CN112427032B - Catalyst for catalyzing and burning vinyl chloride to polymerize wet-containing tail gas and preparation method thereof - Google Patents
Catalyst for catalyzing and burning vinyl chloride to polymerize wet-containing tail gas and preparation method thereof Download PDFInfo
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- CN112427032B CN112427032B CN201910788701.9A CN201910788701A CN112427032B CN 112427032 B CN112427032 B CN 112427032B CN 201910788701 A CN201910788701 A CN 201910788701A CN 112427032 B CN112427032 B CN 112427032B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000010955 niobium Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 229960000892 attapulgite Drugs 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 23
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 230000000536 complexating effect Effects 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 38
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011698 potassium fluoride Substances 0.000 claims description 14
- 235000003270 potassium fluoride Nutrition 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910001729 niobium mineral Inorganic materials 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 125000001153 fluoro group Chemical class F* 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 238000012795 verification Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 35
- 239000000460 chlorine Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 229910052801 chlorine Inorganic materials 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- -1 Carbon dioxide Carbon monoxide Methyl chloride Nitrogen Chemical compound 0.000 description 10
- CXAFSGPCNGYTOZ-UHFFFAOYSA-N chloroethene hydrate Chemical compound O.ClC=C CXAFSGPCNGYTOZ-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 231100000572 poisoning Toxicity 0.000 description 9
- 230000000607 poisoning effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000006298 dechlorination reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000007429 general method Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J37/0207—Pretreatment of the support
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a catalyst for catalyzing and incinerating wet tail gas containing vinyl chloride, which comprises the following preparation steps: (1) preparing active component doped precursor, dissolving mineral containing transition metal niobium with acid, adding fluosalt, fluoridizing and complexing to obtain doped precursor K2[NbOF5](ii) a (2) Preparing doped active component, MnO mixing with doped precursor K2[NbOF5]Mixing, controlling the pH value, adding alkali for coprecipitation to generate an active component emulsion; (3) preparing and modifying a carrier, namely modifying the attapulgite of the carrier by using a modifier solution containing a silane coupling agent; (4) loading active component, vacuum immersing the emulsion of active component, calcining for shaping, and calcining for passivating. Proved by verification on an incineration platform, the catalyst prepared by the method has good effect of catalytic incineration of the wet tail gas containing the chloroethylene.
Description
Technical Field
The invention belongs to the field of chemical tail gas treatment, and particularly relates to a catalyst for catalyzing and incinerating vinyl chloride to polymerize wet tail gas and a preparation method thereof.
Background
The reaction conversion rate of polyvinyl chloride generated by vinyl chloride polymerization is about 80%, and the rest unreacted vinyl chloride is released from a polymerization kettle after the polymerization reaction is finished. For the treatment of the chlorine-containing tail gas (containing chlorine volatile organic compounds, CVOCs, containing a certain amount of moisture), the common practice in industry is to condense and recycle the tail gas, and then send the uncondensed gas to an incinerator for high-temperature incineration (above 1100 ℃), so that the energy consumption is high, and harmful substances such as CO, formaldehyde, formic acid, phosgene and the like can be generated to cause secondary pollution.
The CVOCs can be removed by a direct burning method, a catalytic hydrogenation and dechlorination method, a catalytic steam reforming method, a photocatalytic oxidation method, a catalytic combustion method and the like. Of these, catalytic combustion is the most economical and environmentally friendly. A plurality of related catalysts with certain activity, selectivity and stability have been developed. For such catalysts, the active component is generally selected from Mn, Cu, Cr, Fe and V oxides; the support is generally SiO2、ZrO2、CexZr-xO2Solid solution, SiO2、γ-Al2O3And zeolites, metal honeycombs, woven metal meshes, and the like, and among them, catalysts in which a molecular sieve and a woven metal mesh carrier are used as a carrier have been studied in many cases. However, due to improper selection of the carrier and the auxiliary agent, the problems of poor selectivity of the catalyst to a certain component, poor resistance to poisoning (active site deactivation), insufficient oxidation capacity and the like are easily caused, and the situation of poor catalytic effect is frequently seen.
Therefore, many scholars screen and verify active components or carriers in a large quantity, and some scholars dope simple substances or improve carriers on the active components to achieve the excellent catalysis purpose; weili (Master university paper, Tianjin university, 2007.06) examines the catalyst activity with VOx and/or WOx as active components, and proves that the catalyst has good carbon deposition resistance and chlorine poisoning resistance, but the selectivity of the catalyst is low. The result shows that the manganese-cerium oxide has better catalytic capability to common hydrocarbons CVOCs such as ethane, propane, normal hexane, benzene, toluene and the like or single component CVOC (dichloroethane). The catalytic effect of aqueous multicomponent CVOCs was not evaluated in depth.
