CN108043467B - Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof - Google Patents
Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof Download PDFInfo
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- CN108043467B CN108043467B CN201711204782.0A CN201711204782A CN108043467B CN 108043467 B CN108043467 B CN 108043467B CN 201711204782 A CN201711204782 A CN 201711204782A CN 108043467 B CN108043467 B CN 108043467B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 36
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-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
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 238000001179 sorption measurement Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- PAZXSSIUSRIURW-UHFFFAOYSA-N [methoxy(methyl)phosphoryl]methanamine Chemical compound COP(C)(=O)CN PAZXSSIUSRIURW-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethylene diamine tetra methyl Chemical group 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 17
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000005997 Calcium carbide Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 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 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing 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
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a mercury-free catalyst for improving yield of chloroethylene, which comprises, by mass, 2.8% of titanium tetrachloride, 0.9% of barium chloride, 1.5% of silicomolybdic acid, 1.4% of 2-undecylimidazole, 1.9% of polyvinylpyrrolidone, 1.8% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.15% of water. The invention also provides a preparation method of the catalyst. The mercury-free catalyst is used for the synthesis reaction of chloroethylene, the yield of chloroethylene reaches 98.9%, the selectivity of chloroethylene reaches 99.6%, and the conversion rate of acetylene is 99.3%. The mercury-free catalyst is used for the synthesis reaction of chloroethylene, and reduces the molar ratio of hydrogen chloride to acetylene to 1: 1.
Description
Technical Field
The invention relates to a mercury-free catalyst for improving yield of chloroethylene and a preparation method thereof, belonging to the technical field of catalysts.
Background
Vinyl chloride is a monomer for synthesizing polyvinyl chloride plastics, and the preparation of vinyl chloride through the reaction of acetylene and hydrogen chloride is an important synthetic route of vinyl chloride monomers, which is also called as the production of vinyl chloride by a calcium carbide method.
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.
The prior art adopts acetylene and hydrogen chloride to synthesize vinyl chloride, and has the defects of low yield, low acetylene conversion rate and multiple use of noble metal as the effective component of the catalyst.
Chinese patent CN102698806A adopts cobalt oxalate, cerium chloride and the like as components of a mercury-free catalyst, the conversion rate of acetylene is 86 percent at most, the selectivity of chloroethylene is 92 percent at most, and the yield is less than 80 percent;
the mercury-free catalyst for vinyl chloride synthesis disclosed in chinese patent CN103191764A uses copper phosphotungstate as a main active component, gadolinium chloride, lanthanum nitrate and silver nitrate as auxiliary agents, the highest acetylene conversion rate is 85%, the highest selectivity is 90%, and the yield is less than 80%.
In addition, in order to improve the yield, the prior art generally adopts the method of increasing the molar ratio of the hydrogen chloride and the acetylene and further increasing the feeding amount of the hydrogen chloride, thereby causing the waste of the hydrogen chloride or increasing the recovery cost, and reducing the molar ratio of the hydrogen chloride and the acetylene causes the reduction of the yield.
Disclosure of Invention
The invention provides a mercury-free catalyst for improving the yield of chloroethylene and a preparation method thereof, aiming at solving the defects in the prior art and realizing the following purposes:
(1) the yield of the chloroethylene and the conversion rate of the acetylene are improved;
(2) reducing the molar ratio of hydrogen chloride to acetylene;
(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 mercury-free catalyst for improving yield of chloroethylene is characterized in that: the mercury-free catalyst comprises, by mass, 2.8% of titanium tetrachloride, 0.9% of barium chloride, 1.5% of silicomolybdic acid, 1.4% of 2-undecylimidazole, 1.9% of polyvinylpyrrolidone, 1.8% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.15% of water.
The following is a further improvement of the above technical solution:
the mercury-free catalyst is used for catalytically synthesizing vinyl chloride.
The preparation method of the mercury-free catalyst for improving the yield of the chloroethylene comprises the steps of treating a carrier, adsorbing titanium tetrachloride, carrying out vacuum adsorption and dropwise adding silicomolybdic acid.
Treatment of the support, including acid treatment; and (2) performing acid treatment, namely soaking the activated carbon in an acid solution, wherein the acid comprises citric acid, amino trimethyl phosphinic acid and ethylene diamine tetra methyl phosphinic acid in a mass ratio of 3:4:1, the mass content of the acid solution is 5%, and the mass ratio of the acid solution to the activated carbon is 4:1, and soaking for 2 hours.
