CN117776860A - Method and device for co-producing trichloroethylene and tetrachloroethylene - Google Patents
Method and device for co-producing trichloroethylene and tetrachloroethylene Download PDFInfo
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- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229950011008 tetrachloroethylene Drugs 0.000 title claims abstract description 91
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 title claims abstract description 90
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000010791 quenching Methods 0.000 claims abstract description 148
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims abstract description 140
- 230000000171 quenching effect Effects 0.000 claims abstract description 136
- 238000005406 washing Methods 0.000 claims abstract description 102
- 239000012043 crude product Substances 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000010517 secondary reaction Methods 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 31
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 29
- 238000011084 recovery Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims description 141
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 106
- 239000007789 gas Substances 0.000 claims description 99
- 239000012071 phase Substances 0.000 claims description 52
- 230000003197 catalytic effect Effects 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 25
- 239000000460 chlorine Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 16
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000006200 vaporizer Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 11
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004471 Glycine Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 22
- 239000006227 byproduct Substances 0.000 abstract description 16
- 239000002699 waste material Substances 0.000 abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 238000004523 catalytic cracking Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method and a device for co-producing trichloroethylene and tetrachloroethylene, and relates to the field of production of trichloroethylene and tetrachloroethylene. The method for co-producing trichloroethylene and tetrachloroethylene of the invention comprises the following steps: pretreatment, secondary reaction, quenching rectification and washing recovery. The method and the device for co-producing the trichloroethylene and the tetrachloroethylene can effectively avoid the problems of high yield of the dangerous waste catalyst, difficult post-treatment and high environmental hazard in the catalytic cracking reaction; meanwhile, the problems that the byproduct hydrogen chloride in the production process is low in purity and high in organic carbon content, and byproduct acid cannot be effectively recycled are solved; and further improving the conversion rate of tetrachloroethane, the yields of trichloroethylene and tetrachloroethylene, and the purity of trichloroethylene and tetrachloroethylene in the crude product.
Description
Technical Field
The invention relates to the field of production of trichloroethylene and tetrachloroethane, in particular to a method and a device for co-producing trichloroethylene and tetrachloroethylene.
Background
Trichloroethylene of the formula C 2 HCl 3 The compound is a colorless transparent liquid, is insoluble in water, is soluble in ethanol and diethyl ether, and is miscible in most organic solvents. Trichloroethylene is mainly used as solvent and can also be used in the production processes of degreasing, freezing, pesticides, spices, rubber industry, fabric washing and the like.
Tetrachloroethylene, also known as perchloroethylene, of formula C 2 Cl 4 The compound is a colorless liquid, is insoluble in water, and is miscible in most organic solvents such as ethanol, diethyl ether, chloroform and the like. Tetrachloroethylene is mainly used as an organic solvent, a dry cleaning agent, and can also be used in adhesive solvents, metal degreasing solvents, drying agents, paint removers, insect repellents, fat extractants and organic synthesis.
At present, the existing process for co-producing trichloroethylene and tetrachloroethylene has large production amount of dangerous waste catalysts, particularly active carbon catalysts (adsorbed with active components such as barium chloride and calcium chloride) adopted in catalytic cracking reaction can produce about 240 tons/a of dangerous waste catalysts under the capacity condition of 6 tens of thousands of tons/a of trichloroethylene and tetrachloroethylene, and the dangerous waste catalysts have large post-treatment difficulty and high environmental hazard.
Meanwhile, under the existing process for co-producing trichloroethylene and tetrachloroethylene and the production capacity condition of 6 ten thousand tons/a of trichloroethylene and tetrachloroethylene, 6 ten thousand tons/a of byproduct waste acid can be produced, the purity of the byproduct hydrogen chloride obtained by the existing catalytic reaction method is low, the organic carbon content is high, the byproduct hydrogen chloride can only be used as waste acid for dangerous waste treatment, and the waste acid cannot be effectively recycled, so that the environment hazard is high.
Furthermore, the existing process for co-producing trichloroethylene and tetrachloroethylene also has the problems of low tetrachloroethane conversion rate, low trichloroethylene and tetrachloroethylene yield and low trichloroethylene and tetrachloroethylene purity in the crude product.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method and a device for co-producing trichloroethylene and tetrachloroethylene, which can effectively avoid the problems of high yield of dangerous waste catalyst, difficult post-treatment and high environmental hazard in the catalytic cracking reaction; meanwhile, the problems that the byproduct hydrogen chloride in the production process is low in purity and high in organic carbon content, and byproduct acid cannot be effectively recycled are solved; and further improving the conversion rate of tetrachloroethane, the yields of trichloroethylene and tetrachloroethylene, and the purity of trichloroethylene and tetrachloroethylene in the crude product.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for co-producing trichloroethylene and tetrachloroethylene comprises the following steps: pretreatment, secondary reaction, quenching rectification, washing and recovery;
the pretreatment method comprises the steps of preheating and vaporizing tetrachloroethane, and then separating gas from liquid to obtain gas-phase tetrachloroethane; feeding the gas-phase tetrachloroethane and the preheated chlorine gas into a primary tubular reactor;
the second-stage reaction method comprises the steps that after the gas-phase tetrachloroethane and chlorine carry out first-stage reaction in a first-stage tubular reactor, the gas-phase tetrachloroethane and the chlorine enter a second-stage catalytic reactor filled with a catalyst to carry out second-stage catalytic reaction, and a gas-phase crude product is obtained and fed into a quenching tower;
the quenching and rectifying method is that the gas phase crude product is fed into a quenching tower, cooled and quenched in the quenching tower, and then is rectified by self heat, and the crude product containing trichloroethylene and tetrachloroethylene is extracted from a side line; condensing light components at the top of the quenching tower, refluxing the condensate to the quenching tower, condensing non-condensable gas again, collecting the condensate to obtain a crude product containing trichloroethylene and tetrachloroethylene, removing foam from tail gas, and feeding the tail gas to a primary scrubber;
The method for washing and recycling is that tetrachloroethane is used as a washing liquid, the tail gas is subjected to primary washing and secondary deep cooling washing, and high-purity hydrogen chloride is recycled.
Preferably, in the pretreatment, tetrachloroethane is preheated to 100-150 ℃, then gas-liquid separation is carried out, liquid phase is gasified at 250-280 ℃, and then gas-liquid separation is carried out again, and gas-phase tetrachloroethane is fed into a primary tubular reactor; chlorine is preheated to 90-200 ℃ and then is fed into the primary tubular reactor.
Preferably, in the pretreatment, the feeding rate of the gas-phase tetrachloroethane to the primary tubular reactor is 1200-5000kg/h;
the feed rate of chlorine to the primary tubular reactor was 0-500kg/h.
Preferably, in the secondary reaction, the temperature of the primary reaction is 400-600 ℃;
the temperature of the secondary catalytic reaction is 200-450 ℃;
the filling quantity of the catalyst in the secondary catalytic reactor is 70-80% of the internal volume of the secondary catalytic reactor.
