CN104326865B - A kind of catalyzing acetylene ethylene dichloride prepares the method for vinylchlorid - Google Patents
A kind of catalyzing acetylene ethylene dichloride prepares the method for vinylchlorid Download PDFInfo
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- CN104326865B CN104326865B CN201410532153.0A CN201410532153A CN104326865B CN 104326865 B CN104326865 B CN 104326865B CN 201410532153 A CN201410532153 A CN 201410532153A CN 104326865 B CN104326865 B CN 104326865B
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- ethylene dichloride
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Abstract
The invention discloses the method that vinylchlorid is prepared in the reaction of a kind of catalyzing acetylene ethylene dichloride.The method is: the ratio of acetylene and ethylene dichloride steam 1:1 ~ 1:4 in molar ratio mixed, then pass in the fixed-bed reactor that nitrogen modified catalyst is housed and react, temperature of reaction is 180 ~ 300 DEG C, and air speed is 20 ~ 120h
-1; Described nitrogen modified catalyst take gac as carrier, loaded metal salt compound and nitrogenous compound; In catalyzer total mass, the mass percent of described metal salt compound is 0.01 ~ 10%, and the mass percent of described nitrogenous compound is 0.01 ~ 10%.Utilize method of the present invention to prepare vinylchlorid and have the advantages that conversion of alkyne is high, vinylchlorid selectivity is high; The nitrogen modified catalyst preparation technology adopted in this processing method is simple, with low cost.
Description
Technical field
The invention belongs to vinylchlorid fabricating technology field, be specifically related to a kind of method that catalyzing acetylene ethylene dichloride prepares vinylchlorid.
Background technology
Vinylchlorid is a kind of very important chemical raw material, mainly for the production of polyvinyl chloride (PVC) RESINS.Polyvinyl chloride is one of the world five large-engineering plastics, is widely used in all trades and professions.The industrial preparative method of current vinyl chloride monomer mainly contains acetylene hydrochlorination method and process for oxychlorination of ethylene.Process for oxychlorination of ethylene carries out oxi-chlorination by ethene, hydrogenchloride and oxygen or ethylene chlorination generates ethylene dichloride, ethylene dichloride thermo-cracking generates vinylchlorid, produces byproduct hydrogen chloride simultaneously.Acetylene hydrochlorination method is the method that acetylene and hydrogenchloride catalyzed reaction directly generate vinylchlorid.
China's oil shortage of resources, and coal resources relative abundance can provide sufficient acetylene raw material, so current domestic vinyl chloride monomer produces mainly acetylene hydrochlorination method.But current domestic acetylene method technique generally adopts load mercury chloride on the activated carbon as catalyzer, the volatile loss of this catalyzer, and mercury has high toxicity again, causes serious harm to environment.Elimination mercury catalyst pollutes, and makes catalyzer to low mercuration, mercuryless future development, controls and successive elimination mercury pollution, and finding clean catalysis agent and the operational path of synthesizing chloroethylene, is current chlor-alkali industry urgent need to solve the problem.
Summary of the invention
The object of the invention is, provide a kind of catalyzing acetylene and ethylene dichloride to react the processing method preparing vinylchlorid, solve the technical problem that in prior art, acetylene method technique generally adopts load mercuric chleride catalyst, environmental pollution serious.
The present invention is as follows for solving the problems of the technologies described above adopted technical scheme:
A kind of catalyzing acetylene ethylene dichloride prepares the method for vinylchlorid, the method detailed process is: the ratio of acetylene and ethylene dichloride steam 1:1 ~ 1:4 in molar ratio mixed, then pass in the fixed-bed reactor that nitrogen modified catalyst is housed and react, temperature of reaction is 180 ~ 300 DEG C, and air speed is 20 ~ 120h
-1; Described nitrogen modified catalyst take gac as carrier, loaded metal salt compound and nitrogenous compound, and in catalyzer total mass, the mass percent of described metal salt compound is 0.01 ~ 10%, and the mass percent of described nitrogenous compound is 0.01 ~ 10%.Described acetylene and the ethylene dichloride steam reaction effluent cool to room temperature in fixed-bed reactor, after condensation goes out unreacted ethylene dichloride, by freezing for residual gas compression, namely obtains Liquid vinyl chloride.
Further, the metal salt compound of described nitrogen modified catalyst load is the mixture of strontium salt or barium salt or strontium salt and barium salt, and the nitrogenous compound of load is selected from least one in Guanidinium hydrochloride, acetamidine hydrochloride salt, acrylamide, urea, methylsulfonamides, Malonamide nitrile.
