CN105233875B - A kind of preparation method of ultralow mercury catalyst for VCM synthesis - Google Patents
A kind of preparation method of ultralow mercury catalyst for VCM synthesis Download PDFInfo
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- CN105233875B CN105233875B CN201510703909.8A CN201510703909A CN105233875B CN 105233875 B CN105233875 B CN 105233875B CN 201510703909 A CN201510703909 A CN 201510703909A CN 105233875 B CN105233875 B CN 105233875B
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- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 46
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 52
- 239000012071 phase Substances 0.000 claims abstract description 41
- 238000010521 absorption reaction Methods 0.000 claims abstract description 26
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 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
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 6
- 238000001764 infiltration Methods 0.000 claims description 6
- 150000002730 mercury Chemical class 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 239000003463 adsorbent Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000003610 charcoal Substances 0.000 description 11
- 239000002250 absorbent Substances 0.000 description 9
- 230000002745 absorbent Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002817 coal dust Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- -1 medical industry Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000007420 reactivation Effects 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- LPSCRKGVODJZIB-UHFFFAOYSA-N [I].[C] Chemical class [I].[C] LPSCRKGVODJZIB-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KZIKDWMVGLXOTB-UHFFFAOYSA-N chloranylethene Chemical compound ClC=C.ClC=C KZIKDWMVGLXOTB-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
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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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation method of ultralow mercury catalyst for VCM synthesis, includes preparation, the absorption of activated carbon, and the absorption includes Gas Phase Adsorption mercury chloride and liquid phase adsorption collaboration accelerator；Ultralow mercury catalyst prepared by the present invention, obtained ultralow mercury catalyst is by weight percentage, chloride containing mercury 0.93 1.0%, zinc chloride 2.4 2.5%, barium chloride 1.2 2.5%, tetrabutylammonium chloride 1.2 3.75%, the ammonia palladium 1.25 2.4% of dichloro four, water 0.2%, mechanical strength 96.6 96.9%, 3~6mm of granularity（97‑97.5%）, the 505g/l of bulk density 500；Ultralow mercury catalyst prepared by the present invention, for vinyl chloride synthesis reaction, conversion of alkyne is up to 99.90 99.91%, and vinyl chloride selectivity is up to 99.9 100%, and the yield of vinyl chloride is up to 94.2 94.5%.
Description
Technical field
The present invention relates to a kind of preparation method of the ultralow mercury catalyst for VCM synthesis, belong to fine chemistry technology
Field.
Background technology
The polyvinyl chloride synthesized by VCM（PVC）, it is the thermoplastic articles raw material of yield maximum in the world
One of, it is widely used in the fields such as materials for construction, packaging material, electric equipment products, medical industry, coating and adhesive.
The industrialized production of current synthesis vinyl chloride thereof monomer in the world is based on ethylene process.Fluctuated by crude oil price larger
Influence, occupies critical role at home by acetylene through hydrogen chloride production PVC.Acetylene hydrochlorination reaction industrial at present, mainly
The high mercury catalyst that mercury chloride load capacity is 12% ~ 15% is used, its consumption to mercury accounts for the 60% of domestic mercury usage amount, and
Health to environment and the mankind causes serious harm.
For the rare of mercury resource and the pollution to environment, and both at home and abroad to the increasingly severe of mercury pollution prevention and control policy,
It is raw meeting industry in the urgent need to being had breakthrough in the improvement to mercury chloride performance and the research of high-performance environment protection type catalyst
While production needs, mercury resource consumption and the pollution and harm to environment and human health is greatly lowered.
Existing low-mercury catalyst, has the following disadvantages：
（1）Mercury content is high；
（2）Service life is short；
（3）Catalytic performance is poor, for vinyl chloride synthesis reaction, and conversion of alkyne is less than 99.8%, the selection of vinyl chloride vinyl chloride
Property and yield are low.
The content of the invention
There is provided a kind of ultralow mercury catalyst for VCM synthesis to solve the deficiency that prior art is present by the present invention
Prepare and its mercury recovery method, to realize following goal of the invention：
（1）Ultralow mercury catalyst prepared by the present invention, the adsorbing chlorinated mercury in activated carbon center, obtained ultralow mercury catalysis
Agent by weight percentage, chloride containing mercury 0.93-1.0%, zinc chloride 2.4-2.5%, barium chloride 1.2-2.5%, tetrabutylammonium chloride
1.2-3.75%, the ammonia palladium 1.25-2.4% of dichloro four, water 0.2%, mechanical strength 96.6-96.9%, 3~6mm of granularity（97-97.5%）,
Bulk density 500-505g/l.