During the soaking period, the ultrasonic power density is controlled to be 120W/L, and the ultrasonic frequency is controlled to be 65 KHz.
The carrier treatment also comprises urea treatment; and in the urea treatment, the activated carbon is placed in urea solution with the volume 5 times of that of the activated carbon and the concentration of 3.5wt%, the heating and stirring are carried out until the reflux is carried out for 3.2 hours, the filtration is carried out, the surface moisture is dried at the temperature of 60 ℃, the vacuum drying is carried out at the temperature of 85 ℃ until the constant weight is achieved, and then the calcination is carried out at the temperature of 160 ℃ until the constant weight is achieved.
The vacuum adsorption is to dissolve barium chloride, 2-undecylimidazole, polyvinylpyrrolidone and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 300 times of weight of desalted water to prepare adsorption liquid a; carrying out vacuum adsorption with the mass ratio of the carrier to the adsorption liquid a being 1:5, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.045 MPa and keeping for 20 s; then vacuumizing to-0.068 MPa, keeping for 10s, reducing the pressure to-0.037 MPa, keeping for 10s, restoring to normal pressure, and soaking and adsorbing for 1h at normal pressure.
Dropwise adding silicomolybdic acid, and dropwise adding an aqueous solution of silicomolybdic acid, wherein the dropwise adding temperature is 35 ℃, and the dropwise adding speed is 1.2 ml/min; the aqueous solution of silicomolybdic acid has a silicomolybdic acid content of 10%.
By adopting the technical scheme, the invention has the beneficial effects that:
(1) the mercury-free catalyst is used for the synthesis reaction of chloroethylene, the yield of chloroethylene reaches 98.9%, the selectivity of chloroethylene reaches 99.6%, and the conversion rate of acetylene is 99.3%.
(2) The mercury-free catalyst is used for the synthesis reaction of chloroethylene, and reduces the molar ratio of hydrogen chloride to acetylene to 1: 1.
(3) The mercury-free catalyst prepared by the invention comprises, by mass, 2.8% of titanium tetrachloride, 0.9% of barium chloride, 1.5% of silicomolybdic acid, 1.4% of 2-undecylimidazole, 1.9% of polyvinylpyrrolidone, 1.8% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.15% of water; the balance being carriers.
The catalyst does not contain noble metal, so that the production cost is saved.
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 vinyl chloride yield enhancement
The method comprises the following steps:
(1) selection of vectors
Active carbon is taken as a carrier, the iodine value of the active carbon is 1400mg/g, the methylene blue value is 127mg/g, the carbon tetrachloride adsorption value is 135 percent, the water content is 1.5 percent, the ash content is 0.7 percent, the bulk density is 400g/L, and the specific surface area is 1450m2(iv)/g, the average pore diameter is 3.0-3.2nm, and the average particle diameter of the carrier is 40 μm.
(2) Treatment of the support
A. Acid treatment
Soaking activated carbon in an acid solution, wherein the acid comprises citric acid, amino trimethyl phosphinic acid and ethylene diamine tetra methyl phosphinic acid, the mass ratio of the citric acid to the amino trimethyl phosphinic acid to the ethylene diamine tetra methyl phosphinic acid is 3:4:1, 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, the ultrasonic power density is controlled to be 120W/L and the ultrasonic frequency is 65KHz during soaking, after soaking is finished, the activated carbon is washed by distilled water, the surface moisture is dried at 55 ℃, and then vacuum drying is carried out at 92 ℃ to constant weight;
B. urea treatment
Placing the activated carbon in urea solution with the volume 5 times of that of the activated carbon and the concentration of 3.5wt%, heating and stirring until refluxing is carried out for 3.2 hours, carrying out suction filtration, drying surface moisture at 60 ℃, carrying out vacuum drying at 85 ℃ until the weight is constant, and then placing the activated carbon in a muffle furnace to calcine at 160 ℃ (the decomposition temperature of urea) until the weight is constant, thus obtaining the pretreated activated carbon carrier for later use.