The catalyst used in the secondary catalytic reaction consists of the following steps: pretreatment and compounding;
the pretreatment method comprises the steps of putting hydroxyapatite into N, N-dimethylformamide with the weight being 8-10 times that of the hydroxyapatite, uniformly dispersing the hydroxyapatite by ultrasonic waves, stirring and heating the mixture to 40-45 ℃, and preserving heat; dropwise adding the pretreatment liquid at a dropwise adding rate of 1.5-2mL/min under the stirring condition; after the pretreatment liquid is dripped, continuing to keep the temperature and stir for 2-3 hours, separating out solid matters, washing the solid matters by absolute ethyl alcohol and deionized water, and drying the solid matters to constant weight at 85-90 ℃ to obtain a pretreated matter;
The pretreatment liquid is N, N-dimethylformamide dispersed with glycine, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine.
Preferably, in the pretreatment liquid, the weight ratio of glycine to N, N' -dicyclohexylcarbodiimide to 4-dimethylaminopyridine to N, N-dimethylformamide is 10-12:1.5-2:0.08-0.1:18-20;
the weight ratio of the hydroxyapatite to the pretreatment liquid is 1:3.3-3.5.
The compounding method comprises the steps of adding pretreated matters, terephthalic acid, polyvinylpyrrolidone and triethylamine into N, N-dimethylformamide, uniformly dispersing, heating to 55-60 ℃, keeping the temperature, stirring for 20-30min, continuously adding compound liquid, uniformly mixing, transferring into a high-pressure reactor, sealing the high-pressure reactor, heating to 120-125 ℃, keeping the temperature, reacting for 2-2.5h, naturally cooling to room temperature, and separating out solid matters; washing the solid with N, N-dimethylformamide and deionized water, drying, and granulating to obtain spheres with the diameter of 18-20mm to obtain a catalyst;
the composite liquid is N, N-dimethylformamide dispersed with nickel nitrate and zinc nitrate.
Preferably, the weight ratio of the pretreatment to terephthalic acid to polyvinylpyrrolidone to triethylamine to N, N-dimethylformamide to the composite liquid is 6.2-6.5:3-3.3:14-16:0.4-0.5:330-350:28-30;
In the composite liquid, the content of nickel nitrate is 18.5-20wt% and the content of zinc nitrate is 14-16wt%.
Preferably, in the quenching rectification, the gas-phase crude product obtained by the reaction is fed from a 20 th tray of a quenching tower;
the temperature distribution in the quench tower is: the temperature of the top of the tower is less than 150 ℃, the temperature in the tower is less than 190 ℃, and the temperature of the bottom of the tower is less than 220 ℃.
In the washing recovery, tetrachloroethane is used as a washing liquid, the temperature of the washing liquid is controlled to be not higher than 30 ℃, and the tail gas is subjected to primary washing in a countercurrent washing mode; tetrachloroethane is used as a washing liquid, the temperature of the washing liquid is controlled to be not higher than-10 ℃, and the tail gas is subjected to secondary cryogenic washing in a countercurrent washing mode, and then gas recovery is carried out to obtain high-purity hydrogen chloride.
Preferably, in the washing recovery, in the primary washing, the spraying amount of the washing liquid is 1-5t/h;
in the secondary cryogenic washing, the spraying amount of the washing liquid is 2-6t/h.
A device for co-producing trichloroethylene and tetrachloroethylene for realizing the method comprises: the device comprises a pretreatment unit, a secondary reaction unit, a quenching rectification unit and a washing recovery unit;
the quenching and rectifying unit comprises: the device comprises a quenching tower, a quenching condenser, a reflux tank, a quenching tail gas condenser, a side-draw condenser and a crude product tank;
The bottom feed inlet of the quenching tower is communicated with a discharge outlet pipeline of a secondary catalytic reactor in the secondary reaction unit, a tower top gas outlet of the quenching tower is communicated with a quenching condenser pipeline, a condensate outlet of the quenching condenser is communicated with a feed inlet pipeline of a reflux tank, and a discharge outlet of the reflux tank is communicated with a reflux inlet pipeline at the tower top of the quenching tower;
the middle part of the quenching tower is provided with a side-draw outlet which is communicated with a side-draw condenser feed inlet pipeline, and a side-draw condenser discharge outlet is communicated with a crude product tank feed inlet;
the non-condensable gas outlet of the quenching condenser is communicated with the gas inlet pipeline of the quenching tail gas condenser, the liquid outlet of the quenching tail gas condenser is communicated with the crude product tank feed inlet pipeline, and the gas outlet of the quenching tail gas condenser is communicated with the gas inlet pipeline at the bottom of the primary scrubber in the washing recovery unit.
Further, the washing recovery unit includes: a primary scrubber, a secondary cryogenic scrubber, a cryogenic cooler, and a washing circulation pump;
an air inlet at the bottom of the primary scrubber receives tail gas from a quenching tail gas condenser in the quenching rectification unit; the top liquid inlet of the primary scrubber is respectively communicated with a tetrachloroethane conveying pipeline and a discharge port pipeline of a washing circulating pump, the top gas outlet of the primary scrubber is communicated with a gas inlet pipeline at the bottom of the secondary cryogenic scrubber, the upper liquid inlet of the secondary cryogenic scrubber is communicated with a liquid outlet pipeline of the cryogenic cooler, and the liquid inlet of the cryogenic cooler is communicated with the discharge port pipeline of the washing circulating pump.
Further, the preprocessing unit comprises: the device comprises a preheater, a gas-liquid separator, a circulating pump and a vaporizer;
the feed inlet of the preheater is communicated with a tetrachloroethane conveying pipeline, and the discharge outlet of the preheater is communicated with a liquid phase feed inlet pipeline of the gas-liquid separator; the bottom discharge port of the gas-liquid separator is communicated with the feed port pipeline of the circulating pump; the discharge port of the circulating pump is communicated with the feed port pipeline of the vaporizer; the top discharge port of the gas-liquid separator is communicated with the bottom feed port of the primary tubular reactor of the secondary reaction unit;
the secondary reaction unit comprises: a primary tubular reactor and a secondary catalytic reactor;
the first feed inlet of the primary tubular reactor is communicated with the top discharge outlet pipeline of the gas-liquid separator of the pretreatment unit, the second feed inlet of the primary tubular reactor is communicated with the chlorine conveying pipeline, the discharge outlet of the primary tubular reactor is communicated with the feed inlet of the secondary catalytic reactor, and the discharge outlet of the secondary catalytic reactor is communicated with the bottom feed inlet pipeline of the quenching tower of the quenching rectification unit.
Compared with the prior art, the invention has the beneficial effects that:
1) The method and the device for co-producing the trichloroethylene and the tetrachloroethylene can effectively avoid the problems of high yield of the dangerous waste catalyst, difficult post-treatment and high environmental hazard in the catalytic cracking reaction; the catalyst adopted in the secondary catalytic reaction process has long service life, the whole production period does not need to be replaced, and no hazardous waste catalyst is generated; after 7500 hours of stable production by adopting the method and the device for co-producing the trichloroethylene and the tetrachloroethylene, the conversion rate of the tetrachloroethane after the secondary reaction and the purity of the trichloroethylene and the tetrachloroethylene in the gas-phase crude product have no obvious change. Meanwhile, the method can overcome the defects of low purity of byproduct hydrogen chloride and high organic carbon content in the production process, and can effectively recycle high-purity hydrogen chloride to realize recycling of byproduct hydrogen chloride; and further improving the conversion rate of tetrachloroethane, the yields of trichloroethylene and tetrachloroethylene, and the purity of trichloroethylene and tetrachloroethylene in the crude product.
