CN105233875A - Preparation method for ultralow-mercury catalyst for vinyl chloride synthesis - Google Patents
Preparation method for ultralow-mercury catalyst for vinyl chloride synthesis Download PDFInfo
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- CN105233875A CN105233875A CN201510703909.8A CN201510703909A CN105233875A CN 105233875 A CN105233875 A CN 105233875A CN 201510703909 A CN201510703909 A CN 201510703909A CN 105233875 A CN105233875 A CN 105233875A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title abstract description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 52
- 239000012071 phase Substances 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 37
- 238000010521 absorption reaction Methods 0.000 claims description 33
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 25
- 230000008595 infiltration Effects 0.000 claims description 6
- 238000001764 infiltration Methods 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 16
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011592 zinc chloride Substances 0.000 abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 abstract description 8
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 abstract description 7
- 229910001626 barium chloride Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 6
- 229960002523 mercuric chloride Drugs 0.000 abstract 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 abstract 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 239000003463 adsorbent Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 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
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000002817 coal dust Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000008569 process Effects 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
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 150000002730 mercury Chemical class 0.000 description 4
- 230000007420 reactivation Effects 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000007935 neutral effect Effects 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
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 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
- 238000001514 detection method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000002791 soaking 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
- 230000002194 synthesizing effect Effects 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
- 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit 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
- 230000008859 change Effects 0.000 description 1
- KZIKDWMVGLXOTB-UHFFFAOYSA-N chloranylethene Chemical compound ClC=C.ClC=C KZIKDWMVGLXOTB-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 medical industry Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000003595 mist 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
- 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
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 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
- 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
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
- B01J37/0201—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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A provided preparation method for an ultralow-mercury catalyst for vinyl chloride synthesis comprises preparation of active carbon and adsorption, and the adsorption step comprises a gas phase adsorbs mercuric chloride and a liquid phase adsorbs a synergic promoter. The prepared ultralow-mercury catalyst comprises, in percent by weight, 0.93-1.0% of mercuric chloride, 2.4-2.5% of zinc chloride, 1.2-2.5% of barium chloride, 1.2-3.75% of tetrabutyl ammonium chloride, 1.25-2.4% of tetraamminepalladium dichloride, and 0.2% of water. The catalyst possesses the mechanical strength of 96.6-96.9%, the granularity of 3-6 mm (97-97.5%) and the bulk density of 500-505 g/L. The prepared ultralow-mercury catalyst is applied to vinyl chloride synthesis reaction, the acetylene conversion rate is 99.90-99.91%, the vinyl chloride selectivity is 99.9-100%, and the vinyl chloride yield is 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 technical field.
Background technology
The polyvinyl chloride (PVC) synthesized by VCM, is one of thermoplastic articles raw material that output is maximum in the world, is widely used in the fields such as materials for construction, packaging material, electric equipment products, medical industry, coating and adhesive.
The suitability for industrialized production of current synthesizing chloroethylene monomer is in the world based on ethylene process.By the impact that crude oil price fluctuation is larger, produce PVC by acetylene through hydrochlorinate and occupy critical role at home.Industrial at present acetylene hydrochlorination reaction, mainly use mercury chloride load capacity be 12% ~ 15% high mercury catalyst, it accounts for 60% of domestic mercury use amount to the consumption of mercury, and causes serious harm to the health of environment and the mankind.
For the rare of mercury resource and the pollution to environment, and day by day severe both at home and abroad to mercury pollution prevention and control policy, in the urgent need to haveing breakthrough in the improvement of mercury chloride performance and the research of high-performance environment protection type catalyst, while meeting industrial production needs, significantly reduce mercury resource consumption and to the pollution of environment and human health and harm.
Existing low-mercury catalyst, has the following disadvantages:
(1) mercury content is high;
(2) service life is short;
(3) catalytic performance is poor, and for vinyl chloride synthesis reaction, conversion of alkyne is less than 99.8%, and vinyl chloride vinyl chloride is selective and yield is low.