（2）Ultralow mercury catalyst prepared by the present invention, catalyst long service life.
（3）Catalyst prepared by the present invention is used for vinyl chloride synthesis reaction, and conversion of alkyne reaches 99.90-99.91%, chloroethene
Alkene selectively reaches 99.9-100%, and the yield of vinyl chloride reaches 94.2-94.5%.
To solve above technical problem, the present invention uses following technical scheme：
A kind of preparation method of ultralow mercury catalyst for VCM synthesis, includes preparation, the absorption of activated carbon, described
Absorption includes Gas Phase Adsorption mercury chloride and liquid phase adsorption collaboration accelerator.
The following is the further improvement to above-mentioned technical proposal：
The Gas Phase Adsorption mercury chloride includes first stage Gas Phase Adsorption, the first stage Gas Phase Adsorption, control pressure
For 0.6-0.7MPa, temperature is 540-560 DEG C, and mass space velocity is 7h-1, adsorb 15min.
The Gas Phase Adsorption mercury chloride includes second stage Gas Phase Adsorption, and the second stage Gas Phase Adsorption is depressurized to pressure
Power is 0.4-0.5 MPa, and temperature is 420-440 DEG C, and mass space velocity is 8h-1, adsorb 10min.
The Gas Phase Adsorption mercury chloride includes phase III Gas Phase Adsorption, and the phase III Gas Phase Adsorption boosts to pressure
Power is 0.7-0.8 MPa, and temperature is 560-570 DEG C, and mass space velocity is 6h-1, adsorb 5min.
The Gas Phase Adsorption mercury chloride, the content for controlling mercury chloride is 1.0-1.1%.
The liquid phase adsorption, including immersion absorption, the immersion absorption, soak 2 small under 120-125 DEG C of temperature conditionss
When, dried under 110 DEG C of temperature conditionss to aqueous less than 0.2%.
The liquid phase adsorption, including vacuum infiltration absorption, vacuum infiltration absorption are vacuumized, reach -0.035 ~ -
30s is kept after 0.038MPa pressure, then is recovered to normal pressure, in soaking 5min under normal pressure.
Using above technical scheme, beneficial effects of the present invention are：
（1）Ultralow mercury catalyst prepared by the present invention, the adsorbing chlorinated mercury in activated carbon center, obtained ultralow mercury catalysis
Agent by weight percentage, chloride containing mercury 0.93-1.0%, zinc chloride 2.4-2.5%, barium chloride 1.2-2.5%, tetrabutylammonium chloride
1.2-3.75%, the ammonia palladium 1.25-2.4% of dichloro four, water 0.2%, mechanical strength 96.6-96.9%, 3~6mm of granularity（97-97.5%）,
Bulk density 500-505g/l.
（2）Ultralow mercury catalyst prepared by the present invention, catalyst long service life, up to 8500 hours.
（3）Catalyst prepared by the present invention is used for vinyl chloride synthesis reaction, and conversion of alkyne is 99.90-99.91%, chloroethene
Alkene is selectively 99.9-100%, and the yield of vinyl chloride is 94.2-94.5%.
Embodiment
The preferred embodiments of the present invention are 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 of the ultralow mercury catalyst for VCM synthesis of embodiment 1
The preparation of step 1, activated carbon
（1）The selection of feed coal
The feed coal is anthracite, and moisture is 6%, and content of ashes is 8.5%, and volatile matter content is 14.5%, fixed
Carbon content is 71%.
（2）The deliming of feed coal
By smokeless coal grinding, 100 mesh sieves are crossed, coal dust are put into 30ppm polymeric aluminum chlorides solution, strong agitation, turned
Speed is 5000r/min, after 2 minutes, and rotating speed is reduced to 500r/min, after stirring 10 minutes, filtering, and distillation is washed to during filtrate is in
Property；Add in polyacrylamide solution, polyacrylamide concentration is 0.5ppm, and rotating speed is 400 r/min, after stirring 10 minutes, mistake
Filter, it is in neutral that distillation, which is washed to filtrate, and content of ashes is 1.5% after deliming.
