CN108043467A - 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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- CN108043467A CN108043467A CN201711204782.0A CN201711204782A CN108043467A CN 108043467 A CN108043467 A CN 108043467A CN 201711204782 A CN201711204782 A CN 201711204782A CN 108043467 A CN108043467 A CN 108043467A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 34
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 29
- 229910052753 mercury Inorganic materials 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- PAZXSSIUSRIURW-UHFFFAOYSA-N [methoxy(methyl)phosphoryl]methanamine Chemical class COP(C)(=O)CN PAZXSSIUSRIURW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 0.000 claims 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 claims 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 16
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- LPSCRKGVODJZIB-UHFFFAOYSA-N [I].[C] Chemical class [I].[C] LPSCRKGVODJZIB-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration 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
- 238000002309 gasification Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 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
- 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 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical class CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 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
- 230000000149 penetrating effect Effects 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 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 present invention relates to a kind of catalyst without mercury for improving chloro ethylene yield and preparation method thereof, belong to catalyst technology neck
Domain.
Background technology
Vinyl chloride is the monomer of igelite synthesis, by acetylene and hcl reaction come to prepare vinyl chloride be chlorine
One important route of synthesis of vinyl monomer, also referred to as carbide production vinyl chloride.
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.
The prior art uses acetylene and hydrogen chloride synthesis vinyl chloride, and there are yield is low, conversion of alkyne is low, use your gold more
Belong to the deficiency as catalyst active ingredient.
Chinese patent CN102698806A, using the ingredient as catalyst without mercury such as cobalt oxalate, cerium chloride, acetylene turns
Rate is up to 86%, and vinyl chloride selectively up to 92%, yield is not as good as 80%；
The disclosed catalyst without mercury for being used for VCM synthesis of Chinese patent CN103191764A, based on phosphotungstic acid copper activity into
Point, using gadolinium chloride, lanthanum nitrate, silver nitrate as auxiliary agent, conversion of alkyne is up to 85%, and selectivity up to 90%, yield is less than
80%。
In addition, the molar ratio for improving hydrogen chloride and acetylene is generally taken, and then is improved in order to improve yield in the prior art
The inlet amount of hydrogen chloride causes the waste of hydrogen chloride or increases the cost of recycling, and reduces the molar ratio of hydrogen chloride and acetylene,
It can cause the decline of yield.
The content of the invention
The present invention for solve the shortcomings of the prior art, provide it is a kind of improve chloro ethylene yield catalyst without mercury and its
Preparation method, to realize following goal of the invention：
（1）Improve the yield of vinyl chloride and the conversion ratio of acetylene；
（2）Reduce the molar ratio of hydrogen chloride and acetylene；
（3）It is cost-effective without using noble metal as catalyst raw material.
For solution more than technical problem, the present invention uses following technical scheme：
A kind of catalyst without mercury for improving chloro ethylene yield, it is characterised in that：The catalyst without mercury, is calculated in mass percent,
Including titanium tetrachloride 2.8%, barium chloride 0.9%, silicomolybdic acid 1.5%, 2- undecyl imidazoles 1.4%, polyvinylpyrrolidone 1.9%,
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides 1.8%, water 0.15%.
It is that above-mentioned technical proposal is further improved below：
The catalyst without mercury, for catalyzing and synthesizing vinyl chloride.
A kind of preparation method for the catalyst without mercury for improving chloro ethylene yield, the preparation method, the processing including carrier,
It adsorbs titanium tetrachloride, vacuum suction, silicomolybdic acid is added dropwise.
The processing of the carrier, including acid treatment；The acid treatment impregnates activated carbon with acid solution, the acid, bag
Include citric acid, amino trimethyl phosphinic acids, ethylenediaminetetramethylphosphinic acid, mass ratio 3:4:1, the quality of the acid solution
Content is 5%, and the mass ratio of acid solution and activated carbon is 4:1, when immersion 2 is small.
During immersion, it is 120W/L, supersonic frequency 65KHz to control ultrasonic power density.
The processing of the carrier, further includes Urea treatment；Activated carbon is placed in the dense of 5 times of its volume by the Urea treatment
Spend in the urea liquid for 3.5wt%, heating stirring to flow back 3.2 it is small when after, filter simultaneously in 60 DEG C dry surface moistures, then at
85 DEG C are dried under vacuum to constant weight, are then fired to constant weight in 160 DEG C.
The vacuum suction, by barium chloride, 2- undecyl imidazoles, polyvinylpyrrolidone, 1- (3- dimethylaminos third
Base) -3- ethyl-carbodiimide hydrochlorides, it is dissolved in the desalted water of 300 times of weight, adsorption liquid a is made；Carrier and adsorption liquid a's
Mass ratio is 1:5 into vacuum adsorbed, and the parameter of the vacuum suction is：20s is kept after being evacuated down to -0.045MPa pressure；
Then 10s is kept after being evacuated down to -0.068MPa pressure, then is depressurized under -0.037MPa, keeps 10s, then is recovered to normal pressure,
Absorption 1h is impregnated under normal pressure.
