CN107999139B - Preparation method of mercury-free catalyst for improving purity of vinyl chloride crude product - Google Patents
Preparation method of mercury-free catalyst for improving purity of vinyl chloride crude product Download PDFInfo
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- CN107999139B CN107999139B CN201711207785.XA CN201711207785A CN107999139B CN 107999139 B CN107999139 B CN 107999139B CN 201711207785 A CN201711207785 A CN 201711207785A CN 107999139 B CN107999139 B CN 107999139B
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 239000012043 crude product Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 23
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims abstract description 15
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims abstract description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 238000001179 sorption measurement Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001444 polymaleic acid Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- 238000002309 gasification Methods 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 5
- 238000004587 chromatography analysis Methods 0.000 abstract description 3
- 239000005997 Calcium carbide Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a mercury-free catalyst for improving the purity of a chloroethylene crude product. The mercury-free catalyst is used for chloroethylene synthesis reaction, and the obtained crude product has the purity of chloroethylene up to 98.0v%, the yield of chloroethylene up to 98.3% and the selectivity of chloroethylene up to 99.3% by chromatographic analysis; the mercury-free catalyst is used for chloroethylene synthesis reaction, and the activation time of hydrogen chloride is 20 minutes. The catalyst comprises, by mass, 3.0% of titanium tetrachloride, 1.4% of copper sulfate, 1.5% of silicotungstic acid, 2.0% of 1-ethyl-3-methylimidazole chloride, 1.6% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the balance of a carrier.
Description
Technical Field
The invention relates to a preparation method of a mercury-free catalyst for improving the purity of a chloroethylene crude product, belonging to the technical field of catalysts.
Background
At present, three industrial production methods for synthesizing chloroethylene mainly comprise a calcium carbide method, a petroleum ethylene method and a dichloroethane cracking method, wherein the calcium carbide acetylene method is used for producing chloroethylene.
The catalyst for producing chloroethylene by the calcium carbide method mainly comprises a mercury-containing catalyst and a mercury-free catalyst, and because the mercury resource in China is deficient, and the mercury catalyst is easy to sublimate and run off to cause environmental pollution, the mercury-containing catalyst restricts the development of synthesizing chloroethylene by the calcium carbide method, and the development of a novel environment-friendly mercury-free catalyst is a pressing problem for synthesizing chloroethylene by the calcium carbide method.
Chinese patents CN200910196849X, CN200810044560A, CN2010102726128A, etc. all use precious metals as active ingredients, which are expensive, difficult to recover, and difficult to industrialize.
The prior art adopts acetylene and hydrogen chloride as raw materials for synthesizing chloroethylene by a calcium carbide method, and has the following defects:
(1) the purity of the synthesized chloroethylene crude product is low;
(2) the activation time of hydrogen chloride is long.
Disclosure of Invention
The invention provides a preparation method of a mercury-free catalyst for improving the purity of a chloroethylene crude product, aiming at solving the defects in the prior art and realizing the following purposes:
(1) improving the purity of the chloroethylene crude product;
(2) the activation time of the hydrogen chloride is shortened;
(3) noble metals are not used as catalyst raw materials, so that the cost is saved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a mercury-free catalyst for improving the purity of a chloroethylene crude product is characterized by comprising the following steps: the preparation method comprises the steps of selection of a carrier, treatment of the carrier, adsorption of titanium tetrachloride, vacuum adsorption and adsorption of silicotungstic acid.
The following is a further improvement of the above technical solution:
the carrier is selected from coconut shell activated carbon, wherein the activated carbon has an iodine value of 1250mg/g, a methylene blue value of 115mg/g, a carbon tetrachloride adsorption value of 130%, water content of 1.8%, ash content of 1.2%, bulk density of 370 g/L and specific surface area of 1400m2(iv)/g, average pore diameter is 2.5-2.8nm, and average particle diameter of the carrier is 40 μm.