2) The method and the device for co-producing trichloroethylene and tetrachloroethylene have the advantages that the tetrachloroethane conversion rate is over 96.2 percent after secondary reaction; the purity of the crude product obtained by rectification in the quenching tower 107 is more than 98.3 percent; the total yield of trichloroethylene and tetrachloroethylene obtained by the reaction is more than 97.3 percent.
3) The method for co-producing trichloroethylene and tetrachloroethylene has the advantages of high purity of more than 98.8 percent, high purity, low organic carbon content (lower than 400 ppm) in the hydrogen chloride, capability of being directly matched with raw materials of downstream products, no byproduct hydrochloric acid generation and no environmental risk.
Drawings
FIG. 1 is a schematic diagram of an apparatus for co-producing trichloroethylene and tetrachloroethylene according to the present invention.
In the figure: 101-a preheater; 102-a gas-liquid separator; 103-a circulation pump; 104-a vaporizer; 105-primary tubular reactor; 106-a secondary catalytic reactor; 107-a quench tower; 108-side offtake condenser; 109-a reflux drum; 110-quench condenser; 111-quench tail gas condenser; 112-a demister; 113-primary scrubber; 114-a secondary cryogenic scrubber; 115-a cryocooler; 116-a washing circulation pump; 117-crude tank.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The embodiment provides a method for co-producing trichloroethylene and tetrachloroethylene, which specifically comprises the following steps:
1. pretreatment of
Tetrachloroethane is preheated to 120 ℃ by a preheater 101 and then is fed into a gas-liquid separator 102 for gas-liquid separation; the liquid phase of the gas-liquid separator 102 is led into a vaporizer 104 (the heat medium is heat conduction oil) through a circulating pump 103, heated to 270 ℃, and then fed into the gas-liquid separator 102 again for gas-liquid separation; the gas phase in the gas-liquid separator 102 is fed to the primary tubular reactor 105 through a feed pipe; meanwhile, after the chlorine gas is preheated to 180 ℃ by a heater, it is fed into the primary tubular reactor 105.
Wherein the feed rate of the gaseous tetrachloroethane to the primary tubular reactor 105 was 9500kg/h.
The feed rate of chlorine gas to the primary tubular reactor 105 was 10kg/h.
2. Secondary reaction
Feeding gas-phase tetrachloroethane and chlorine into a primary tubular reactor 105, controlling the temperature of the primary tubular reactor 105 to be 510 ℃, performing primary reaction, then entering into a secondary catalytic reactor 106 filled with a catalyst, controlling the temperature of the secondary catalytic reactor 106 to be 400 ℃, performing secondary reaction, and then entering a gas-phase crude product obtained by the reaction into a quenching tower 107 for subsequent treatment.
Wherein, the tetrachloroethane conversion rate after the secondary reaction is 96.5%.
The catalyst in the secondary catalytic reactor 106 is prepared by the following method:
1) Pretreatment of
Adding hydroxyapatite into N, N-dimethylformamide with the weight being 8 times that of the hydroxyapatite, stirring and heating to 40 ℃ after uniform ultrasonic dispersion, and preserving heat; dropwise adding the pretreatment liquid at a dropwise adding rate of 1.5mL/min under the stirring condition; after the pretreatment liquid is added dropwise, continuing to keep the temperature and stir for 2 hours, separating out solid matters, washing the solid matters by absolute ethyl alcohol and deionized water, and drying the solid matters to constant weight at 85 ℃ to obtain the pretreatment matters.
Wherein the pretreatment liquid is N, N-dimethylformamide solution in which glycine, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine are dispersed. In the pretreatment liquid, the weight ratio of glycine to N, N' -dicyclohexylcarbodiimide to 4-dimethylaminopyridine to N, N-dimethylformamide is 10:1.5:0.08:18.
The weight ratio of the hydroxyapatite to the pretreatment liquid is 1:3.3.
2) Composite material
Adding the pretreated substance, terephthalic acid, polyvinylpyrrolidone and triethylamine into N, N-dimethylformamide, after ultrasonic dispersion, heating to 55 ℃, keeping the temperature and stirring for 20min, continuously adding the composite liquid, after uniform mixing, transferring into a high-pressure reactor, sealing the high-pressure reactor, heating to 120 ℃, keeping the temperature and reacting for 2h, naturally cooling to room temperature, and separating out solid substances; washing the solid with N, N-dimethylformamide and deionized water, drying and granulating to obtain spheres with the diameter of 18mm, and preparing the catalyst.
Wherein the weight ratio of the pretreatment to terephthalic acid to polyvinylpyrrolidone to triethylamine to N, N-dimethylformamide to the composite liquid is 6.2:3:14:0.4:330:28.
The composite liquid is N, N-dimethylformamide dispersed with nickel nitrate and zinc nitrate; in the composite liquid, the content of nickel nitrate is 18.5wt% and the content of zinc nitrate is 14wt%.
The catalyst loading was 75% of the internal volume of the secondary catalytic reactor 106.
The total purity of trichloroethylene and tetrachloroethylene in the gas phase crude product obtained by the reaction is more than 98 weight percent.
3. Quenching and rectifying
Feeding the gas-phase crude product from a 20 th column plate of a quenching tower 107 (plate type rectifying tower), cooling and quenching in the quenching tower 107, and utilizing self heat to realize rectifying treatment; the temperature distribution in quench tower 107 is specifically: the temperature of the top of the tower is 130 ℃, the temperature of the middle of the tower is 180 ℃, and the temperature of the bottom of the tower is 215 ℃; in the rectification treatment process, after the tower top light component is condensed at 120 ℃ in a quenching condenser 110, condensate flows back into a quenching tower 107 through a reflux tank 109, and mass and heat transfer are carried out on the condensate and a gas phase crude product in the quenching tower 107, so that the rectification is carried out after the cooling and quenching of the gas phase crude product; the crude product is extracted from the side line of the quenching tower 107 and is led into a crude product tank 117 after being condensed (the total purity of the trichloroethylene and the tetrachloroethylene in the crude product is 98.5 weight percent, and the weight ratio of the trichloroethylene to the tetrachloroethylene is 5:1); the high boiling point substances (including tetrachloroethane, pentachloroethane, hexachloroethane, hexachloroprene, pentachloromethane, etc.) in the quenching tower 107 are reduced to the tower kettle of the quenching tower 107, the tower kettle materials of the quenching tower 107 are periodically led out and recycled to the primary tubular reactor 105, and the secondary reaction step is carried out again to be converted into trichloroethylene and tetrachloroethylene, thereby further improving the total yield of the trichloroethylene and the tetrachloroethylene to 97.5 percent.