CN201710423251 discloses a non-coated metal matrix monolithic catalyst carrier/catalyst, wherein the catalyst is a carrier, and a porous alumina layer is loaded with 0-10 wt% of noble metal elements. Can be applied to the catalytic combustion purification of the chlorine-containing volatile organic compounds such as DCM, o-DCB and the like in the waste gas in the field of atmospheric environmental protection. CN 107626327A provides a catalyst for dechlorination of carbon tetrachloride by passing through Al2O3The modified activated carbon is used as a carrier, Pt and metal M are used as active components, and the metal M is any one or more than two of Cr, Mn, Co and Ba. In both of the above patents, noble metals are used as active components, and although the amount used is not large, the cost is still high for industrial exhaust gas applications. CN109107567A discloses M-MnOX-CeO2Catalyst with MnOX、CeO2As an active component, FeOx, CuO, CoOx or K2O is taken as a dopant, one of cordierite and spherical 4A or 13X molecular sieves is taken as a carrier, and the generated catalyst can be used for catalytic oxidation of gaseous formaldehyde under the normal temperature condition or thermal catalytic oxidation of CVOCs by adjusting a proper proportion. The invention considers the oxide doping of the active component, but still uses a single carrier, and the actual effect on the thermal catalysis of CVOCs is unknown.
In conclusion, dechlorination catalysts are researched more and more, the effect is different after the active components or carriers are changed, and the influence of the preparation process is also very critical. At present, a dechlorination catalyst with high catalytic activity, strong anti-poisoning capability and good economical efficiency and excellent comprehensive performance is difficult to prepare.
Disclosure of Invention
The reason why the existing dechlorination catalyst has problems is that: the catalytic reaction of CVOCs is divided into dehalogenation reaction and oxidation reaction, wherein the dehalogenation reaction is a control step and is determined by the acid position B or the acid position L of the active center of the catalyst, and the number of the acid positions influences the catalytic activity. In the actual catalytic reaction process, on one hand, the active center is easily covered due to carbon deposition of the active center, and reactant molecules cannot approach the acid site of B, so that the loss of the function of the acid site of B (namely, alkali poisoning) is one of the reasons for catalyst deactivation. On the other hand, the generated Cl reacts with active components (such as Cl-Mn, Cl-V combination), and the reduction of active components (i.e. chlorine poisoning) is another cause of the catalyst deactivation. In the support aspect, if the support is not properly selected, not only does it not provide a large active surface, but it may also increase the manufacturing cost of the industrial catalyst.
Aiming at the problems and reasons of the prior dechlorination catalyst, the invention aims to provide a preparation method of a catalyst for catalyzing and incinerating vinyl chloride to polymerize wet tail gas, and the catalyst obtained by the method has the advantages of high catalytic activity, obvious dechlorination effect, strong poisoning resistance, low carrier cost and special water-resistant effect.
In order to achieve the above purpose and achieve the above technical effects, the technical solution of the present invention is as follows:
a preparation method of a catalyst for catalyzing and incinerating vinyl chloride to polymerize wet tail gas comprises the following steps:
(1) preparing an active component doped precursor: dissolving mineral containing metal niobium with acid, adding fluorine salt, fluorinating and complexing to obtain doped precursor K2[NbOF5]；
(2) Preparing a doped active component: mixing active component MnO with doped precursor K2[NbOF5]Mixing, controlling the pH value, adding alkali for coprecipitation to generate active component emulsion;
(3) preparing and modifying a carrier: modifying a carrier Attapulgite (ATP) with a modifier solution containing a silane coupling agent;
(4) loading active components: vacuum soaking the modified carrier with the active component emulsion, roasting to form, deactivating with steam, cooling and other steps.
In the present invention, the metal-containing niobium mineral in the step (1) is refined niobium mineral, such as Nb2O5Refined niobium ore grade 36.48 wt%, the mineral dissolving acid being hydrofluoric acid, e.g. a 40 wt% hydrofluoric acid solution, and the fluoride salt being potassium fluoride, e.g. a 40 wt% potassium fluoride solution, wherein the niobium concentrate: hydrofluoric acid: the mass ratio of the potassium fluoride is 1 (3-5) to 0.8-1.
In the step (1), a transition metal element niobium is added, the niobium reacts with fluorine at room temperature, reacts with chlorine, hydrogen and air at about 200 ℃, reacts with hydrogen and nitrogen at about 400 ℃, is directly combined with sulfur, nitrogen and carbon at high temperature (>400 ℃), and can resist the corrosion of molten alkali and various acids. Therefore, at about 200 ℃, Cl generated by dechlorinating the chlorine-containing tail gas is firstly selected to react with niobium, and active elements (such as Mn) are not consumed; at high temperature (>400 ℃), carbon deposition generated by chlorine-containing organic matters is combined with niobium, so that the carrier can be well protected, and the carbon deposition is prevented from being attached to an active site, therefore, the addition of niobium can play a positive protection role on both the active component and the carrier, and meanwhile, the catalyst is prevented from being inactivated by alkali poisoning and chlorine poisoning.
In the invention, in the step (2), the active component MnO and the doped precursor K are2[NbOF5]Mixing according to the weight ratio of (10-50) g to 300 g; adding excess NH4And controlling the pH value of OH to be 8-10. The blend prepared by the stepThe mixed active component contains niobium hydroxide, MnO, etc. and is a mixed emulsion.