The nitrogen modified catalyst of described catalyzing acetylene ethylene dichloride reaction, its preparation method comprises the steps:
Step 1, gac is carried out pickling, pickling time is 5 ~ 10 hours, described Acidwash solution is the mixing solutions of one or more in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, described acid concentration is 0.1 ~ 5.0mol/L, gac is placed in 60 ~ 120 DEG C of dryings after pickling, time of drying is 6 ~ 24 hours, and the gac after process is for subsequent use as carrier; Described gac is selected from least one in coal mass active carbon, active fruit shell carbon or cocoanut active charcoal;
Step 2, is dissolved in deionized water by metal salt compound and nitrogenous compound, is mixed with steeping fluid; In described steeping fluid, the concentration of metal salt compound is 0.01 ~ 20%, and the concentration of described nitrogenous compound is 0.01 ~ 20%; Described metal salt compound is the mixture of strontium salt or barium salt or strontium salt and barium salt, and described nitrogenous compound is selected from least one in Guanidinium hydrochloride, acetamidine hydrochloride salt, acrylamide, urea, methylsulfonamides, Malonamide nitrile;
Step 3, flooded 0.1 ~ 24 hour in the steeping fluid of aforementioned preparation by the absorbent charcoal carrier after aforementioned processing, then activate in 200 ~ 800 DEG C under nitrogen protection, soak time is 3 ~ 12 hours, obtained described nitrogen modified catalyst.
Compared with prior art, the present invention has following beneficial effect: the catalyzer adopted in processing method provided by the invention has the features such as conversion of alkyne is high, vinylchlorid selectivity is high, not easily run off, with low cost, preparation technology is simple.Compared with preparing the method for vinylchlorid with domestic existing acetylene method, the invention solves mercury pollution problem, decrease synthesis and the process for refining of hydrogenchloride.Compared with traditional ethylene process, solve the high temperature energy consumption problem of wherein ethylene dichloride thermolysis, turn avoid the complex apparatus of oxychlorination operating unit.
Embodiment
Technical scheme of the present invention is described in detail below by way of specific embodiment.Raw material used in the present invention and reagent are all commercially.
The HCl treatment of gac: active carbon from coal 2mol/L hydrochloric acid soln is soaked 8 hours afterwash, then in 110 DEG C of dryings 10 hours.Described gac also can adopt active fruit shell carbon or cocoanut active charcoal, and Acidwash solution also can adopt the mixed solution of sulfuric acid, nitric acid or phosphoric acid or several acid.
Embodiment 1
5g strontium chloride and 7.5g Malonamide nitrile are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal after 100g HCl treatment, after mixing, dipping 4h, 650 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 42h
-1, temperature of reaction controls at 260 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 80%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 2
5g strontium chloride and 7.5g Malonamide nitrile are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 100g after with HCl treatment, mix, after dipping 6h, 650 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 42h
-1, temperature of reaction controls at 240 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 60%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 3
2g strontium chloride and 5g acrylamide are dissolved in 100ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 50g after with HCl treatment, mix, after room temperature immersion 12h, 600 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.1 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 42h
-1, temperature of reaction controls at 260 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 80%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 4
5g strontium chloride and 10g acrylamide are dissolved in 250ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 150g after with HCl treatment, mix, after room temperature immersion 2h, 700 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.1 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 82h
-1, temperature of reaction controls at 260 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 55%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 5
7.5g strontium chloride and 10g urea are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 100g after with HCl treatment, mix, after room temperature immersion 2h, 650 DEG C of high temperature lead to nitrogen activation 8h, obtained nitrogen modified catalyst.Mixed by 1: 1.5 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 55h
-1, temperature of reaction controls at 240 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 60%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 6
10g strontium chloride and 10g methylsulfonamides are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 100g after with HCl treatment, mix, h after room temperature immersion 4,650 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 42h
-1, temperature of reaction controls at 260 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 70%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 7
10g strontium chloride and 10g B amidine hydrochloric acid salt are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 100g after with HCl treatment, mix rear room temperature immersion 2h, 650 DEG C of high temperature lead to nitrogen activation 6h, obtained catalyzer.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 42h
-1, temperature of reaction controls at 260 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 70%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 8
6g strontium chloride and 10g Guanidinium hydrochloride are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 100g after with HCl treatment, mix rear room temperature immersion 6h, 650 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.1 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 63h
-1, temperature of reaction controls at 250 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 60%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 9
4g strontium chloride, 2g bariumchloride and 10g acrylamide are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 120g after with HCl treatment, mix rear room temperature immersion 4h, 650 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 42h
-1, temperature of reaction controls at 200 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 18%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 10
8g strontium chloride, 2g bariumchloride and 10g acrylamide are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 120g after with HCl treatment, mix rear room temperature immersion 2h, 650 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 55h
-1, temperature of reaction controls at 240 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 55%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 11
4g strontium chloride, 2g bariumchloride and 8g Malonamide nitrile are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 120g after with HCl treatment, mix rear room temperature immersion 4h, 700 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 42h
-1, temperature of reaction controls at 220 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 30%, and the selectivity of vinylchlorid reaches more than 90%.