4. Washing recovery
In the quenching and rectifying process, after the top light component of the quenching tower 107 is condensed by a quenching condenser 110, noncondensable gas (mainly hydrogen chloride with purity of more than 90 percent and a small amount of chlorine, trichloroethylene and tetrachloroethylene) is condensed again in a quenching tail gas condenser 111 at 35 ℃, liquid phase is returned and collected to a crude product tank 117, gas phase (tail gas) is defoamed by a defoamer 112, enters a primary scrubber 113 from the bottom, tetrachloroethane is adopted as a washing liquid, the temperature of the washing liquid is controlled to be 20 ℃, the spraying amount is 2.5t/h, the tail gas is subjected to primary washing in a countercurrent washing mode, then enters a secondary cryogenic scrubber 114 from the bottom, tetrachloroethane is adopted as the washing liquid, the temperature of the washing liquid is controlled to be-15 ℃, the spraying amount is 4t/h, and after the tail gas is subjected to secondary cryogenic washing in a countercurrent washing mode, the gas is recovered to obtain high-purity hydrogen chloride (the purity is 99wt%, the organic carbon content is lower than 400ppm, and the chlorine content is lower than 0.02 wt%); meanwhile, the washing liquid in the primary washing and the secondary cryogenic washing can be used as raw materials to be recycled to the pretreatment step, so that the materials can be effectively recycled, and no waste gas or waste liquid is generated in the production process.
The embodiment provides a device for co-producing trichloroethylene and tetrachloroethylene for realizing the method, which specifically comprises the following components: the device comprises a pretreatment unit, a secondary reaction unit, a quenching rectification unit and a washing recovery unit.
The pretreatment unit comprises a preheater 101, a gas-liquid separator 102, a circulating pump 103 and a vaporizer 104.
Wherein, the feed inlet of the preheater 101 is communicated with a tetrachloroethane conveying pipeline, and the discharge outlet of the preheater 101 is communicated with a liquid phase feed inlet pipeline of the gas-liquid separator 102; so that after the tetrachloroethane is preheated, it is fed to the gas-liquid separator 102 for gas-liquid separation.
The bottom discharge port of the gas-liquid separator 102 is communicated with the feed port of the circulating pump 103 through a pipeline; the discharge port of the circulating pump 103 is communicated with the feed port of the vaporizer 104 through a pipeline; the discharge port of the vaporizer 104 is communicated with a reflux port pipeline of the gas-liquid separator 102, and the top discharge port of the gas-liquid separator 102 is communicated with the bottom feed port of the primary tubular reactor 105 of the secondary reaction unit; so that the tetrachloroethane liquid after the gas-liquid separation is vaporized and returned to the gas-liquid separator 102 for the gas-liquid separation again, and the tetrachloroethane gas is fed to the first-stage tubular reactor 105.
The secondary reaction unit comprises a primary tubular reactor 105 and a secondary catalytic reactor 106.
Wherein, the first feed inlet of the primary tubular reactor 105 is communicated with the top feed outlet pipeline of the gas-liquid separator 102 of the pretreatment unit, the second feed inlet of the primary tubular reactor 105 is communicated with the chlorine gas conveying pipeline, the feed inlet of the primary tubular reactor 105 is communicated with the feed inlet of the secondary catalytic reactor 106, and the feed outlet of the secondary catalytic reactor 106 is communicated with the bottom feed inlet pipeline of the quench tower 107 of the quench rectification unit; so that the gas-phase tetrachloroethane and the chlorine are fed into the primary tubular reactor 105, are fed into the secondary catalytic reactor 106 after the primary reaction, and enter the quenching tower 107 for subsequent quenching and rectifying treatment after the secondary reaction.
The quenching and rectifying unit comprises a quenching tower 107, a quenching condenser 110, a reflux tank 109, a quenching tail gas condenser 111, a foam remover 112, a side-draw condenser 108 and a crude product tank 117.
The bottom feed inlet of the quenching tower 107 is communicated with the discharge outlet pipeline of the secondary catalytic reactor 106 in the secondary reaction unit, the top gas outlet of the quenching tower 107 is communicated with the pipeline of the quenching condenser 110, the condensate outlet of the quenching condenser 110 is communicated with the feed inlet pipeline of the reflux drum 109, and the discharge outlet of the reflux drum 109 is communicated with the pipeline of the reflux port of the top of the quenching tower 107, so that after the light components at the top of the quenching tower 107 are condensed, the condensate flows back into the quenching tower 107, and the condensate carries out mass and heat transfer with the gas-phase crude product in the quenching tower 107, thereby realizing the rectification after the cooling and quenching of the gas-phase crude product; the middle part of the quenching tower 107 is provided with a side extraction outlet which is communicated with a feed inlet pipeline of a side extraction condenser 108, and a discharge outlet of the side extraction condenser 108 is communicated with a feed inlet of a crude product tank 117 so as to obtain trichloroethylene and tetrachloroethylene products by condensing the side extraction product of the quenching tower 107 and then introducing the condensed product into the crude product tank 117; the non-condensable gas outlet of the quenching condenser 110 is communicated with the gas inlet pipeline of the quenching tail gas condenser 111, the liquid outlet of the quenching tail gas condenser 111 is communicated with the feed inlet pipeline of the crude product tank 117, the gas outlet of the quenching tail gas condenser 111 is communicated with the gas inlet pipeline of the foam remover 112, the gas outlet of the foam remover 112 is communicated with the gas inlet pipeline at the bottom of the primary scrubber 113 in the washing and recycling unit, so that after the non-condensable gas of the quenching condenser 110 is condensed again, condensate is collected to the crude product tank 117, and the non-condensable gas (tail gas) is subjected to subsequent washing and recycling treatment.
The washing recovery unit comprises a primary washer 113, a secondary cryogenic washer 114, a cryogenic cooler 115 and a washing circulating pump 116.
The bottom air inlet of the primary scrubber 113 is communicated with an air outlet pipeline of a foam remover 112 in the quenching and rectifying unit, the top liquid inlet of the primary scrubber 113 is respectively communicated with a tetrachloroethane conveying pipeline and a discharge port pipeline of a washing circulating pump 116, the top air outlet of the primary scrubber 113 is communicated with an air inlet pipeline at the bottom of a secondary cryogenic scrubber 114, the upper liquid inlet of the secondary cryogenic scrubber 114 is communicated with a liquid outlet pipeline of a cryogenic cooler 115, and the liquid inlet of the cryogenic cooler 115 is communicated with a discharge port pipeline of the washing circulating pump 116; so that after the tetrachloroethane with the temperature lower than 30 ℃ is used for countercurrent washing of the noncondensable gas (tail gas), the tetrachloroethane with the temperature lower than-10 ℃ is used for countercurrent washing of the noncondensable gas (tail gas), and the circulation of the tetrachloroethane in the washer and the secondary cryogenic washer 114 is realized.