（3）Charing
By by the coal dust of deliming, in the case where N2 flows are 20ml/mim protection, carbonized, carbonization temperature initial temperature
For 300 DEG C, with 2 DEG C/min heating rate, 400 DEG C are risen to, carbonizes 2.5 hours, obtains carbonized material.
（4）Once activate
By the coal dust acid dip after charing, described acid, including：60% phosphoric acid, tartaric acid, stearic acid, mass ratio
For 3:1:2, acid is 3 with the mass ratio of fixed carbon in coal dust:1, soak 5 hours, wash, dry.
（5）Re-activation
In coal dust after once activating, the mixed liquor for being placed in re-activation agent, soak 2 hours, the re-activation
Agent is zinc chloride, bismuth chloride, magnesium chloride, plumbi nitras, and mass ratio is 3:2:1:1, the mass ratio of re-activation agent and fixed carbon
For 1:0.8, it is then 10ml/mim, at 480 DEG C in N2 flows, activates 2 hours.
（6）Post processing
Activated material to be come out of the stove and be cooled to room temperature after cooling, is put into immersion in the hydrochloric acid solution that weight/mass percentage composition is 4% 12 small
When, distilled water flushing to neutrality, drying.
The activated carbon iodine number 1250mg/g of preparation, methylene blue value 135mg/g, mesoporous is up to 97.5%, and carbon tetrachloride is adsorbed
Value is that 120%, moisture content 2%, ash 1.5%, fixed carbon content are 75%, mechanical strength 98%, bulk density 398g/L, specific surface area
For 1950m2/ g, average pore size is 2.7-3.1nm.
The preparation of step 2, carrier
（1）Prepare hydrochloric acid solution
500 kilograms of the hydrochloric acid solution that mass fraction is 0.5% is prepared with high purity hydrochloric acid and desalted water, room temperature is standby；
（2）Handle activated carbon
100 kilograms of selected activated carbons are put into（1）Soaked in the hydrochloric acid solution of preparation 30 minutes, during which using circulation
Pump makes hydrochloric acid solution constantly flow, and then takes out filtering or is filtered dry, is done under 200 DEG C of temperature conditionss with centrifuge drying dehydration
Dry to aqueous less than 3%, carrier is made.
Step 3, the preparation for cooperateing with accelerator adsorption liquid
PH=3 15% hydrochloric acid solution is prepared with hydrochloric acid and desalted water, appropriate collaboration accelerator is added, collaboration accelerator
Mass content is 10%, and collaboration accelerator includes：Zinc chloride, barium chloride, tetrabutylammonium chloride, the ammonia palladium of dichloro four, mass ratio
For：2:1:1:2.
Step 4, absorption
（1）Gas Phase Adsorption mercury chloride
A, pre-treatment
Activated carbon by pretreatment is fitted into adsorbent bed, high-purity mercury chloride is subjected to heating and gasifying, the chlorine of gas phase
Change mercury to enter in the adsorbent bed equipped with activated carbon, first with nitrogen purge system, the foreign gas such as discharge oxygen, carbon dioxide,
B, first stage Gas Phase Adsorption
Control pressure is 0.6MPa, and temperature is 540 DEG C, and mass space velocity is 7h-1, adsorbent bed upper end is equipped with condenser, condensation
Liquid reenters adsorbent bed after being regasified and adsorbed, after absorption 15min；
C, second stage Gas Phase Adsorption
Step-down processing is carried out, pressure is 0.4MPa in adsorbent bed after step-down, temperature is 420 DEG C, and mass space velocity is 8h-1, inhale
Attached 10min；
D, phase III Gas Phase Adsorption
It is 0.7MPa to carry out after boosting processing, boosting pressure in adsorbent bed again, and temperature is 560 DEG C, and mass space velocity is 6h-1,
5min is adsorbed, as a circulation, after the circulation is completed, the circulation is repeated, during which detects the mercury chloride of charcoal absorption
Content, the content for controlling mercury chloride is 1.0%, stops absorption.