And (2) treating the carrier, namely soaking the activated carbon in an acid solution, wherein the acid comprises ethylene diamine tetraacetic acid, polymaleic acid and hydroxyethylidene diphosphonic acid in a mass ratio of 2:4:1, the mass content of the acid solution is 5%, the mass ratio of the acid solution to the activated carbon is 4:1, soaking is carried out for 2 hours, during soaking, the ultrasonic power density is controlled to be 120W/L, the ultrasonic frequency is 65KHz, and after soaking is finished, washing with water and drying until the water content is below 1.5%.
The method comprises the steps of placing an activated carbon carrier in a chemical vapor deposition device, heating to 180 ℃, purging for 2 hours under the protection of 120ml/min of nitrogen, removing moisture, heating titanium tetrachloride to 170 ℃, mixing gasified titanium tetrachloride with nitrogen, introducing into the chemical vapor deposition device, enabling the flow rate of titanium tetrachloride vapor to be 1.2ml/min and the flow rate of nitrogen to be 68ml/min, raising the temperature of the chemical vapor deposition device to 300 ℃ at the speed of 5 ℃/min, keeping for 30 minutes, raising the temperature to 450 ℃ at the speed of 3 ℃/min, keeping for 1 hour, cooling the chemical vapor deposition device to 200 ℃, purging for 2 hours with 100 ml/min of nitrogen, and cooling to room temperature to obtain the carrier adsorbing titanium tetrachloride.
The vacuum adsorption is to dissolve copper sulfate, 1-ethyl-3-methylimidazole chloride and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 200 times of desalted water by weight to prepare adsorption liquid a; putting a carrier for adsorbing titanium tetrachloride into the prepared adsorption solution a, wherein the mass ratio of the carrier to the adsorption solution a is 1:5, and performing vacuum adsorption, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.065 MPa and keeping for 10 s; then reducing the pressure to-0.045 MPa, keeping the pressure for 20s, reducing the pressure to-0.030 MPa, keeping the pressure for 10s, recovering to the normal pressure, and soaking and adsorbing for 1h at the normal pressure.
By adopting the technical scheme, the invention has the beneficial effects that:
(1) the mercury-free catalyst is used for vinyl chloride synthesis reaction, and the obtained crude product has the purity of vinyl chloride up to 98.0v%, the yield of vinyl chloride up to 98.3% and the selectivity of vinyl chloride up to 99.3% by chromatographic analysis.
(2) The mercury-free catalyst is used for chloroethylene synthesis reaction, and the activation time of hydrogen chloride is 20 minutes.
(3) The catalyst comprises, by mass, 3.0% of titanium tetrachloride, 1.4% of copper sulfate, 1.5% of silicotungstic acid, 2.0% of 1-ethyl-3-methylimidazole chloride, 1.6% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the balance of a carrier.
The invention does not use noble metal as the raw material of the catalyst, thereby saving the cost.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
EXAMPLE 1 preparation of Mercury-free catalyst for improving purity of crude chloroethylene
The method comprises the following steps:
(1) selection of vectors
The coconut shell activated carbon is used as a carrier, the iodine value of the activated carbon is 1250mg/g, the methylene blue value is 115mg/g, the carbon tetrachloride adsorption value is 130%, the moisture content is 1.8%, the ash content is 1.2%, the bulk density is 370 g/L, and the specific surface area is 1400m2(iv)/g, average pore diameter is 2.5-2.8nm, and average particle diameter of the carrier is 40 μm.
(2) Treatment of the support
Soaking activated carbon in an acid solution, wherein the acid comprises ethylene diamine tetraacetic acid, polymaleic acid and hydroxyethylidene diphosphonic acid in a mass ratio of 2:4:1, the mass content of the acid solution is 5%, the mass ratio of the acid solution to the activated carbon is 4:1, soaking is carried out for 2 hours, during soaking, the ultrasonic power density is controlled to be 120W/L, the ultrasonic frequency is 65KHz, and after soaking, washing and drying are carried out until the water content is below 1.5%.