The method and the device for co-producing trichloroethylene and tetrachloroethylene can effectively avoid the problems of high yield of dangerous waste catalyst, difficult post-treatment and high environmental hazard in the catalytic cracking reaction; the catalyst adopted in the secondary catalytic reaction process has long service life, the whole production period does not need to be replaced, and no hazardous waste catalyst is generated; after 7500 hours of stable production by adopting the method and the device for co-producing the trichloroethylene and the tetrachloroethylene, the conversion rate of the tetrachloroethane after the secondary reaction and the purity of the trichloroethylene and the tetrachloroethylene in the gas-phase crude product have no obvious change. Meanwhile, the method can overcome the defects of low purity of byproduct hydrogen chloride and high organic carbon content in the production process, and can effectively recycle high-purity hydrogen chloride to realize recycling of byproduct hydrogen chloride; and further improving the conversion rate of tetrachloroethane, the yields of trichloroethylene and tetrachloroethylene, and the purity of trichloroethylene and tetrachloroethylene in the crude product.
Example 2
The embodiment provides a method for co-producing trichloroethylene and tetrachloroethylene, which specifically comprises the following steps:
1. pretreatment of
Tetrachloroethane is preheated to 130 ℃ by a preheater 101 and then is fed into a gas-liquid separator 102 for gas-liquid separation; the liquid phase of the gas-liquid separator 102 is led into a vaporizer 104 (the heat medium is heat conduction oil) through a circulating pump 103, heated to 260 ℃, and then fed into the gas-liquid separator 102 again for gas-liquid separation; the gas phase in the gas-liquid separator 102 is fed to the primary tubular reactor 105 through a feed pipe; meanwhile, after the chlorine gas was preheated to 150 ℃ by a superheater, it was fed into the primary tubular reactor 105.
Wherein the feed rate of the gaseous tetrachloroethane to the primary tubular reactor 105 was 10500kg/h.
The feed rate of chlorine gas to the primary tubular reactor 105 was 12kg/h.
2. Secondary reaction
The gas-phase tetrachloroethane and chlorine are fed into a primary tubular reactor 105, the temperature of the primary tubular reactor 105 is controlled to be 480 ℃, the primary tubular reactor 105 is subjected to primary reaction, then the gas-phase tetrachloroethane and the chlorine enter a secondary catalytic reactor 106 filled with a catalyst, the temperature of the secondary catalytic reactor 106 is controlled to be 380 ℃, after the secondary reaction, a gas-phase crude product obtained by the reaction enters a quenching tower 107 for subsequent treatment.
Wherein, the tetrachloroethane conversion rate after the secondary reaction is 96.2 percent.
The catalyst in the secondary catalytic reactor 106 is prepared by the following method:
1) Pretreatment of
Adding hydroxyapatite into N, N-dimethylformamide with the weight being 9 times that of the hydroxyapatite, stirring and heating to 43 ℃ after uniform ultrasonic dispersion, and preserving heat; dropwise adding the pretreatment liquid at a dropwise adding rate of 1.8mL/min under the stirring condition; after the pretreatment liquid is added dropwise, continuing to keep the temperature and stir for 2.5 hours, separating out solid matters, washing the solid matters by absolute ethyl alcohol and deionized water, and drying the solid matters to constant weight at 88 ℃ to obtain the pretreatment matters.
Wherein the pretreatment liquid is N, N-dimethylformamide solution in which glycine, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine are dispersed. In the pretreatment liquid, the weight ratio of glycine to N, N' -dicyclohexylcarbodiimide to 4-dimethylaminopyridine to N, N-dimethylformamide is 11:1.7:0.09:19.
The weight ratio of the hydroxyapatite to the pretreatment liquid is 1:3.4.
2) Composite material
Adding the pretreated substance, terephthalic acid, polyvinylpyrrolidone and triethylamine into N, N-dimethylformamide, after ultrasonic dispersion is uniform, heating to 58 ℃, keeping the temperature and stirring for 25min, continuously adding the composite liquid, after uniform mixing, transferring into a high-pressure reactor, sealing the high-pressure reactor, heating to 122 ℃, keeping the temperature and reacting for 2.3h, naturally cooling to room temperature, and separating out solid substances; washing the solid with N, N-dimethylformamide and deionized water, drying and granulating to obtain spheres with the diameter of 19mm, and obtaining the catalyst.
Wherein the weight ratio of the pretreatment to terephthalic acid to polyvinylpyrrolidone to triethylamine to N, N-dimethylformamide to the composite liquid is 6.3:3.2:15.5:0.47:345:29.
The composite liquid is N, N-dimethylformamide dispersed with nickel nitrate and zinc nitrate; in the composite liquid, the content of nickel nitrate is 19.5wt% and the content of zinc nitrate is 15.5wt%.
The catalyst loading was 80% of the internal volume of the secondary catalytic reactor 106.
The total purity of trichloroethylene and tetrachloroethylene in the gas phase crude product obtained by the reaction is more than 98 weight percent.
3. Quenching and rectifying
Feeding the gas-phase crude product from a 20 th column plate of a quenching tower 107 (plate type rectifying tower), cooling and quenching in the quenching tower 107, and utilizing self heat to realize rectifying treatment; the temperature distribution in quench tower 107 is specifically: the temperature of the top of the tower is 125 ℃, the temperature of the middle of the tower is 175 ℃, and the temperature of the bottom of the tower is 210 ℃; in the rectification treatment process, after the tower top light component is condensed at 110 ℃ in a quenching condenser 110, condensate flows back into a quenching tower 107 through a reflux tank 109, and mass and heat transfer are carried out on the condensate and a gas phase crude product in the quenching tower 107, so that the rectification is carried out after the cooling and quenching of the gas phase crude product; the crude product is extracted from the side line of the quenching tower 107 and is led into a crude product tank 117 after being condensed (the total purity of the trichloroethylene and the tetrachloroethylene in the crude product is 98.3 weight percent, and the weight ratio of the trichloroethylene to the tetrachloroethylene is 5:1); the high boiling point substances (including tetrachloroethane, pentachloroethane, hexachloroethane, hexachloroprene, pentachloromethane, etc.) in the quenching tower 107 are reduced to the tower kettle of the quenching tower 107, the tower kettle materials of the quenching tower 107 are periodically led out and recycled to the primary tubular reactor 105, and the secondary reaction step is carried out again to be converted into trichloroethylene and tetrachloroethylene, thereby further improving the total yield of the trichloroethylene and the tetrachloroethylene to 97.3 percent.
4. Washing recovery
In the quenching and rectifying process, after the top light component of the quenching tower 107 is condensed by a quenching condenser 110, noncondensable gas (mainly hydrogen chloride with purity of more than 90 percent and a small amount of chlorine, trichloroethylene and tetrachloroethylene) is condensed again in a quenching tail gas condenser 111 at 37 ℃, liquid phase is returned and collected to a crude product tank 117, gas phase (tail gas) is defoamed by a defoamer 112, enters a primary scrubber 113 from the bottom, tetrachloroethane is adopted as a washing liquid, the temperature of the washing liquid is controlled to be 25 ℃, the spraying amount is 3.7t/h, the tail gas is subjected to primary washing in a countercurrent washing mode, then enters a secondary cryogenic scrubber 114 from the bottom, tetrachloroethane is adopted as the washing liquid, the temperature of the washing liquid is controlled to be-12 ℃, the spraying amount is 4.5t/h, and after the tail gas is subjected to secondary cryogenic washing in a countercurrent washing mode, the gas is recovered to obtain high-purity hydrogen chloride (the purity is 98.8wt%, the organic carbon content is lower than 400ppm, and the chlorine content is lower than 0.02 wt%); meanwhile, the washing liquid in the primary washing and the secondary cryogenic washing can be used as raw materials to be recycled to the pretreatment step, so that the materials can be effectively recycled, and no waste gas or waste liquid is generated in the production process.
