CN107999139A - A kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity - Google Patents
A kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity Download PDFInfo
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- CN107999139A CN107999139A CN201711207785.XA CN201711207785A CN107999139A CN 107999139 A CN107999139 A CN 107999139A CN 201711207785 A CN201711207785 A CN 201711207785A CN 107999139 A CN107999139 A CN 107999139A
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- Prior art keywords
- catalyst
- vinyl chloride
- carrier
- mercury
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 25
- 239000012043 crude product Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 24
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 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 12
- 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
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 11
- 238000007654 immersion Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 8
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 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
- LPSCRKGVODJZIB-UHFFFAOYSA-N [I].[C] Chemical class [I].[C] LPSCRKGVODJZIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000001177 diphosphate Substances 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 238000002309 gasification Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 7
- 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
- 238000004587 chromatography analysis Methods 0.000 abstract description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 abstract 1
- -1 dimethylamino-propyl Chemical group 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- BXGTVNLGPMZLAZ-UHFFFAOYSA-N n'-ethylmethanediimine;hydrochloride Chemical compound Cl.CCN=C=N BXGTVNLGPMZLAZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 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 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 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
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 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
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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
Landscapes
- 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 present invention provides a kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity, the preparation method, including the selection of carrier, the processing of carrier, absorption titanium tetrachloride, vacuum suction, absorption silico-tungstic acid.Catalyst without mercury of the present invention, for vinyl chloride synthesis reaction, obtained crude product, through chromatography, the purity of vinyl chloride reaches 98.0v%, and the yield of vinyl chloride is up to 98.3%, and the selectivity of vinyl chloride is up to 99.3%；Catalyst without mercury of the present invention, for vinyl chloride synthesis reaction, hydrogen chloride soak time is 20 minutes.Catalyst of the present invention, be calculated in mass percent, including titanium tetrachloride 3.0%, copper sulphate 1.4%, silico-tungstic acid 1.5%, 1 ethyl of chlorination, 3 methylimidazole 2.0%, 1 (3 dimethylamino-propyl), 3 ethyl-carbodiimide hydrochloride 1.6%, remaining be carrier.
Description
Technical field
The present invention relates to a kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity, belong to catalyst technology
Field.
Background technology
The industrial process of synthesis vinyl chloride thereof mainly has three kinds at present, and carbide, oil ethylene process and dichloroethanes are split
Solution, wherein carbide acetylene method production vinyl chloride are main production methods.
Carbide produces the catalyst of vinyl chloride, is broadly divided into containing mercury catalyst and catalyst without mercury, since China's mercury provides
Source is deficienter, and the easy sublimation of mercury catalyst causes environmental pollution, and carbide synthesis vinyl chloride thereof is constrained containing mercury catalyst
Development, develop new environmentally protective catalyst without mercury, be the pressing problem that carbide synthesis vinyl chloride thereof faces.
Chinese patent CN200910196849X, CN200810044560A, CN2010102726128A etc. are with noble metal
As active ingredient, cost is higher, and recycling is more difficult, it is difficult to industrialize.
Prior art carbide synthesis vinyl chloride thereof is to use acetylene and hydrogen chloride also to be had the following disadvantages for raw material：
（1）The purity of the vinyl chloride crude product of synthesis is low；
（2）The soak time length of hydrogen chloride.
The content of the invention
The present invention is solution the shortcomings of the prior art, there is provided a kind of catalyst without mercury for improving vinyl chloride crude product purity
Preparation method, to realize following goal of the invention：
（1）Improve the purity of vinyl chloride crude product；
（2）Shorten the soak time of hydrogen chloride；
（3）It is cost-effective without using noble metal as catalyst raw material.
To solve above technical problem, the present invention uses following technical scheme：
A kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity, it is characterised in that：The preparation method, including
The selection of carrier, the processing of carrier, absorption titanium tetrachloride, vacuum suction, absorption silico-tungstic acid.