The aqueous solution of silicomolybdic acid is added dropwise in the dropwise addition silicomolybdic acid, and dropping temperature is 35 DEG C, rate of addition 1.2ml/min；
The aqueous solution of the silicomolybdic acid, the content of silicomolybdic acid is 10%.
Using above technical scheme, beneficial effects of the present invention are：
（1）Catalyst without mercury of the present invention, for the synthetic reaction of vinyl chloride, the yield of vinyl chloride up to 98.9%, vinyl chloride
For selectivity up to 99.6%, the conversion ratio of acetylene is 99.3%.
（2）Catalyst without mercury of the present invention, for the synthetic reaction of vinyl chloride, the molar ratio of reduction hydrogen chloride and acetylene
To 1:1.
（3）Catalyst without mercury prepared by the present invention, is calculated in mass percent, including titanium tetrachloride 2.8%, barium chloride 0.9%,
Silicomolybdic acid 1.5%, 2- undecyl imidazoles 1.4%, polyvinylpyrrolidone 1.9%, 1- (3- dimethylamino-propyls) -3- ethyl carbon
Diimmonium salt hydrochlorate 1.8%, water 0.15%；Remaining is carrier.
Noble metal is not contained in catalyst of the present invention, saves production cost.
Specific embodiment
The preferred embodiment of the present invention is illustrated below, it should be understood 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 chloro ethylene yield of embodiment 1
Comprise the following steps：
（1）The selection of carrier
Using activated carbon as carrier, the activated carbon iodine number 1400mg/g, methylene blue value 127mg/g, Penetrating curve is
135%th, moisture content 1.5%, ash 0.7%, bulk density 400g/L, specific surface area 1450m2/ g, average pore size 3.0-3.2nm,
Carrier average grain diameter is 40 μm.
（2）The processing of carrier
A, acid treatment
Activated carbon is impregnated with acid solution, the acid, including citric acid, amino trimethyl phosphinic acids, ethylenediamine tetraacetic methyl
Phosphonic acids, mass ratio 3:4:1, the mass content of the acid solution is 5%, and the mass ratio of acid solution and activated carbon is 4:1,
Impregnate 2 it is small when, during immersion, ultrasonic power density is controlled as 120W/L, supersonic frequency 65KHz, after immersion, by work
Property charcoal is washed with distilled water, and surface moisture is dried at 55 DEG C, constant weight is dried under vacuum to then at 92 DEG C；
B, Urea treatment
By the activated carbon be placed in 5 times of its volume concentration be 3.5wt% urea liquid in, heating stirring to flow back 3.2 it is small when
Afterwards, filter and dry surface moisture in 60 DEG C, be dried under vacuum to constant weight then at 85 DEG C, be subsequently placed in Muffle furnace in 160 DEG C（Urine
The decomposition temperature of element）Constant weight is fired to, obtains the absorbent charcoal carrier that pretreatment is completed, it is spare.
（3）The selection of catalyst raw material
The catalyst, in parts by weight, including following raw material components：2.8 parts of titanium tetrachloride, 1.0 parts of barium chloride, silicomolybdic acid
1.5 parts, 1.5 parts of 2- undecyl imidazoles, 2.0 parts of polyvinylpyrrolidone, 1- (3- dimethylamino-propyls) -3- ethyls carbon two it is sub-
1.8 parts of amine hydrochlorate, 89.4 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
It puts, 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
By barium chloride, 2- undecyl imidazoles, polyvinylpyrrolidone, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride is dissolved in the desalted water of 300 times of weight, and adsorption liquid a is made；
The carrier for adsorbing titanium tetrachloride is put into the adsorption liquid a of above-mentioned preparation, adsorbs the carrier of titanium tetrachloride and adsorption liquid a
Mass ratio be 1:5, it is put into stainless-steel vacuum tank, is vacuumized with vacuum pump, into vacuum adsorbed, the ginseng of the vacuum suction
Number is：20s is kept after being evacuated down to -0.045MPa pressure；Then 10s is kept after being evacuated down to -0.068MPa pressure, then is depressured
Under to -0.037MPa, 10s is kept, then is recovered to normal pressure, absorption 1h is impregnated under normal pressure.
（6）Silicomolybdic acid is added dropwise
To step（5）In mixed liquor after the completion of absorption, the aqueous solution of silicomolybdic acid is added dropwise, dropping temperature is 35 DEG C, rate of addition
For 1.2ml/min, while dropwise addition, ultrasonic wave auxiliary absorption, ultrasonic power density 95W/L, supersonic frequency are carried out to solution
Rate is 70KHz, while is passed through compressed air, and the air pressure of air-flow is advisable with 1.1Mpa, and the flow velocity of air draught is 30L/h, is added dropwise
After, filtering, drying to water content is 0.15%, obtains catalyst of the present invention.