Summary of the invention
The present invention is the deficiency solving prior art existence, provides a kind of preparation and mercury recovery method thereof of the ultralow mercury catalyst for VCM synthesis, to realize following goal of the invention:
(1) the ultralow mercury catalyst prepared of the present invention, the adsorbing chlorinated mercury in active carbon center, obtained ultralow mercury catalyst 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%, dichloro four ammonia palladium 1.25-2.4%, water 0.2%, mechanical strength 96.6-96.9%, granularity 3 ~ 6mm(97-97.5%), bulk density 500-505g/l.
(2) the ultralow mercury catalyst prepared of the present invention, catalyst long service life.
(3) catalyst prepared of the present invention is for vinyl chloride synthesis reaction, and conversion of alkyne reaches 99.90-99.91%, and vinyl chloride is selective reaches 99.9-100%, and the yield of vinyl chloride reaches 94.2-94.5%.
For solving above technical problem, the present invention by the following technical solutions:
For a preparation method for the ultralow mercury catalyst of VCM synthesis, comprise the preparation of active carbon, absorption, described absorption comprises Gas Phase Adsorption mercury chloride and liquid phase adsorption works in coordination with promoter.
Below the further improvement to technique scheme:
Described Gas Phase Adsorption mercury chloride comprises first stage Gas Phase Adsorption, described first stage Gas Phase Adsorption, and controlled pressure is 0.6-0.7MPa, and temperature is 540-560 DEG C, and mass space velocity is 7h
-1, absorption 15min.
Described Gas Phase Adsorption mercury chloride comprises second stage Gas Phase Adsorption, described second stage Gas Phase Adsorption, and being depressurized to pressure is 0.4-0.5MPa, and temperature is 420-440 DEG C, and mass space velocity is 8h
-1, absorption 10min.
Described Gas Phase Adsorption mercury chloride comprises phase III Gas Phase Adsorption, described phase III Gas Phase Adsorption, and boosting to pressure is 0.7-0.8MPa, and temperature is 560-570 DEG C, and mass space velocity is 6h
-1, absorption 5min.
Described Gas Phase Adsorption mercury chloride, the content controlling mercury chloride is 1.0-1.1%.
Described liquid phase adsorption, comprises and soaks absorption, and described immersion absorption, soaks 2 hours, under the temperature conditions of 110 DEG C, be dried to moisture less than 0.2% under the temperature conditions of 120-125 DEG C.
Described liquid phase adsorption, comprises vacuum infiltration absorption, and described vacuum infiltration absorption, vacuumizes, keep 30s, then return to normal pressure after reaching-0.035 ~-0.038MPa pressure, under normal pressure, soak 5min.
adopt above technical scheme, beneficial effect of the present invention is:
(1) the ultralow mercury catalyst prepared of the present invention, the adsorbing chlorinated mercury in active carbon center, obtained ultralow mercury catalyst 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%, dichloro four ammonia palladium 1.25-2.4%, water 0.2%, mechanical strength 96.6-96.9%, granularity 3 ~ 6mm(97-97.5%), bulk density 500-505g/l.
(2) the ultralow mercury catalyst prepared of the present invention, catalyst long service life, reaches 8500 hours.
(3) catalyst prepared of the present invention is for vinyl chloride synthesis reaction, and conversion of alkyne is 99.90-99.91%, and vinyl chloride is selective is 99.9-100%, and the yield of vinyl chloride is 94.2-94.5%.
Detailed description of the invention
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
embodiment 1 one kinds is for the preparation method of the ultralow mercury catalyst of VCM synthesis
the preparation of step 1, active carbon
(1) selection of feed coal
Described feed coal is anthracite, and moisture is 6%, and content of ashes is 8.5%, and volatile matter content is 14.5%, and fixed carbon content is 71%.
(2) deliming of feed coal
Ground by anthracite, cross 100 mesh sieves, coal dust is put into the polymeric aluminum chlorides solution of 30ppm, strong agitation, rotating speed is 5000r/min, and after 2 minutes, rotating speed is reduced to 500r/min, stirs after 10 minutes, filters, and distilled water is washed till filtrate in neutral; Add in polyacrylamide solution, polyacrylamide concentration is 0.5ppm, and rotating speed is 400r/min, stirs after 10 minutes, filters, and distilled water is washed till filtrate in neutral, and after deliming, content of ashes is 1.5%.