(3) Selection of catalyst feedstock
The catalyst comprises the following raw material components in parts by weight: 3.0 parts of titanium tetrachloride, 1.5 parts of copper sulfate, 1.6 parts of silicotungstic acid, 2.2 parts of 1-ethyl-3-methylimidazole chloride, 1.7 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride and 90 parts of a carrier.
Weighing the raw materials of the catalyst according to the formula.
(4) Adsorption of titanium tetrachloride
Placing the activated carbon carrier in a chemical vapor deposition device, heating to 180 ℃, purging for 2 hours under the protection of 120ml/min of nitrogen, removing moisture, heating titanium tetrachloride to 170 ℃, mixing the gasified titanium tetrachloride with the nitrogen, introducing the mixture into the chemical vapor deposition device, enabling the flow rate of titanium tetrachloride vapor to be 1.2ml/min and the flow rate of nitrogen to be 68ml/min, raising the temperature of the chemical vapor deposition device to 300 ℃ at the speed of 5 ℃/min, keeping the temperature for 30 minutes, then raising the temperature to 450 ℃ at the speed of 3 ℃/min, keeping the temperature for 1 hour, then cooling the chemical vapor deposition device to 200 ℃, purging for 2 hours with 100 ml/min of nitrogen, and reducing the temperature to room temperature to obtain the carrier adsorbing titanium tetrachloride.
(5) Vacuum adsorption
Dissolving copper sulfate, 1-ethyl-3-methylimidazole chloride and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in 200 times of desalted water by weight to prepare an adsorption solution a;
putting a carrier for adsorbing titanium tetrachloride into the prepared adsorption solution a, wherein the mass ratio of the carrier for adsorbing titanium tetrachloride to the adsorption solution a is 1:5, putting the carrier into a stainless steel vacuum tank, and vacuumizing by using a vacuum pump to perform vacuum adsorption, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.065 MPa and keeping for 10 s; then reducing the pressure to-0.045 MPa, keeping the pressure for 20s, reducing the pressure to-0.030 MPa, keeping the pressure for 10s, recovering to the normal pressure, and soaking and adsorbing for 1h at the normal pressure.
(6) Adsorption silicotungstic acid
And (3) dropwise adding a silicotungstic acid aqueous solution into the mixed solution after adsorption in the step (5), wherein the dropwise adding temperature is 45 ℃, the dropwise adding speed is 0.5ml/min, ultrasonic-assisted adsorption is carried out on the solution while dropwise adding, the ultrasonic power density is 90W/L, the ultrasonic frequency is 75KHz, compressed air is introduced simultaneously, the air pressure of the air flow is preferably 0.9MPa, the flow rate of the air flow is 25L/h, and after dropwise adding, filtering and drying are carried out until the water content is 0.2% to obtain the catalyst.
The content of silicotungstic acid in the aqueous solution of silicotungstic acid is 10 percent.
The catalyst comprises, by mass, 3.0% of titanium tetrachloride, 1.4% of copper sulfate, 1.5% of silicotungstic acid, 2.0% of 1-ethyl-3-methylimidazole chloride, 1.6% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the balance of a carrier.
Example 2 use of the above catalyst in vinyl chloride Synthesis reactions
In the reaction of preparing chloroethylene by hydrochlorinating acetylene, the molar ratio of the reaction raw material gas is C2H2HCl =1/1.03, acetylene space velocity is 70h-1The reaction temperature is 110 ℃, and the reaction pressure is 0.030 MPa;
the hydrogen chloride activation time was 20 minutes.
The mercury-free catalyst in embodiment 1 of the invention is used for chloroethylene synthesis reaction, and the obtained crude product has the purity of chloroethylene up to 98.0v%, the yield of chloroethylene up to 98.3% and the selectivity of chloroethylene up to 99.3% by chromatographic analysis;
after the crude product of the vinyl chloride is rectified, the purity of the obtained vinyl chloride reaches 99.999v%, and the acetylene content is less than 0.0001 v%.