（2）Liquid phase adsorption cooperates with accelerator
A, immersion absorption
Absorbent charcoal carrier after Gas Phase Adsorption mercury chloride is put into the collaboration accelerator adsorption liquid that step 3 is prepared
In, the mass ratio of absorbent charcoal carrier and adsorption liquid is 1:5, soaked under 120 DEG C of temperature conditionss 2 hours, during which using circulation
Pump makes adsorbent solution constantly flow, and then takes out filtering or is filtered dry with centrifuge drying dehydration, baking oven is put into, in 110 DEG C of temperature
Dried under the conditions of degree to aqueous less than 0.2%；
B, vacuum infiltration absorption
Then will by immersion absorption absorbent charcoal carrier be placed again into collaboration accelerator adsorption liquid in, absorbent charcoal carrier with
The mass ratio of adsorption liquid is 1:4, place into stainless-steel vacuum tank, vacuumized with vavuum pump, reach and protected after -0.035MPa pressure
30s is held, then is recovered to normal pressure, 5min is soaked under normal pressure, filtering is then taken out or is filtered dry with centrifuge drying dehydration, put
Enter baking oven, dried under 110 DEG C of temperature conditionss to aqueous less than 0.2%, ultralow mercury catalyst is made.
Ultralow mercury catalyst prepared by the present invention, the adsorbing chlorinated mercury in activated carbon center, obtained ultralow mercury catalyst
By weight percentage, chloride containing mercury 0.93%, zinc chloride 2.4%, barium chloride 1.2%, tetrabutylammonium chloride 1.2%, the ammonia of dichloro four
Palladium 2.4%, water 0.2%, mechanical strength 96.6%, 3~6mm of granularity（97%）, bulk density 500g/l.
A kind of preparation method of the ultralow mercury catalyst for VCM synthesis of embodiment 2
Using the preparation method of embodiment 1, the parameter of change is as follows：
Step 3, the preparation for cooperateing with accelerator adsorption liquid
PH=2.5 16% hydrochloric acid solution is prepared with hydrochloric acid and desalted water, appropriate collaboration accelerator is added, cooperates with accelerator
Mass content be 12%, collaboration accelerator include：Zinc chloride, barium chloride, tetrabutylammonium chloride, the ammonia palladium of dichloro four, mass ratio
For：2:2:3:1.
Step 4, absorption
（1）Gas Phase Adsorption mercury chloride
A, pre-treatment
It will be fitted into by absorbent charcoal carrier in adsorbent bed, high-purity mercury chloride is subjected to heating and gasifying, the mercury chloride of gas phase
Enter in the adsorbent bed equipped with activated carbon, first with nitrogen purge system, the foreign gas such as discharge oxygen, carbon dioxide；
B, first stage Gas Phase Adsorption
Then control pressure is 0.7MPa, and temperature is 560 DEG C, and mass space velocity is 7h-1, adsorbent bed upper end be equipped with condenser,
Condensate liquid reenters adsorbent bed after being regasified and adsorbed, and adsorbs 15min；
C, second stage Gas Phase Adsorption
Step-down processing is carried out, pressure is 0.5 MPa in adsorbent bed after step-down, temperature is 440 DEG C, and mass space velocity is 8h-1, inhale
Attached 10min；
D, phase III Gas Phase Adsorption
It is 0.8 MPa to carry out after boosting processing, boosting pressure in adsorbent bed again, and temperature is 570 DEG C, and mass space velocity is 6h-1,
5min is adsorbed, as a circulation, after the circulation is completed, the circulation is repeated, during which detects the mercury chloride of charcoal absorption
Content, the content for controlling mercury chloride is 1.1%.
（2）Liquid phase adsorption cooperates with accelerator
A, immersion absorption
Absorbent charcoal carrier after Gas Phase Adsorption mercury chloride is put into the collaboration accelerator adsorption liquid that step 3 is prepared
In, the mass ratio of absorbent charcoal carrier and adsorption liquid is 1:5, soaked under 125 DEG C of temperature conditionss 2 hours, during which using circulation
Pump makes adsorbent solution constantly flow, and then takes out filtering or is filtered dry with centrifuge drying dehydration, baking oven is put into, in 110 DEG C of temperature
Dried under the conditions of degree to aqueous less than 0.2%；
B, vacuum infiltration absorption
Then it will be placed again into by the absorbent charcoal carrier for soaking absorption in the collaboration accelerator adsorption liquid that step 3 is prepared,
The mass ratio of absorbent charcoal carrier and adsorption liquid is 1:5, place into stainless-steel vacuum tank, vacuumized with vavuum pump, reach-
30s is kept after 0.038MPa pressure, then is recovered to normal pressure, 5min is soaked under normal pressure, filtering is then taken out or uses centrifuge
Drying dehydration is filtered dry, and is put into baking oven, is dried under 110 DEG C of temperature conditionss to aqueous less than 0.2%, and ultralow mercury catalyst is made.