It is that the further of above-mentioned technical proposal is improved below：
The selection of the carrier, using cocoanut active charcoal as carrier, the activated carbon iodine number 1250mg/g, methylene blue value 115mg/
G, Penetrating curve 130%, moisture content 1.8%, ash 1.2%, bulk density 370g/L, specific surface area 1400m2/ g, puts down
Equal aperture is 2.5-2.8nm, and carrier average grain diameter is 40 μm.
The processing of the carrier, activated carbon is impregnated with acid solution, the acid, including ethylenediamine tetra-acetic acid, poly- Malaysia
Acid, hydroxy ethylidene-diphosphate, mass ratio 2:4:1, the mass content of the acid solution is 5%, acid solution and activated carbon
Mass ratio be 4:1, when immersion 2 is small, during immersion, it is 120W/L, supersonic frequency 65KHz to control ultrasonic power density,
After immersion, washing is dry to aqueous less than 1.5%.
The absorption titanium tetrachloride, absorbent charcoal carrier is placed in chemical vapor deposition unit, is warming up to 180 DEG C,
When the lower purging 2 of nitrogen protection of 120ml/min is small, moisture is removed, titanium tetrachloride is heated to 170 DEG C, is mixed after gasification with nitrogen
After conjunction, chemical vapor deposition unit is passed through, the flow of titanium tetrachloride vapors is 1.2ml/min, nitrogen flow 68ml/min, is incited somebody to action
The temperature of chemical vapor deposition unit is increased to 300 DEG C with the speed of 5 DEG C/min, is kept for 30 minutes, then with the speed of 3 DEG C/min
Degree is increased to 450 DEG C, when holding 1 is small, chemical vapor deposition unit then is cooled to 200 DEG C, the nitrogen of 100 ml/min is blown
Sweep 2 it is small when, be down to room temperature, obtain absorption titanium tetrachloride carrier.
The vacuum suction, by copper sulphate, chlorination 1- ethyl-3-methylimidazoles, 1- (3- dimethylamino-propyls) -3- ethyls
Carbodiimide hydrochloride, is dissolved in the desalted water of 200 times of weight, and adsorption liquid a is made；The carrier for adsorbing titanium tetrachloride is put into
In the adsorption liquid a of above-mentioned preparation, the mass ratio of carrier and adsorption liquid a are 1:5, into vacuum adsorbed, the ginseng of the vacuum suction
Number is：10s is kept after being evacuated down to -0.065MPa pressure；Then 20s is kept after being depressured to -0.045MPa pressure, then is depressured
Under to -0.030MPa, 10s is kept, then is recovered to normal pressure, the immersion absorption 1h under normal pressure.
Using above technical scheme, beneficial effects of the present invention are：
（1）Catalyst without mercury of the present invention, for vinyl chloride synthesis reaction, obtained crude product, through chromatography, vinyl chloride
Purity reach 98.0v%, the yield of vinyl chloride is up to 98.3%, and the selectivity of vinyl chloride is up to 99.3%.
（2）Catalyst without mercury of the present invention, for vinyl chloride synthesis reaction, hydrogen chloride soak time is 20 minutes.
（3）Catalyst of the present invention, is calculated in mass percent, including titanium tetrachloride 3.0%, copper sulphate 1.4%, silico-tungstic acid
1.5%th, chlorination 1- ethyl-3-methylimidazoles 2.0%, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides 1.6%, its
Remaining is carrier.
The present invention without using noble metal as catalyst raw material, it is cost-effective.
Embodiment
The preferred embodiment of the present invention is illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
A kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity of embodiment 1
Comprise the following steps：
（1）The selection of carrier
Using cocoanut active charcoal as carrier, the activated carbon iodine number 1250mg/g, methylene blue value 115mg/g, carbon tetrachloride absorption
It is worth for 130%, moisture content 1.8%, ash 1.2%, bulk density 370g/L, specific surface area 1400m2/ g, average pore size 2.5-
2.8nm, carrier average grain diameter are 40 μm.