The apparatus for co-producing trichloroethylene and tetrachloroethylene used in this example was the same as that used in example 1.
The method and the device for co-producing trichloroethylene and tetrachloroethylene can effectively avoid the problems of high yield of dangerous waste catalyst, difficult post-treatment and high environmental hazard in the catalytic cracking reaction; the catalyst adopted in the secondary catalytic reaction process has long service life, the whole production period does not need to be replaced, and no hazardous waste catalyst is generated; after 7500 hours of stable production by adopting the method and the device for co-producing the trichloroethylene and the tetrachloroethylene, the conversion rate of the tetrachloroethane after the secondary reaction and the purity of the trichloroethylene and the tetrachloroethylene in the gas-phase crude product have no obvious change. Meanwhile, the method can overcome the defects of low purity of byproduct hydrogen chloride and high organic carbon content in the production process, and can effectively recycle high-purity hydrogen chloride to realize recycling of byproduct hydrogen chloride; and further improving the conversion rate of tetrachloroethane, the yields of trichloroethylene and tetrachloroethylene, and the purity of trichloroethylene and tetrachloroethylene in the crude product.
Example 3
The embodiment provides a method for co-producing trichloroethylene and tetrachloroethylene, which specifically comprises the following steps:
1. pretreatment of
Tetrachloroethane is preheated to 100 ℃ by a preheater 101 and then is fed into a gas-liquid separator 102 for gas-liquid separation; the liquid phase of the gas-liquid separator 102 is led into a vaporizer 104 (the heat medium is heat conduction oil) through a circulating pump 103, heated to 250 ℃, and then fed into the gas-liquid separator 102 again for gas-liquid separation; the gas phase in the gas-liquid separator 102 is fed to the primary tubular reactor 105 through a feed pipe; meanwhile, after the chlorine gas was preheated to 100 ℃ by a superheater, it was fed into the primary tubular reactor 105.
Wherein the feed rate of the gaseous tetrachloroethane to the primary tubular reactor 105 was 9500kg/h.
The feed rate of chlorine gas to the primary tubular reactor 105 was 10kg/h.
2. Secondary reaction
The gas-phase tetrachloroethane and chlorine are fed into a primary tubular reactor 105, the temperature of the primary tubular reactor 105 is controlled to be 400 ℃, the primary tubular reactor 105 is subjected to primary reaction, then the gas-phase tetrachloroethane and the chlorine enter a secondary catalytic reactor 106 filled with a catalyst, the temperature of the secondary catalytic reactor 106 is controlled to be 210 ℃, and after the secondary reaction, a gas-phase crude product obtained by the reaction enters a quenching tower 107 for subsequent treatment.
Wherein, the tetrachloroethane conversion rate after the secondary reaction is 97.6 percent.
The catalyst in the secondary catalytic reactor 106 is prepared by the following method:
1) Pretreatment of
Adding hydroxyapatite into N, N-dimethylformamide with the weight being 10 times that of the hydroxyapatite, stirring and heating to 45 ℃ after uniform ultrasonic dispersion, and preserving heat; dropwise adding the pretreatment liquid at a dropwise adding rate of 2mL/min under the stirring condition; after the pretreatment liquid is added dropwise, continuing to keep the temperature and stir for 3 hours, separating out solid matters, washing the solid matters by absolute ethyl alcohol and deionized water, and drying the solid matters to constant weight at 90 ℃ to obtain the pretreatment matters.
Wherein the pretreatment liquid is N, N-dimethylformamide solution in which glycine, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine are dispersed. In the pretreatment liquid, the weight ratio of glycine to N, N' -dicyclohexylcarbodiimide to 4-dimethylaminopyridine to N, N-dimethylformamide is 12:2:0.1:20.
The weight ratio of the hydroxyapatite to the pretreatment liquid is 1:3.5.
2) Composite material
Adding the pretreated substance, terephthalic acid, polyvinylpyrrolidone and triethylamine into N, N-dimethylformamide, after ultrasonic dispersion is uniform, heating to 60 ℃, keeping the temperature and stirring for 30min, continuously adding the composite liquid, after uniform mixing, transferring into a high-pressure reactor, sealing the high-pressure reactor, heating to 125 ℃, keeping the temperature and reacting for 2.5h, naturally cooling to room temperature, and separating out solid substances; washing the solid with N, N-dimethylformamide and deionized water, drying and granulating to obtain spheres with the diameter of 20mm, and preparing the catalyst.
Wherein the weight ratio of the pretreatment to terephthalic acid to polyvinylpyrrolidone to triethylamine to N, N-dimethylformamide to the composite liquid is 6.5:3.3:16:0.5:350:30.
The composite liquid is N, N-dimethylformamide dispersed with nickel nitrate and zinc nitrate; in the composite liquid, the content of nickel nitrate is 20wt% and the content of zinc nitrate is 16wt%.
The catalyst loading was 70% of the internal volume of the secondary catalytic reactor 106.
The total purity of trichloroethylene and tetrachloroethylene in the gas phase crude product obtained by the reaction is more than 98 weight percent.
3. Quenching and rectifying
Feeding the gas-phase crude product from a 20 th column plate of a quenching tower 107 (plate type rectifying tower), cooling and quenching in the quenching tower 107, and utilizing self heat to realize rectifying treatment; the temperature distribution in quench tower 107 is specifically: the temperature of the top of the tower is 120 ℃, the temperature of the middle of the tower is 170 ℃, and the temperature of the bottom of the tower is 205 ℃; in the rectification treatment process, after the tower top light component is condensed at 110 ℃ in a quenching condenser 110, condensate flows back into a quenching tower 107 through a reflux tank 109, and mass and heat transfer are carried out on the condensate and a gas phase crude product in the quenching tower 107, so that the rectification is carried out after the cooling and quenching of the gas phase crude product; the crude product is extracted from the side line of the quenching tower 107 and is led into a crude product tank 117 after being condensed (the total purity of the trichloroethylene and the tetrachloroethylene in the crude product is 98.9 weight percent, and the weight ratio of the trichloroethylene to the tetrachloroethylene is 5:1); the high boiling point substances (including tetrachloroethane, pentachloroethane, hexachloroethane, hexachloroprene, pentachloromethane, etc.) in the quenching tower 107 are reduced to the tower kettle of the quenching tower 107, the tower kettle materials of the quenching tower 107 are periodically led out and recycled to the primary tubular reactor 105, and the secondary reaction step is carried out again to be converted into trichloroethylene and tetrachloroethylene, thereby further improving the total yield of the trichloroethylene and the tetrachloroethylene to 98.2 percent.