(3) carbonize
By the coal dust through deliming, be under the protection of 20ml/mim at N2 flow, carbonize, carbonization temperature initial temperature is 300 DEG C, with the heating rate of 2 DEG C/min, rises to 400 DEG C, carbonizes 2.5 hours, obtains carbonized material.
(4) once activate
By charing after coal dust acid dip, described acid, comprising: phosphoric acid, tartaric acid, the stearic acid of 60%, and mass ratio is 3:1:2, acid with coal dust in fixed carbon mass ratio be 3:1, soaks 5 hours, washing, drying.
(5) re-activation
Coal dust after once activating, be placed in the mixed liquor of re-activation agent, soak 2 hours, described re-activation agent is zinc chloride, bismuth chloride, magnesium chloride, plumbi nitras, mass ratio is 3:2:1:1, the mass ratio of re-activation agent and fixed carbon is 1:0.8, is then 10ml/mim at N2 flow, at 480 DEG C, activates 2 hours.
(6) post processing
Activated material is come out of the stove after cooling and is cooled to room temperature, put into mass percentage be 4% hydrochloric acid solution soak 12 hours, distilled water flushing, to neutral, is dried.
The active carbon iodine number 1250mg/g of preparation, methylene blue value 135mg/g, mesoporous reaches 97.5%, and Penetrating curve is 120%, moisture content 2%, ash 1.5%, fixed carbon content are 75%, mechanical strength 98%, bulk density 398g/L, specific area are 1950m
2/ g, average pore size is 2.7-3.1nm.
the preparation of step 2, carrier
(1) hydrochloric acid solution is prepared
With the hydrochloric acid solution 500 kilograms that high purity hydrochloric acid and desalted water preparation mass fraction are 0.5%, normal temperature is placed, for subsequent use;
(2) active carbon is processed
Selected 100 kilograms of active carbons are put in the hydrochloric acid solution (1) prepared and soak 30 minutes, period uses circulating pump that hydrochloric acid solution is constantly flowed, then take out and filter or be filtered dry with centrifuge drying dehydration, under the temperature conditions of 200 DEG C, be dried to moisture less than 3%, obtained carrier.
the preparation of step 3, collaborative promoter adsorption liquid
The hydrochloric acid solution of 15% of pH=3 is prepared with hydrochloric acid and desalted water, add appropriate collaborative promoter, the mass content of collaborative promoter is 10%, and collaborative promoter comprises: zinc chloride, barium chloride, tetrabutylammonium chloride, dichloro four ammonia palladium, mass ratio is: 2:1:1:2.
step 4, absorption
(1) Gas Phase Adsorption mercury chloride
A, pre-treatment
To load in adsorbent bed through pretreated active carbon, high-purity mercury chloride is carried out heating and gasifying, and the mercury chloride of gas phase enters into the adsorbent bed that active carbon is housed, and first uses nitrogen purge system, discharges the foreign gas such as oxygen, carbon dioxide,
B, first stage Gas Phase Adsorption
Controlled pressure is 0.6MPa, and temperature is 540 DEG C, and mass space velocity is 7h
-1, condenser is equipped with in adsorbent bed upper end, reenters adsorbent bed and adsorb after condensate liquid gasifies again, after absorption 15min;
C, second stage Gas Phase Adsorption
Carry out step-down process, after step-down, in adsorbent bed, pressure is 0.4MPa, and temperature is 420 DEG C, and mass space velocity is 8h
-1, absorption 10min;
D, phase III Gas Phase Adsorption
Carry out boosting process again, after boosting, in adsorbent bed, pressure is 0.7MPa, and temperature is 560 DEG C, and mass space velocity is 6h
-1, absorption 5min, as a circulation, after this circulation completes, repeats this circulation, and the Hg chloride content of period detection of active charcoal absorption, the content controlling mercury chloride is 1.0%, stops absorption.