（2）The processing of carrier
Activated carbon is impregnated with acid solution, the acid, including ethylenediamine tetra-acetic acid, poly, hydroxy ethylidene-diphosphate,
Mass ratio is 2:4:1, the mass content of the acid solution is 5%, and the mass ratio of acid solution and activated carbon is 4:1, immersion 2
Hour, during immersion, it is 120W/L, supersonic frequency 65KHz to control ultrasonic power density, after immersion, is washed, dry
To aqueous less than 1.5%.
（3）The selection of catalyst raw material
The catalyst, in parts by weight, including following raw material components：3.0 parts of titanium tetrachloride, 1.5 parts of copper sulphate, silico-tungstic acid
1.6 parts, 2.2 parts of chlorination 1- ethyl-3-methylimidazoles, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides 1.7
Part, 90 parts of carrier.
According to above-mentioned formula, each raw material of catalyst is weighed.
（4）Adsorb titanium tetrachloride
Absorbent charcoal carrier is placed in chemical vapor deposition unit, is warming up to 180 DEG C, is blown under the nitrogen protection of 120ml/min
Sweep 2 it is small when, remove moisture, titanium tetrachloride is heated to 170 DEG C, after mix after gasification with nitrogen, be passed through chemical vapor deposition fill
Put, the flow of titanium tetrachloride vapors is 1.2ml/min, nitrogen flow 68ml/min, by the temperature of chemical vapor deposition unit
300 DEG C are increased to the speed of 5 DEG C/min, is kept for 30 minutes, is then increased to 450 DEG C with the speed of 3 DEG C/min, holding 1 is small
When, chemical vapor deposition unit is then cooled to 200 DEG C, when the nitrogen purging 2 of 100 ml/min is small, room temperature is down to, obtains
Adsorb the carrier of titanium tetrachloride.
（5）Vacuum suction
It is molten by copper sulphate, chlorination 1- ethyl-3-methylimidazoles, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides
In the desalted water of 200 times of weight, adsorption liquid a is made；
The carrier for adsorbing titanium tetrachloride is put into the adsorption liquid a of above-mentioned preparation, adsorbs carrier vector and the suction of titanium tetrachloride
The mass ratio of attached liquid a is 1:5, it is put into stainless-steel vacuum tank, is vacuumized with vacuum pump, into vacuum adsorbed, the vacuum suction
Attached parameter is：10s is kept after being evacuated down to -0.065MPa pressure；Then 20s is kept after being depressured to -0.045MPa pressure, then
It is depressurized under -0.030MPa, keeps 10s, then recovers to normal pressure, the immersion absorption 1h under normal pressure.
（6）Adsorb silico-tungstic acid
To step（5）In mixed liquor after the completion of absorption, the aqueous solution of silico-tungstic acid is added dropwise, dropping temperature is 45 DEG C, rate of addition
For 0.5ml/min, while dropwise addition, ultrasonic wave auxiliary absorption, ultrasonic power density 90W/L, supersonic frequency are carried out to solution
Rate is 75KHz, while is passed through compressed air, and the air pressure of air-flow is advisable with 0.9Mpa, and the flow velocity of air draught is 25L/h, is added dropwise
After, filtering, drying to water content is 0.2%, obtains catalyst of the present invention.
The aqueous solution of the silico-tungstic acid, the content of silico-tungstic acid is 10%.
Catalyst of the present invention, is calculated in mass percent, including titanium tetrachloride 3.0%, copper sulphate 1.4%, silico-tungstic acid 1.5%, chlorine
Change 1- ethyl-3-methylimidazoles 2.0%, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides 1.6%, remaining is carries
Body.
Application of the 2 above-mentioned catalyst of embodiment in vinyl chloride synthesis reaction
In the reaction for preparing chloroethylene by acetylene hydrochlorination, the mol ratio of reactor feed gas is catalyst of the present invention
C2H2/ HCl=1/1.03, acetylene air speed are 70h-1, 110 DEG C of reaction temperature, reaction pressure 0.030MPa；
Hydrogen chloride soak time is 20 minutes.