4. Washing recovery
In the quenching and rectifying process, after the top light component of the quenching tower 107 is condensed by a quenching condenser 110, noncondensable gas (mainly hydrogen chloride with purity of more than 90 percent and a small amount of chlorine, trichloroethylene and tetrachloroethylene) is condensed again in a quenching tail gas condenser 111 at 35 ℃, liquid phase is returned and collected to a crude product tank 117, gas phase (tail gas) is defoamed by a defoamer 112, enters a primary scrubber 113 from the bottom, tetrachloroethane is adopted as a washing liquid, the temperature of the washing liquid is controlled to be 25 ℃, the spraying amount is 3t/h, the tail gas is subjected to primary washing in a countercurrent washing mode, then enters a secondary cryogenic scrubber 114 from the bottom, the temperature of the washing liquid is controlled to be-15 ℃, the spraying amount is 3.5t/h, and after the tail gas is subjected to secondary cryogenic washing in a countercurrent washing mode, the gas is recovered to obtain high-purity hydrogen chloride (the purity is 99.3wt%, the organic carbon content is lower than 400ppm, and the chlorine content is lower than 0.02 wt%); meanwhile, the washing liquid in the primary washing and the secondary cryogenic washing can be used as raw materials to be recycled to the pretreatment step, so that the materials can be effectively recycled, and no waste gas or waste liquid is generated in the production process.
The apparatus for co-producing trichloroethylene and tetrachloroethylene used in this example was the same as that used in example 1.
The method and the device for co-producing trichloroethylene and tetrachloroethylene can effectively avoid the problems of high yield of dangerous waste catalyst, difficult post-treatment and high environmental hazard in the catalytic cracking reaction; the catalyst adopted in the secondary catalytic reaction process has long service life, no replacement is needed in the whole production period, no hazardous waste catalyst is generated, the temperature required by the secondary catalytic reaction can be effectively reduced, and the reaction effect of 380-400 ℃ in the original process can be realized under the temperature condition of 210 ℃; after 12000 hours of stable production by adopting the method and the device for co-producing the trichloroethylene and the tetrachloroethylene, the conversion rate of the tetrachloroethylene after the secondary reaction and the purity of the trichloroethylene and the tetrachloroethylene in the gas-phase crude product have no obvious change. Meanwhile, the method can overcome the defects of low purity of byproduct hydrogen chloride and high organic carbon content in the production process, and can effectively recycle high-purity hydrogen chloride to realize recycling of byproduct hydrogen chloride; and further improving the conversion rate of tetrachloroethane, the yields of trichloroethylene and tetrachloroethylene, and the purity of trichloroethylene and tetrachloroethylene in the crude product.
Comparative example 1
The technical scheme of the embodiment 1 is adopted, and the difference is that: the feed rate of the gaseous tetrachloroethane to the primary tubular reactor 105 was 8700kg/h, and the feed rate of the chlorine to the primary tubular reactor 105 was 100kg/h; in the secondary reaction process, the temperature of the primary tubular reactor 105 is controlled to be 530 ℃, the temperature of the secondary catalytic reactor 106 is controlled to be 410 ℃, after the secondary reaction is carried out, the secondary reaction is rectified by the quenching tower 107, the non-condensable gas is directly condensed by the quenching condenser 110 for re-condensation, and the tail gas is collected by the demister 112; the washing recovery process is omitted.
The detection shows that the content of hydrogen chloride in the tail gas is 95wt%, the content of trichloroethylene and tetrachloroethylene is 4wt%, and the content of chlorine is 1wt%. Meanwhile, in comparative example 1, the yields of trichloroethylene and tetrachloroethylene obtained were 93.1%.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: in the preparation of the catalyst used in the secondary catalytic reactor 106, the pretreatment step is omitted, and the use of zinc nitrate in the composite liquid in the composite step is omitted; and controlling the temperature of the secondary reactor to be 460 ℃; quenching and rectifying the gas-phase crude product after the secondary reaction by adopting a quenching tower 107, wherein the temperature of the top of the quenching tower 107 is 170 ℃, and the tetrachloroethane content in the gas-phase crude product extracted from the side line is 10wt% and the total content of trichloroethylene and tetrachloroethylene is 80wt%.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for co-producing trichloroethylene and tetrachloroethylene is characterized by comprising the following steps: pretreatment, secondary reaction, quenching rectification, washing and recovery;
the pretreatment method comprises the steps of preheating and vaporizing tetrachloroethane, and then separating gas from liquid to obtain gas-phase tetrachloroethane; feeding the gas-phase tetrachloroethane and the preheated chlorine gas into a primary tubular reactor (105);
the second-stage reaction method comprises the steps that after the gas-phase tetrachloroethane and chlorine carry out first-stage reaction in a first-stage tubular reactor (105), the gas-phase tetrachloroethane and the chlorine enter a second-stage catalytic reactor (106) filled with a catalyst to carry out second-stage catalytic reaction, and a gas-phase crude product is obtained and is fed into a quenching tower (107);
The catalyst adopted in the secondary catalytic reaction is prepared by the following steps: pretreatment and compounding;
the pretreatment method comprises the steps of adding hydroxyapatite into N, N-dimethylformamide, uniformly dispersing, heating to 40-45 ℃, and preserving heat; stirring and dripping the pretreatment liquid; after the pretreatment liquid is dripped, continuing to keep the temperature and stir, separating out solid matters, washing the solid matters by absolute ethyl alcohol and deionized water, and drying to obtain a pretreatment matter;
the pretreatment liquid is N, N-dimethylformamide dispersed with glycine, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine;
the method comprises the steps of adding pretreated matters, terephthalic acid, polyvinylpyrrolidone and triethylamine into N, N-dimethylformamide, uniformly dispersing, heating to 55-60 ℃, keeping the temperature, stirring, continuously adding composite liquid, uniformly mixing, transferring into a high-pressure reactor, sealing the high-pressure reactor, heating to 120-125 ℃, keeping the temperature, reacting, naturally cooling to room temperature, and separating out solid matters; washing the solid by using N, N-dimethylformamide and deionized water, drying and granulating to obtain a catalyst;
the composite liquid is N, N-dimethylformamide dispersed with nickel nitrate and zinc nitrate;
The quenching and rectifying method is that the gas phase crude product is fed into a quenching tower (107), cooled and quenched in the quenching tower (107), and then rectified by self heat, and a crude product containing trichloroethylene and tetrachloroethylene is extracted from a side line; condensing light components at the top of the quenching tower (107), refluxing condensate to the quenching tower (107), condensing noncondensable gas again, collecting condensate to obtain a crude product containing trichloroethylene and tetrachloroethylene, removing foam from tail gas, and feeding the tail gas to a primary scrubber (113);
the method for washing and recycling is that tetrachloroethane is used as a washing liquid, the tail gas is subjected to primary washing and secondary deep cooling washing, and high-purity hydrogen chloride is recycled.