(2) liquid phase adsorption works in coordination with promoter
A, immersion absorption
Absorbent charcoal carrier after Gas Phase Adsorption mercury chloride is put in the collaborative promoter adsorption liquid that step 3 prepares, the mass ratio of absorbent charcoal carrier and adsorption liquid is 1:5, soak 2 hours under the temperature conditions of 120 DEG C, period uses circulating pump that adsorbent solution is constantly flowed, then take out and filter or be filtered dry with centrifuge drying dehydration, put into baking oven, under the temperature conditions of 110 DEG C, be dried to moisture less than 0.2%;
B, vacuum infiltration adsorb
Then the absorbent charcoal carrier through soaking absorption is put into collaborative promoter adsorption liquid again, the mass ratio of absorbent charcoal carrier and adsorption liquid is 1:4, put into stainless-steel vacuum tank again, with vacuum pump evacuation, after reaching-0.035MPa pressure, keep 30s, return to normal pressure again, under normal pressure, soak 5min again, then take out and filter or be filtered dry with centrifuge drying dehydration, put into baking oven, moisture less than 0.2% is dried to, obtained ultralow mercury catalyst under the temperature conditions of 110 DEG C.
Ultralow mercury catalyst prepared by the present invention, the adsorbing chlorinated mercury in active 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%, dichloro four ammonia palladium 2.4%, water 0.2%, mechanical strength 96.6%, granularity 3 ~ 6mm(97%), bulk density 500g/l.
embodiment 2 one kinds is for the preparation method of the ultralow mercury catalyst of VCM synthesis
Adopt the preparation method of embodiment 1, the parameter of change is as follows:
the preparation of step 3, collaborative promoter adsorption liquid
The hydrochloric acid solution of 16% of pH=2.5 is prepared with hydrochloric acid and desalted water, add appropriate collaborative promoter, the mass content of collaborative promoter is 12%, and collaborative promoter comprises: zinc chloride, barium chloride, tetrabutylammonium chloride, dichloro four ammonia palladium, mass ratio is: 2:2:3:1.
step 4, absorption
(1) Gas Phase Adsorption mercury chloride
A, pre-treatment
To load in adsorbent bed through absorbent charcoal carrier, high-purity mercury chloride is carried out heating and gasifying, the mercury chloride of gas phase enters into the adsorbent bed that active carbon is housed, and first uses nitrogen purge system, discharges the foreign gas such as oxygen, carbon dioxide;
B, first stage Gas Phase Adsorption
Then controlled pressure is 0.7MPa, and temperature is 560 DEG C, and mass space velocity is 7h
-1, condenser is equipped with in adsorbent bed upper end, reenters adsorbent bed and adsorb after condensate liquid gasifies again, absorption 15min;
C, second stage Gas Phase Adsorption
Carry out step-down process, after step-down, in adsorbent bed, pressure is 0.5MPa, and temperature is 440 DEG C, and mass space velocity is 8h
-1, absorption 10min;
D, phase III Gas Phase Adsorption
Carry out boosting process again, after boosting, in adsorbent bed, pressure is 0.8MPa, and temperature is 570 DEG C, and mass space velocity is 6h
-1, absorption 5min, as a circulation, after this circulation completes, repeats this circulation, and the Hg chloride content of period detection of active charcoal absorption, the content controlling mercury chloride is 1.1%.
(2) liquid phase adsorption works in coordination with promoter
A, immersion absorption
Absorbent charcoal carrier after Gas Phase Adsorption mercury chloride is put in the collaborative promoter adsorption liquid that step 3 prepares, the mass ratio of absorbent charcoal carrier and adsorption liquid is 1:5, soak 2 hours under the temperature conditions of 125 DEG C, period uses circulating pump that adsorbent solution is constantly flowed, then take out and filter or be filtered dry with centrifuge drying dehydration, put into baking oven, under the temperature conditions of 110 DEG C, be dried to moisture less than 0.2%;
B, vacuum infiltration adsorb
Then the absorbent charcoal carrier through soaking absorption is put into again the collaborative promoter adsorption liquid that step 3 is prepared, the mass ratio of absorbent charcoal carrier and adsorption liquid is 1:5, put into stainless-steel vacuum tank again, with vacuum pump evacuation, after reaching-0.038MPa pressure, keep 30s, return to normal pressure again, under normal pressure, soak 5min again, then take out and filter or be filtered dry with centrifuge drying dehydration, put into baking oven, moisture less than 0.2% is dried to, obtained ultralow mercury catalyst under the temperature conditions of 110 DEG C.