Without mercury catalyst described in the embodiment of the present invention 1, for vinyl chloride synthesis reaction, obtained crude product, through chromatography,
The purity of vinyl chloride reaches 98.0v%, and the yield of vinyl chloride is up to 98.3%, and the selectivity of vinyl chloride is up to 99.3%；
After carrying out rectifying to vinyl chloride crude product, the purity for obtaining vinyl chloride reaches 99.999v%, and acetylene is less than 0.0001v%%.
The unit consumption of catalyst prepared by the present invention is low, and catalyst consumption is 0.0015-0.0017 g/ml vinyl chloride.
Unless otherwise indicated, the percentage employed in the present invention is percetage by weight, and ratio of the present invention, is matter
Amount ratio.
The basic principle and main feature and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (6)
- A kind of 1. preparation method for the catalyst without mercury for improving vinyl chloride crude product purity, it is characterised in that：The preparation method, bag Include the selection of carrier, the processing of carrier, absorption titanium tetrachloride, vacuum suction, absorption silico-tungstic acid.
- 2. a kind of preparation method of catalyst without mercury for improving vinyl chloride crude product purity according to claim 1, its feature It is：The selection of the carrier, using cocoanut active charcoal as carrier, the activated carbon iodine number 1250mg/g, methylene blue value 115mg/g, Penetrating curve 130%, moisture content 1.8%, ash 1.2%, bulk density 370g/L, specific surface area are 1400m2/ g, average pore size 2.5-2.8nm, carrier average grain diameter are 40 μm.
- 3. a kind of preparation method of catalyst without mercury for improving vinyl chloride crude product purity according to claim 1, its feature It is：The processing of the carrier, activated carbon is impregnated with acid solution, the acid, including ethylenediamine tetra-acetic acid, poly, Hydroxy ethylidene-diphosphate, mass ratio 2:4:1, the mass content of the acid solution is 5%, acid solution and activated carbon Mass ratio is 4:1, when immersion 2 is small, during immersion, it is 120W/L, supersonic frequency 65KHz to control ultrasonic power density, is soaked After bubble, washing is dry to aqueous less than 1.5%.
- 4. a kind of preparation method of catalyst without mercury for improving vinyl chloride crude product purity according to claim 1, its feature It is：The absorption titanium tetrachloride, absorbent charcoal carrier is placed in chemical vapor deposition unit, 180 DEG C is warming up to, in 120ml/ When the lower purging 2 of nitrogen protection of min is small, moisture is removed, titanium tetrachloride is heated to 170 DEG C, after being mixed after gasification with nitrogen, is led to Enter chemical vapor deposition unit, the flow of titanium tetrachloride vapors is 1.2ml/min, nitrogen flow 68ml/min, by chemical gas The temperature of phase precipitation equipment is increased to 300 DEG C with the speed of 5 DEG C/min, is kept for 30 minutes, is then raised with the speed of 3 DEG C/min To 450 DEG C, when holding 1 is small, chemical vapor deposition unit is then cooled to 200 DEG C, the nitrogen purging 2 of 100 ml/min is small When, room temperature is down to, obtains the carrier of absorption titanium tetrachloride.
- 5. a kind of preparation method of catalyst without mercury for improving vinyl chloride crude product purity according to claim 1, its feature It is：The vacuum suction, by copper sulphate, chlorination 1- ethyl-3-methylimidazoles, 1- (3- dimethylamino-propyls) -3- ethyl carbon Diimmonium salt hydrochlorate, is dissolved in the desalted water of 200 times of weight, and adsorption liquid a is made；The carrier for adsorbing titanium tetrachloride is put into In the adsorption liquid a for stating preparation, the mass ratio of carrier and adsorption liquid a are 1:5, into vacuum adsorbed, the parameter of the vacuum suction For：10s is kept after being evacuated down to -0.065MPa pressure；Then 20s is kept after being depressured to -0.045MPa pressure, then be depressurized to - Under 0.030MPa, 10s is kept, then is recovered to normal pressure, the immersion absorption 1h under normal pressure.