2. The method for co-producing trichloroethylene and tetrachloroethylene according to claim 1, wherein in the pretreatment, tetrachloroethane is preheated to 100-150 ℃ and then subjected to gas-liquid separation, the liquid phase is vaporized at 250-280 ℃ and then subjected to gas-liquid separation again, and the gas-phase tetrachloroethane is fed into the primary tubular reactor (105) at a feeding rate of 1200-5000 kg/h; chlorine is preheated to 90-200 ℃ and then fed into the primary tubular reactor (105) at a feed rate of 0-500 kg/h.
3. The method for co-producing trichloroethylene and tetrachloroethylene according to claim 1, wherein the temperature of the primary reaction is 400-600 ℃;
the temperature of the secondary catalytic reaction is 200-450 ℃;
the filling quantity of the catalyst in the secondary catalytic reactor (106) is 70-80% of the internal volume of the secondary catalytic reactor (106).
4. The method for co-producing trichloroethylene and tetrachloroethylene according to claim 1, wherein in said quenching and rectifying, the crude gas phase obtained by the reaction is fed from the 20 th tray of the quenching tower (107);
the temperature distribution in the quenching tower (107) is as follows: the temperature of the top of the tower is less than 150 ℃, the temperature in the tower is less than 190 ℃, and the temperature of the bottom of the tower is less than 220 ℃.
5. The method for co-producing trichloroethylene and tetrachloroethylene according to claim 1, wherein in the washing and recycling, tetrachloroethane is used as a washing liquid, the temperature of the washing liquid is controlled to be not higher than 30 ℃, the spraying amount is 1-5t/h, and the tail gas is subjected to primary washing in a countercurrent washing mode; tetrachloroethane is used as a washing liquid, the temperature of the washing liquid is controlled to be not higher than-10 ℃, the spraying amount is controlled to be 2-6t/h, and the tail gas is subjected to secondary cryogenic washing in a countercurrent washing mode, and then gas recovery is carried out to obtain high-purity hydrogen chloride.
6. The method for co-producing trichloroethylene and tetrachloroethylene according to claim 1, wherein in the pretreatment, the weight ratio of hydroxyapatite to N, N-dimethylformamide is 1:8-10;
the dropping speed of the pretreatment liquid is 1.5-2mL/min;
the weight ratio of the hydroxyapatite to the pretreatment liquid is 1:3.3-3.5;
in the pretreatment liquid, the weight ratio of glycine to N, N' -dicyclohexylcarbodiimide to 4-dimethylaminopyridine to N, N-dimethylformamide is 10-12:1.5-2:0.08-0.1:18-20.
7. The method for co-producing trichloroethylene and tetrachloroethylene according to claim 1, wherein the weight ratio of the pretreated matter, terephthalic acid, polyvinylpyrrolidone, triethylamine, N-dimethylformamide and the composite liquid in the composite is 6.2-6.5:3-3.3:14-16:0.4-0.5:330-350:28-30;
in the composite liquid, the content of nickel nitrate is 18.5-20wt% and the content of zinc nitrate is 14-16wt%.
8. An apparatus for co-producing trichloroethylene and tetrachloroethylene for carrying out the process of any one of claims 1 to 7, comprising: the device comprises a pretreatment unit, a secondary reaction unit, a quenching rectification unit and a washing recovery unit;
the quenching and rectifying unit comprises: a quench tower (107), a quench condenser (110), a reflux tank (109), a quench tail gas condenser (111), a side draw condenser (108) and a crude product tank (117);
The bottom feed inlet of the quenching tower (107) is communicated with a discharge outlet pipeline of a secondary catalytic reactor (106) in the secondary reaction unit, a top gas outlet of the quenching tower (107) is communicated with a quenching condenser (110) pipeline, a condensate outlet of the quenching condenser (110) is communicated with a feed inlet pipeline of a reflux tank (109), and a discharge outlet of the reflux tank (109) is communicated with a reflux inlet pipeline at the top of the quenching tower (107);
a side offtake outlet is arranged in the middle of the quenching tower (107), and is communicated with a feed inlet pipeline of a side offtake condenser (108), and a discharge outlet of the side offtake condenser (108) is communicated with a feed inlet of a crude product tank (117);
the non-condensable gas outlet of the quenching condenser (110) is communicated with the gas inlet pipeline of the quenching tail gas condenser (111), the liquid outlet of the quenching tail gas condenser (111) is communicated with the feed inlet pipeline of the crude product tank (117), and the gas outlet of the quenching tail gas condenser (111) is communicated with the gas inlet pipeline at the bottom of the primary scrubber (113) in the washing recovery unit.
9. The apparatus for co-producing trichloroethylene and tetrachloroethylene according to claim 8, wherein said washing and recovering unit comprises: a primary scrubber (113), a secondary cryogenic scrubber (114), a cryogenic cooler (115), and a scrubbing circulation pump (116);
An air inlet at the bottom of the primary scrubber (113) receives tail gas from a quenching tail gas condenser (111) in the quenching rectification unit; the top liquid inlet of the primary scrubber (113) is respectively communicated with a tetrachloroethane conveying pipeline and a discharge port pipeline of a washing circulating pump (116), the top air outlet of the primary scrubber (113) is communicated with an air inlet pipeline at the bottom of the secondary cryogenic scrubber (114), the upper liquid inlet of the secondary cryogenic scrubber (114) is communicated with a liquid outlet pipeline of a cryogenic cooler (115), and the liquid inlet of the cryogenic cooler (115) is communicated with the discharge port pipeline of the washing circulating pump (116).
10. The apparatus for co-producing trichloroethylene and tetrachloroethylene according to claim 8, wherein said pretreatment unit comprises: a preheater (101), a gas-liquid separator (102), a circulating pump (103) and a vaporizer (104);
the feed inlet of the preheater (101) is communicated with a tetrachloroethane conveying pipeline, and the discharge outlet of the preheater (101) is communicated with a liquid phase feed inlet pipeline of the gas-liquid separator (102); the bottom discharge port of the gas-liquid separator (102) is communicated with the feed port pipeline of the circulating pump (103); a discharge port of the circulating pump (103) is communicated with a feed port pipeline of the vaporizer (104); the discharge port of the vaporizer (104) is communicated with a reflux port pipeline of the gas-liquid separator (102), and the top discharge port of the gas-liquid separator (102) is communicated with the bottom feed port of a primary tubular reactor (105) of the secondary reaction unit;
The secondary reaction unit comprises: a primary tubular reactor (105) and a secondary catalytic reactor (106);
the first feed inlet of the primary tubular reactor (105) is communicated with the top discharge outlet pipeline of the gas-liquid separator (102) of the pretreatment unit, the second feed inlet of the primary tubular reactor (105) is communicated with the chlorine conveying pipeline, the discharge outlet of the primary tubular reactor (105) is communicated with the feed inlet of the secondary catalytic reactor (106), and the discharge outlet of the secondary catalytic reactor (106) is communicated with the bottom feed inlet pipeline of the quenching tower (107) of the quenching rectification unit.
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