Ultralow mercury catalyst prepared by the present invention, the adsorbing chlorinated mercury in activated carbon center, obtained ultralow mercury catalyst
By weight percentage, chloride containing mercury 1.0%, zinc chloride 2.5%, barium chloride 2.5%, tetrabutylammonium chloride 3.75%, the ammonia of dichloro four
Palladium 1.25%, water 0.2%, mechanical strength 96.9%, 3~6mm of granularity（97.5%）, bulk density 505g/l.
The above-mentioned catalyst of embodiment 3 is used for vinyl chloride synthesis reaction
（1）Loading catalyst catalyst
Check that reactor is inside and outside without leak source before loading catalyst catalyst, tubulation inwall is clean, dry, no-sundries；Will
Catalyst of the present invention is encased in each tubulation of reactor immediately after opening packaging, and loading catalyst will be completed in 0.5h, sincerely
Moisture proof.
（2）Preheating
It is passed through 90~100 DEG C of drying HCl, 7~8m of speed control3/ h, continuous 8~10h, during which every 2h by reactor
Put acid once in bottom.
（3）Synthesis vinyl chloride thereof is reacted
The molar ratio of acetylene, hydrogen chloride is controlled 1：1.1~1：1.3（100% purity）, preheated temperature is up to 90 DEG C
Mixed gas above is passed through reactor, and culture period 1 month adjusts acetylene gas intake, control according to reactor cooling capacity
Temperature processed is between 110~125 DEG C；After culture period terminates, acetylene gas intake is adjusted according to reactor cooling capacity（30~
50h-1）, by reaction temperature control at 130 DEG C.
Catalyst of the present invention is used for vinyl chloride synthesis reaction, and conversion of alkyne reaches 99.90-99.91%, vinyl chloride selectivity
Up to 99.9-100%, the yield of vinyl chloride reaches 94.2-94.5%, catalyst long service life, up to 8500 hours.
" mass space velocity " of the present invention, is defined as：The mass flow of mercury chloride（㎏·h-1）The quality of/activated carbon
（kg）.
Unless otherwise indicated, the percentage employed in the present invention is percetage by weight, ratio of the present invention,
For mass ratio.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Art personnel are it should be appreciated that the present invention is not limited to the above embodiments, and described in above-described embodiment and specification is explanation
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 appending claims and
Its equivalent thereof.
Claims (4)
1. a kind of preparation method of ultralow mercury catalyst for VCM synthesis, it is characterised in that：Preparation including activated carbon,
Absorption, the absorption includes Gas Phase Adsorption mercury chloride and liquid phase adsorption collaboration accelerator；
The ultralow mercury catalyst, the adsorbing chlorinated mercury in activated carbon center, obtained ultralow mercury catalyst is with percentage by weight
Meter, chloride containing mercury 0.93-1.0%, zinc chloride 2.4-2.5%, barium chloride 1.2-2.5%, tetrabutylammonium chloride 1.2-3.75%, dichloro
Four ammonia palladium 1.25-2.4%, water 0.2%；
The Gas Phase Adsorption mercury chloride includes first stage Gas Phase Adsorption, the first stage Gas Phase Adsorption, and control pressure is
0.6-0.7MPa, temperature is 540-560 DEG C, and mass space velocity is 7h-1, adsorb 15min；
The Gas Phase Adsorption mercury chloride include second stage Gas Phase Adsorption, the second stage Gas Phase Adsorption, being depressurized to pressure is
0.4-0.5 MPa, temperature is 420-440 DEG C, and mass space velocity is 8h-1, adsorb 10min；
The Gas Phase Adsorption mercury chloride include phase III Gas Phase Adsorption, the phase III Gas Phase Adsorption, boosting to pressure is
0.7-0.8 MPa, temperature is 560-570 DEG C, and mass space velocity is 6h-1, adsorb 5min.
