tower, condensing to obtain liquid-phase water, and recovering the gas-phase mixed gas. CuCl obtained again after HCl absorption of salt solution2Discharging the-CuCl-KCl salt solution through a liquid phase discharge port of the HCl absorption tower, circulating to the step 1) and continuing to react with C2H4And (4) reacting.
TABLE 1 detection results of 1, 2-dichloroethane prepared by ethylene chlorination
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 (5)
1. A method for preparing 1, 2-dichloroethane, comprising: step 1), introducing an ethylene chlorinating agent from a liquid-phase feed inlet of a chlorination tower, and introducing the ethylene chlorinating agent into a gas inlet of the chlorination tower, wherein the gas inlet of the chlorination tower contains C2H4Is counter-currently contacted with a gas containing C2H4With an ethylene chlorinating agent, C2H4Is chlorinated to obtain 1, 2-dichloroethane, CuCl in ethylene chlorinating agent2Is reduced into CuCl to obtain gas containing 1, 2-dichloroethane and mixed salt solution containing CuCl, the gas containing 1, 2-dichloroethane is discharged from a gas outlet of a chlorination tower, and the salt solution containing CuCl is discharged from a liquid phase discharge port of the chlorination tower; the ethylene chlorinating agent comprises CuCl2And KCl, CuCl2: the molar ratio of KCl is 2.5-0.5: 1, and the ethylene chlorinating agent is a mixed salt solution; step 2), enabling the salt solution containing CuCl discharged from the liquid phase discharge port of the chlorination tower to enter the oxidation tower from the liquid phase feed port of the oxidation tower, introducing oxygen from the gas inlet of the oxidation tower, reversely contacting the salt solution containing CuCl, completely or partially oxidizing the CuCl into copper oxychloride to obtain the salt solution containing copper oxychloride, and discharging the salt solution containing copper oxychloride from the liquid phase discharge port of the oxidation tower; in the step 3), the salt solution containing copper chloride and discharged from the liquid phase discharge port of the oxidation tower enters the HCl absorption tower through the liquid phase feed port of the HCl absorption tower, reversely contacts with the gas containing HCl and introduced from the gas inlet of the HCl absorption tower, and the copper chloride oxide reacts with the HCl to obtain CuCl2And water vapor to obtain the ethylene chlorinating agent and gas containing the water vapor, wherein the gas containing the water vapor is discharged from a gas outlet of the HCl absorption tower, and the ethylene chlorinating agent is discharged from a liquid-phase discharge hole of the HCl absorption tower.
2. The method according to claim 1, wherein step 1) further comprises one or more of the following technical features:
1)C2H4with CuCl2In a molar ratio of 1: 2.1-10;
2) the reaction temperature is 200-300 ℃;
3) containing C2H4The gas of (A) is a low boiling point metal chloride and C2H6The mixed gas obtained by the mixing reaction is BiCl which is the low boiling point metal chloride3Or SnCl2；
4) The obtained gas containing 1, 2-dichloroethane is condensed, rectified and separated to obtain refined 1, 2-dichloroethane.
3. The method of claim 1, further comprising at least one of the following technical features:
1) the ethylene chlorinating agent further comprises CuCl, CuCl: the molar ratio of KCl is less than or equal to 1.25;
2) the melting point of the ethylene chlorinating agent is 200-300 ℃.
4. The method according to claim 1, wherein step 2) further comprises one or more of the following technical features:
1) the molar ratio of CuCl to oxygen is 2-3: 1;
2) the reaction temperature is 250-400 ℃.
5. The method according to claim 1, wherein step 3) further comprises one or more of the following technical features:
1) the molar ratio of copper oxychloride to HCl is 1: 2 to 2.1;
2) the reaction temperature is 180-230 ℃;
3) recycling the ethylene chlorinating agent obtained in the step 3) to the step 1) to react with C2H4The gas of (2) reacts.
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| US3879480A (en) * | 1967-12-07 | 1975-04-22 | Lummus Co | Vinyl chloride process |
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| US2915565A (en) * | 1953-09-25 | 1959-12-01 | Knapsack Ag | Process of preparing vinylidene halide |
| GB1099878A (en) * | 1965-02-23 | 1968-01-17 | Du Pont | Chlorination process |
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