In the aqueous solution of the silicomolybdic acid, the content of silicomolybdic acid is 10%.
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=1/1.0, acetylene air speed are 65h-1, 102 DEG C of reaction temperature, reaction pressure 0.030MPa；
Hydrogen chloride soak time is 30 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 97.0v%, and up to 98.9%, the selectivity of vinyl chloride is up to 99.6%, the conversion ratio of acetylene for the yield of vinyl chloride
99.3%。
After carrying out rectifying to vinyl chloride crude product, the purity of vinyl chloride is obtained up to 99.999v%, acetylene is less than
0.0001v%%。
The unit consumption of catalyst prepared by the present invention is low, and catalyst consumption is 0.0012-0.0013g/ml vinyl chloride.
Unless otherwise indicated, the percentage employed in the present invention is weight percent, and ratio of the present invention is matter
Amount ratio.
Basic principle of the invention and main feature and advantages 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 (8)
1. a kind of catalyst without mercury for improving chloro ethylene yield, it is characterised in that：The catalyst without mercury, with mass percent
Meter, including titanium tetrachloride 2.8%, barium chloride 0.9%, silicomolybdic acid 1.5%, 2- undecyl imidazoles 1.4%, polyvinylpyrrolidone
1.9%th, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides 1.8%, water 0.15%.
2. a kind of catalyst without mercury for improving chloro ethylene yield according to claim 1, it is characterised in that：The mercury-free is urged
Agent, for catalyzing and synthesizing vinyl chloride.
3. a kind of preparation method for the catalyst without mercury for improving chloro ethylene yield, it is characterised in that：The preparation method, including carrying
The processing of body, absorption titanium tetrachloride, vacuum suction, dropwise addition silicomolybdic acid.
4. a kind of preparation method of catalyst without mercury for improving chloro ethylene yield according to claim 3, it is characterised in that：
The processing of the carrier, including acid treatment；The acid treatment impregnates activated carbon with acid solution, the acid, including lemon
Acid, amino trimethyl phosphinic acids, ethylenediaminetetramethylphosphinic acid, mass ratio 3:4:1, the mass content of the acid solution is
5%, the mass ratio of acid solution and activated carbon is 4:1, when immersion 2 is small.
5. a kind of preparation method of catalyst without mercury for improving chloro ethylene yield according to claim 4, it is characterised in that：
During immersion, it is 120W/L, supersonic frequency 65KHz to control ultrasonic power density.
6. a kind of preparation method of catalyst without mercury for improving chloro ethylene yield according to claim 3, it is characterised in that：
The processing of the carrier, further includes Urea treatment；The Urea treatment, the concentration that activated carbon is placed in 5 times of its volume are
In the urea liquid of 3.5wt%, heating stirring to flow back 3.2 it is small when after, filter simultaneously in 60 DEG C dry surface moistures, then at 85 DEG C
Constant weight is dried under vacuum to, is then fired to constant weight in 160 DEG C.
7. a kind of preparation method of catalyst without mercury for improving chloro ethylene yield according to claim 3, it is characterised in that：
The vacuum suction, by barium chloride, 2- undecyl imidazoles, polyvinylpyrrolidone, 1- (3- dimethylamino-propyls) -3- ethyls
Carbodiimide hydrochloride is dissolved in the desalted water of 300 times of weight, and adsorption liquid a is made；The mass ratio of carrier and adsorption liquid a are 1:5
Into vacuum adsorbed, the parameter of the vacuum suction is：20s is kept after being evacuated down to -0.045MPa pressure；Then vacuumize
10s is kept after to -0.068MPa pressure, then is depressurized under -0.037MPa, keeps 10s, then is recovered to normal pressure, under normal pressure
Impregnate absorption 1h.
8. a kind of preparation method of catalyst without mercury for improving chloro ethylene yield according to claim 3, it is characterised in that：
The aqueous solution of silicomolybdic acid is added dropwise in the dropwise addition silicomolybdic acid, and dropping temperature is 35 DEG C, rate of addition 1.2ml/min；The silicon molybdenum
The aqueous solution of acid, the content of silicomolybdic acid is 10%.
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| CN109647523A (en) * | 2018-12-25 | 2019-04-19 | 南开大学 | A kind of preparation method and its application method of the non-metal catalyst for fixed bed preparing chloroethylene by acetylene hydrochlorination |
| CN113004204A (en) * | 2021-03-25 | 2021-06-22 | 湖北江大化工股份有限公司 | Preparation method of 2-undecylimidazoline |
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