2. a kind of preparation method of ultralow mercury catalyst for VCM synthesis according to claim 1, its feature exists
In the Gas Phase Adsorption mercury chloride, the content for controlling mercury chloride is 1.0-1.1%.
3. a kind of preparation method of ultralow mercury catalyst for VCM synthesis according to claim 1, its feature exists
In, the liquid phase adsorption, including immersion absorption, the immersion absorption, soaked 2 hours under 120-125 DEG C of temperature conditionss,
Dried under 110 DEG C of temperature conditionss to aqueous less than 0.2%.
4. a kind of preparation method of ultralow mercury catalyst for VCM synthesis according to claim 1, its feature exists
In, the liquid phase adsorption, including vacuum infiltration absorption, the vacuum infiltration absorption, vacuumize, reach -0.035 ~ -0.038MPa
30s is kept after pressure, then is recovered to normal pressure, in soaking 5min under normal pressure.
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| CN201710442649.2A CN107376998B (en) | 2015-10-27 | 2015-10-27 | Preparation method of ultralow-mercury catalyst for catalyzing acetylene and hydrogen chloride to synthesize vinyl chloride |
| CN201510703909.8A CN105233875B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of ultralow mercury catalyst for VCM synthesis |
| CN201710443693.5A CN107321389B (en) | 2015-10-27 | 2015-10-27 | Preparation method of ultralow-mercury catalyst for catalytic synthesis of chloroethylene |
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| CN110841666A (en) * | 2019-12-02 | 2020-02-28 | 新晃新中化工有限责任公司 | Preparation method of ultralow-mercury catalyst for vinyl chloride synthesis |
| CN114272885A (en) * | 2021-12-28 | 2022-04-05 | 厦门中科易工化学科技有限公司 | Tower reactor for synthesizing chloroethylene and application thereof |
| CN115532281A (en) * | 2022-09-28 | 2022-12-30 | 宁夏新龙蓝天科技股份有限公司 | Non-noble metal mercury-free catalyst for synthesizing chloroethylene and preparation method thereof |
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| CN1067594A (en) * | 1991-06-11 | 1993-01-06 | 贵州汞矿 | Method for preparing mercuric chloride catalyst |
| CN102380407A (en) * | 2011-08-25 | 2012-03-21 | 成都惠恩精细化工有限责任公司 | Low-mercury catalyst for acetylene hydrochlorination |
| CN103551139A (en) * | 2013-11-17 | 2014-02-05 | 那风换 | Ultralow-mercury catalyst and production process thereof |
| CN103816944A (en) * | 2014-01-20 | 2014-05-28 | 云南契合投资有限公司 | Environment-friendly continuous production process for low-mercury catalyst and device thereof |
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| CN100363101C (en) * | 2006-03-01 | 2008-01-23 | 那风换 | Composite metal chloride catalyst and its production process |
| CN101890360B (en) * | 2010-08-05 | 2012-07-25 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
| CN102151573B (en) * | 2011-01-21 | 2012-10-03 | 南开大学 | Preparation method of low-mercury catalyst for preparing vinyl chloride |
| CN102500421B (en) * | 2011-11-02 | 2013-04-17 | 天津海驰化工科技有限公司 | Preparation method of low-mercury compound catalyst for producing vinyl chloride |
| EP2617698A1 (en) * | 2012-06-27 | 2013-07-24 | Solvay Sa | Process for the hydrohalogenation of an unsaturated hydrocarbon and for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN102962082A (en) * | 2012-11-26 | 2013-03-13 | 中昊(大连)化工研究设计院有限公司 | Low-mercury catalyst used for synthesizing vinyl chloride |
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| CN1067594A (en) * | 1991-06-11 | 1993-01-06 | 贵州汞矿 | Method for preparing mercuric chloride catalyst |
| CN102380407A (en) * | 2011-08-25 | 2012-03-21 | 成都惠恩精细化工有限责任公司 | Low-mercury catalyst for acetylene hydrochlorination |
| CN103551139A (en) * | 2013-11-17 | 2014-02-05 | 那风换 | Ultralow-mercury catalyst and production process thereof |
| CN103816944A (en) * | 2014-01-20 | 2014-05-28 | 云南契合投资有限公司 | Environment-friendly continuous production process for low-mercury catalyst and device thereof |
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| CN107376998B (en) | 2020-03-13 |
| CN107376998A (en) | 2017-11-24 |
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