Embodiment 12
4g strontium chloride, 2g bariumchloride and 8g Malonamide nitrile are dissolved in 200ml deionized water, are mixed with steeping fluid.Add the active carbon from coal 120g after with HCl treatment, mix rear room temperature immersion 6h, 700 DEG C of high temperature lead to nitrogen activation 6h, obtained nitrogen modified catalyst.Mixed by 1: 1.2 with ethylene dichloride steam by acetylene, pass in the fixed-bed reactor that described obtained nitrogen modified catalyst is housed and react, reaction velocity is 55h
-1, temperature of reaction controls at 260 DEG C, and reacted gas, through cool to room temperature, is first isolated liquid unreacted ethylene dichloride, then by freezing for residual gas compression, can be obtained Liquid vinyl chloride.By acetylene, one time transformation efficiency reaches more than 65%, and the selectivity of vinylchlorid reaches more than 90%.
Above are only part preferred embodiment of the present invention, the present invention is not limited in the content of embodiment.To those skilled in the art, can have various change and change in the concept of technical solution of the present invention, any change done and change, all within scope.
Claims (3)
1. a catalyzing acetylene ethylene dichloride prepares the method for vinylchlorid, it is characterized in that, the method is: the ratio of acetylene and ethylene dichloride steam 1:1 ~ 1:4 in molar ratio mixed, then pass in the fixed-bed reactor that nitrogen modified catalyst is housed and react, temperature of reaction is 180 ~ 300 DEG C, and air speed is 20 ~ 120h-1; Described nitrogen modified catalyst take gac as carrier, loaded metal salt compound and nitrogenous compound, and in catalyzer total mass, the mass percent of described metal salt compound is 0.01 ~ 10%, and the mass percent of described nitrogenous compound is 0.01 ~ 10%.
2. catalyzing acetylene ethylene dichloride as claimed in claim 1 prepares the method for vinylchlorid, it is characterized in that: the metal salt compound of described nitrogen modified catalyst load is the mixture of strontium salt or barium salt or strontium salt and barium salt, the nitrogenous compound of load is selected from least one in Guanidinium hydrochloride, acetamidine hydrochloride salt, acrylamide, urea, methylsulfonamides, Malonamide nitrile.
3. catalyzing acetylene ethylene dichloride as claimed in claim 1 prepares the method for vinylchlorid, it is characterized in that described method also comprises: described acetylene and the ethylene dichloride steam reaction effluent cool to room temperature in fixed-bed reactor, after condensation goes out unreacted ethylene dichloride, by freezing for residual gas compression, namely obtain Liquid vinyl chloride.
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| GB201509019D0 (en) * | 2015-05-27 | 2015-07-08 | Johnson Matthey Plc | Process and catalyst |
| CN107008465B (en) * | 2017-03-31 | 2020-04-07 | 清华大学 | Copper-based catalyst with high activity and stability for hydrochlorination of acetylene |
| CN109293470B (en) * | 2018-09-27 | 2021-06-04 | 浙江工业大学 | Process method for HCFC-142b catalytic cracking and acetylene hydrochlorination coupling reaction |
| CN111454118A (en) * | 2019-01-22 | 2020-07-28 | 中国科学院上海有机化学研究所 | Method for preparing chloroethylene by reacting acetylene with dichloroethane |
| CN112844460B (en) * | 2019-11-27 | 2022-06-03 | 中国科学院大连化学物理研究所 | Catalyst for preparing chloroethylene by acetylene and dichloroethane coupling reaction and application thereof |
| EP4196264A1 (en) * | 2020-08-11 | 2023-06-21 | SCG Chemicals Public Company Limited | Catalyst for catalytic cracking of ethylenedichloride to vinyl chloride |
| CN112473744B (en) * | 2020-11-27 | 2021-11-30 | 浙江工业大学 | Front-rear stage two-section type combined catalyst and application thereof |
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