(3) Selection of catalyst feedstock
The catalyst comprises the following raw material components in parts by weight: 2.8 parts of titanium tetrachloride, 1.0 part of barium chloride, 1.5 parts of silicomolybdic acid, 1.5 parts of 2-undecylimidazole, 2.0 parts of polyvinylpyrrolidone, 1.8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 89.4 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 barium chloride, 2-undecylimidazole, polyvinylpyrrolidone and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in 300 times of weight of desalted water to prepare an adsorption liquid 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 for vacuum adsorption, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.045 MPa and keeping for 20 s; then vacuumizing to-0.068 MPa, keeping for 10s, reducing the pressure to-0.037 MPa, keeping for 10s, restoring to normal pressure, and soaking and adsorbing for 1h at normal pressure.
(6) Dropwise adding silicomolybdic acid
And (3) dropwise adding the aqueous solution of silicomolybdic acid into the mixed solution after adsorption in the step (5), wherein the dropwise adding temperature is 35 ℃, the dropwise adding speed is 1.2ml/min, ultrasonic-assisted adsorption is carried out on the solution while dropwise adding, the ultrasonic power density is 95W/L, the ultrasonic frequency is 70KHz, compressed air is introduced simultaneously, the air pressure of the air flow is preferably 1.1MPa, the flow rate of the air flow is 30L/h, and after dropwise adding, filtering and drying are carried out until the water content is 0.15% to obtain the catalyst.
The silicomolybdic acid content of the aqueous solution of silicomolybdic acid is 10%.
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 =1/1.0, acetylene space velocity 65h-1The reaction temperature is 102 ℃, and the reaction pressure is 0.030 MPa;
the hydrogen chloride activation time was 30 minutes.
The mercury-free catalyst of embodiment 1 of the present invention is used for vinyl chloride synthesis reaction, and the obtained crude product has, by chromatographic analysis, a purity of vinyl chloride of 97.0v%, a yield of vinyl chloride of 98.9%, a selectivity of vinyl chloride of 99.6%, and a conversion rate of acetylene of 99.3%.
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 0.0012-0.0013g/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 mercury-free catalyst for improving yield of chloroethylene is characterized in that: the mercury-free catalyst comprises, by mass, 2.8% of titanium tetrachloride, 0.9% of barium chloride, 1.5% of silicomolybdic acid, 1.4% of 2-undecylimidazole, 1.9% of polyvinylpyrrolidone, 1.8% of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.15% of water;
the mercury-free catalyst is used for catalytically synthesizing chloroethylene;
the preparation method of the mercury-free catalyst comprises the steps of treating a carrier, adsorbing titanium tetrachloride, carrying out vacuum adsorption, and dropwise adding silicomolybdic acid;
treatment of the support, including acid treatment; the acid treatment comprises the steps of dipping the activated carbon in an acid solution, wherein the acid comprises citric acid, amino trimethyl phosphinic acid and ethylene diamine tetra methyl phosphinic acid, the mass ratio of the acid solution is 3:4:1, the mass content of the acid solution is 5%, the mass ratio of the acid solution to the activated carbon is 4:1, and the dipping is carried out for 2 hours;
during the soaking period, the ultrasonic power density is controlled to be 120W/L, and the ultrasonic frequency is controlled to be 65 KHz;
the vacuum adsorption is to dissolve barium chloride, 2-undecylimidazole, polyvinylpyrrolidone and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 300 times of weight of desalted water to prepare adsorption liquid a; carrying out vacuum adsorption with the mass ratio of the carrier to the adsorption liquid a being 1:5, wherein the parameters of the vacuum adsorption are as follows: vacuumizing to-0.045 MPa and keeping for 20 s; then vacuumizing to-0.068 MPa, keeping for 10s, regulating the pressure to-0.037 MPa, keeping for 10s, recovering to normal pressure, and soaking and adsorbing for 1h at normal pressure;
dropwise adding silicomolybdic acid, and dropwise adding an aqueous solution of silicomolybdic acid, wherein the dropwise adding temperature is 35 ℃, and the dropwise adding speed is 1.2 ml/min; the aqueous solution of silicomolybdic acid has a silicomolybdic acid content of 10%.
2. The method for preparing mercury-free catalyst for increasing yield of vinyl chloride according to claim 1, wherein: the carrier treatment also comprises urea treatment; and in the urea treatment, the activated carbon is placed in urea solution with the volume 5 times of that of the activated carbon and the concentration of 3.5wt%, the heating and stirring are carried out until the reflux is carried out for 3.2 hours, the filtration is carried out, the surface moisture is dried at the temperature of 60 ℃, the vacuum drying is carried out at the temperature of 85 ℃ until the constant weight is achieved, and then the calcination is carried out at the temperature of 160 ℃ until the constant weight is achieved.
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