Ultralow mercury catalyst prepared by the present invention, the adsorbing chlorinated mercury in active 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%, dichloro four ammonia palladium 1.25%, water 0.2%, mechanical strength 96.9%, granularity 3 ~ 6mm(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 before loading catalyst catalyst that reactor is inside and outside without leak source, tubulation inwall is clean, dry, no-sundries; Be encased in immediately after catalyst of the present invention is opened packaging in each tubulation of reactor, loading catalyst will complete in 0.5h, guard against damp.
(2) preheating
Pass into the dry HCl of 90 ~ 100 DEG C, speed control 7 ~ 8m
3/ h, continuous 8 ~ 10h, period puts acid once every 2h by reactor bottom.
(3) synthesizing chloroethylene reaction
The molar ratio of acetylene, hydrogen chloride is controlled in 1:1.1 ~ 1:1.3(100% purity), the mist that to reach more than 90 DEG C through preheat temperature passes into reactor, culture period 1 month, regulate acetylene gas intake according to reactor cooling capacity, control temperature is between 110 ~ 125 DEG C; After culture period terminates, regulate acetylene gas intake (30 ~ 50h according to reactor cooling capacity
-1), reaction temperature is controlled 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%, and vinyl chloride is selective reaches 99.9-100%, and the yield of vinyl chloride reaches 94.2-94.5%, and catalyst long service life reaches 8500 hours.
" mass space velocity " of the present invention, is defined as: the mass flow (㎏ h of mercury chloride
-1the quality (kg) of)/active carbon.
Except as otherwise noted, the percentage adopted in the present invention is percetage by weight, and ratio of the present invention, is mass ratio.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (7)
1. for a preparation method for the ultralow mercury catalyst of VCM synthesis, it is characterized in that: comprise the preparation of active carbon, absorption, described absorption comprises Gas Phase Adsorption mercury chloride and liquid phase adsorption works in coordination with promoter.
2. the preparation method of a kind of ultralow mercury catalyst for VCM synthesis according to claim 1, it is characterized in that, described Gas Phase Adsorption mercury chloride comprises first stage Gas Phase Adsorption, described first stage Gas Phase Adsorption, controlled pressure is 0.6-0.7MPa, temperature is 540-560 DEG C, and mass space velocity is 7h
-1, absorption 15min.
3. the preparation method of a kind of ultralow mercury catalyst for VCM synthesis according to claim 1, it is characterized in that, described Gas Phase Adsorption mercury chloride comprises second stage Gas Phase Adsorption, described second stage Gas Phase Adsorption, being depressurized to pressure is 0.4-0.5MPa, temperature is 420-440 DEG C, and mass space velocity is 8h
-1, absorption 10min.
4. the preparation method of a kind of ultralow mercury catalyst for VCM synthesis according to claim 1, it is characterized in that, described Gas Phase Adsorption mercury chloride comprises phase III Gas Phase Adsorption, described phase III Gas Phase Adsorption, boosting to pressure is 0.7-0.8MPa, temperature is 560-570 DEG C, and mass space velocity is 6h
-1, absorption 5min.
5. the preparation method of a kind of ultralow mercury catalyst for VCM synthesis according to claim 1, is characterized in that, described Gas Phase Adsorption mercury chloride, and the content controlling mercury chloride is 1.0-1.1%.
6. the preparation method of a kind of ultralow mercury catalyst for VCM synthesis according to claim 1, it is characterized in that, described liquid phase adsorption, comprise and soak absorption, described immersion absorption, soak 2 hours under the temperature conditions of 120-125 DEG C, under the temperature conditions of 110 DEG C, be dried to moisture less than 0.2%.
7. the preparation method of a kind of ultralow mercury catalyst for VCM synthesis according to claim 1, it is characterized in that, described liquid phase adsorption, comprise vacuum infiltration absorption, described vacuum infiltration absorption, vacuumizes, keeps 30s after reaching-0.035 ~-0.038MPa pressure, return to normal pressure again, under normal pressure, soak 5min.
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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 |
| 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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| CN108043467A (en) * | 2017-11-27 | 2018-05-18 | 宁夏新龙蓝天科技股份有限公司 | Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof |
| 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 |
| 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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| 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 |
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| CN107321389A (en) | 2017-11-07 |
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