- 6. a kind of preparation method of catalyst without mercury for improving vinyl chloride crude product purity according to claim 1, its feature It is：The catalyst without mercury, is calculated in mass percent, including titanium tetrachloride 3.0%, copper sulphate 1.4%, silico-tungstic acid 1.5%, chlorine Change 1- ethyl-3-methylimidazoles 2.0%, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides 1.6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711207785.XA CN107999139B (en) | 2017-11-27 | 2017-11-27 | Preparation method of mercury-free catalyst for improving purity of vinyl chloride crude product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711207785.XA CN107999139B (en) | 2017-11-27 | 2017-11-27 | Preparation method of mercury-free catalyst for improving purity of vinyl chloride crude product |
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| Publication Number | Publication Date |
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| CN107999139A true CN107999139A (en) | 2018-05-08 |
| CN107999139B CN107999139B (en) | 2020-07-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517085A (en) * | 2020-12-30 | 2021-03-19 | 李通 | Non-noble metal catalyst and process for producing vinyl chloride by adopting same |
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 |
| CN103191764A (en) * | 2013-04-23 | 2013-07-10 | 新疆天业（集团）有限公司 | Mercury-free catalyst for synthesizing vinyl chloride through acetylene hydrochlorination and preparation method thereof |
| CN104437564A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Catalyst for environment-friendly catalytic production of chloroethylene and method for producing chloroethylene by using catalyst |
| CN106215977A (en) * | 2016-07-25 | 2016-12-14 | 宁夏新龙蓝天科技股份有限公司 | A kind of high synthesis vinyl chloride of activity that is catalyzed is without mercury catalyst and preparation method thereof |
| CN106268963A (en) * | 2016-07-29 | 2017-01-04 | 宁夏新龙蓝天科技股份有限公司 | A kind of service life length synthesis vinyl chloride without mercury catalyst and preparation method thereof |
| CN106378122A (en) * | 2016-08-26 | 2017-02-08 | 天津南化催化剂有限公司 | Silica gel loaded titanium catalyst, preparation method and application thereof |
-
2017
- 2017-11-27 CN CN201711207785.XA patent/CN107999139B/en active Active
Patent 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 |
| CN103191764A (en) * | 2013-04-23 | 2013-07-10 | 新疆天业（集团）有限公司 | Mercury-free catalyst for synthesizing vinyl chloride through acetylene hydrochlorination and preparation method thereof |
| CN104437564A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Catalyst for environment-friendly catalytic production of chloroethylene and method for producing chloroethylene by using catalyst |
| CN106215977A (en) * | 2016-07-25 | 2016-12-14 | 宁夏新龙蓝天科技股份有限公司 | A kind of high synthesis vinyl chloride of activity that is catalyzed is without mercury catalyst and preparation method thereof |
| CN106268963A (en) * | 2016-07-29 | 2017-01-04 | 宁夏新龙蓝天科技股份有限公司 | A kind of service life length synthesis vinyl chloride without mercury catalyst and preparation method thereof |
| CN106378122A (en) * | 2016-08-26 | 2017-02-08 | 天津南化催化剂有限公司 | Silica gel loaded titanium catalyst, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| HUI DAI ET AL.: ""Activated Carbon Supported Mo-Ti-N Binary Transition Metal Nitride as Catalyst for Acetylene Hydrochlorination"", 《CATALYSTS》 * |
| 沈永嘉 主编: "《有机颜料-品种与应用》", 31 July 2001, 化学工业出版社 * |
| 沈玉龙 等编: "《绿色化学 第三版》", 30 April 2016, 中国环境出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517085A (en) * | 2020-12-30 | 2021-03-19 | 李通 | Non-noble metal catalyst and process for producing vinyl chloride by adopting same |
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