The catalyst prepared by the invention has low unit consumption, and the unit consumption of the catalyst is 0.0015-0.0017 g/ml of chloroethylene.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (2)
1. A preparation method of a mercury-free catalyst for improving the purity of a chloroethylene crude product is characterized by comprising the following steps: the preparation method comprises the steps of selecting a carrier, treating the carrier, adsorbing titanium tetrachloride, performing vacuum adsorption, and adsorbing silicotungstic acid;
the carrier is selected by taking coconut shell activated carbon as the carrier, wherein the iodine value of the activated carbon is 1250mg/g, the methylene blue value is 115mg/g, the carbon tetrachloride adsorption value is 130%, the moisture content is 1.8%, the ash content is 1.2%, and the activated carbon is stackedThe density is 370 g/L, and the specific surface area is 1400m2Per g, the average pore diameter is 2.5-2.8nm, and the average particle diameter of the carrier is 40 mu m;
treating the carrier, namely soaking activated carbon in an acid solution, wherein the acid comprises ethylene diamine tetraacetic acid, polymaleic acid and hydroxyethylidene diphosphonic acid in a mass ratio of 2:4:1, the mass content of the acid solution is 5%, the mass ratio of the acid solution to the activated carbon is 4:1, soaking is carried out for 2 hours, during soaking, the ultrasonic power density is controlled to be 120W/L, the ultrasonic frequency is 65KHz, and after soaking is finished, washing with water and drying until the water content is below 1.5%;
the vacuum adsorption is to dissolve copper sulfate, 1-ethyl-3-methylimidazole chloride and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 200 times of desalted water by weight to prepare adsorption liquid a; putting a carrier for adsorbing titanium tetrachloride into the prepared adsorption solution a, wherein the mass ratio of the carrier to the adsorption solution a is 1:5, and performing vacuum adsorption, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.065 MPa and keeping for 10 s; then regulating the pressure to-0.045 MPa, keeping the pressure for 20s, regulating the pressure to-0.030 MPa, keeping the pressure for 10s, recovering to the normal pressure, and soaking and adsorbing for 1h at the normal pressure;
the adsorption of the silicotungstic acid is to drop aqueous solution of the silicotungstic acid into the mixed solution after the completion of vacuum adsorption, the dropping temperature is 45 ℃, the dropping speed is 0.5m L/min, ultrasonic-assisted adsorption is carried out on the solution while dropping, the ultrasonic power density is 90W/L, the ultrasonic frequency is 75KHz, compressed air is introduced simultaneously, the air pressure of the air flow is preferably 0.9Mpa, the flow rate of the air flow is 25L/h, after the dropping is finished, filtration is carried out, and drying is carried out until the water content is 0.2%, so as to obtain the mercury-free catalyst;
the content of silicotungstic acid in the aqueous solution of silicotungstic acid is 10 percent;
the mercury-free catalyst comprises, by mass, 3.0% of titanium tetrachloride, 1.4% of copper sulfate, 1.5% of silicotungstic acid, 2.0% of 1-ethyl-3-methylimidazole chloride and 1.6% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
2. The method for preparing a mercury-free catalyst for improving the purity of crude chloroethylene, as claimed in claim 1, wherein the carrier for adsorbing titanium tetrachloride is prepared by placing the activated carbon carrier in a chemical vapor deposition device, heating to 180 ℃, purging for 2 hours under the protection of 120m L/min nitrogen, removing water, heating titanium tetrachloride to 170 ℃, mixing with nitrogen after gasification, introducing into the chemical vapor deposition device, increasing the flow rate of titanium tetrachloride vapor to 1.2m L/min and the flow rate of nitrogen to 68m L/min, increasing the temperature of the chemical vapor deposition device to 300 ℃ at the speed of 5 ℃/min, keeping the temperature for 30 minutes, increasing the temperature to 450 ℃ at the speed of 3 ℃/min, keeping the temperature for 1 hour, cooling the chemical vapor deposition device to 200 ℃, purging for 2 hours with 100 m L/min nitrogen, and reducing the temperature to room temperature.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737594A (en) * | 1982-07-06 | 1988-04-12 | Produits Chimiques Ugine Kuhlmann | Process for the manufacture of vinyl chloride |
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