In the invention, ATP used for modification in the step (3) is 200-300 mesh components, and the modifier solution comprises ethanol, hydrofluoric acid, aluminum nitrate, magnesium nitrate and a silane coupling agent in a volume ratio of 4:1:2:2: 1; the ratio of the dosage of the modifier solution to ATP is (1-2) L:100 g; the modification process is stirring for 30-60 min at 45-75 ℃, and drying at 90-110 ℃ after modification.
In the step (3), because ATP is a natural magnesium-aluminum-rich silicate clay mineral, the structural unit of ATP contains a large amount of SiO which can be used as a catalyst carrier2MgO and gamma-Al2O3And is a natural mineral with a nano-channel structure. ATP is cheap and rich, has a large specific surface area, an excellent pore structure and ion exchange property, can effectively improve the effective active site of an acid catalyst in a catalytic reaction, is easy to regulate and control surface acidity, and has good adsorption performance. The preparation process of ATP powder in the step refers to a general method for preparing powder in patent CN 102794169B. Specifically, the attapulgite flakes are obtained by pre-stacking and homogenizing clay, mixing with water, and extruding and shearing with a roller or multiple rollers (this process is intended to disaggregate and disperse ATP crystal bundles). Then, the sheet-like material is dried and pulverized.
In the step (3), the modifier functions as follows: under a mutual dissolving system established by ethanol, a small amount of hydrofluoric acid plays a proper role in reducing silicon; the introduction of aluminum nitrate and magnesium nitrate can adjust the Si/Mg ratio and the Si/Al ratio, and the aim is to optimize the molecular structure of the carrier.
In the invention, the silane coupling agent in the step (3) is one or more of KH550, KH560, 570, Si-69 and LM-N308. The silane coupling agent is used for improving the wettability of the surface of the carrier, and the main principle is that silane is grafted with carrier molecules to enable the surface of the carrier to generate hydrophobic groups, so that the hydrophobic effect is achieved, and the 'water-resistant' effect is achieved when the water-containing organic matter is catalytically incinerated.
In the invention, when dipping is carried out in the step (4), the proportion of the doped active component emulsion to the modified carrier is (200-300) ml:100g, and the dipping time is 5-8 h. In the dipping process, the mixture is placed in a water bath environment of 80 ℃ for shaking so as to ensure that emulsion particles are fully contacted with the carrier, and the mixture is taken out for natural draining after dipping.
In the step (4), during the dipping process, colloidal particles (with negative charges) formed by the modified ATP in the solution interact with metal ion (Nb) hydrolysis hydroxide (with positive charges) in the active component emulsion, so that the doped active component is uniformly loaded on the surface of the modified ATP.
In the invention, the step (4) is roasted for 7-10 h at 550-700 ℃, air containing water vapor is introduced for passivation in the roasting stage, and the concentration of the water vapor is less than 800ppm based on the mass of the air containing the water vapor. The roasting process of the step is finished in a muffle furnace, and the roasting is naturally cooled to finish the preparation of the catalyst.
In the step (4), after the calcination, the doped active component is firmly combined with the carrier. After firing, Nb is converted from hydroxide to oxide structure (Nb)2O5) At this time, the passivation with water vapor (oxide with crystal water) of not more than 800ppm is used to form the niobic acid structure (Nb)2O5·nH2O), the surface of the niobic acid contains a B acid center (Nb-OH) and a coordination unsaturated L acid center (Nb)5 +)。Nb2O5The strength of B acid on the surface is greater than that of B acid on the surface of MnO, when the doping amount is increased, the proportion of Mn-O-Mn and Mn-O-Nb species is reduced, and the proportion of Nb-O-Nb species is increased.
Moreover, through the steam passivation step, the resistance effect of the catalyst on the moisture in the tail gas is enhanced again, and the catalytic effect is obviously enhanced.
Further, Nb contained in the calcined catalyst2O5The active element Mn is not easy to generate electron transfer and lose due to strong interaction with Mn metal, so that the electron cloud density of Mn is increased.
Another object of the present invention is to provide a catalyst prepared by the above preparation method.
A catalyst for tail gas incineration treatment is prepared by the preparation method.
The invention has the following positive effects:
(1) the doped active component prepared by introducing the metal niobium effectively prevents the loss of the active component and the carbon deposition of the active site, improves the anti-poisoning capability of the catalyst, and simultaneously avoids the alkali poisoning inactivation and the chlorine poisoning inactivation of the catalyst.
(2) A modified attapulgite carrier is selected, so that a larger active surface or acid site is provided, and meanwhile, the acid center of the catalyst B is enhanced through a water vapor passivation step, so that the activity of the catalyst is improved.
(3) The catalyst has good dechlorination effect on wet CVOCs, and can reduce chloroethylene in chloroethylene incineration tail gas to 20-41ppm and reduce chloromethane to 1-16 ppm.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention.
The sources of the raw materials and the reagents of the catalyst of the invention are detailed in the following table 1, and the reagents are all analytically pure (AR).
TABLE 1 catalyst raw materials and reagents
The catalytic incineration pilot plant is designed by itself, and relevant design parameters and evaluation conditions are detailed in the following table 2. The evaluation tail gas comes from a laboratory small-scale polymerization kettle, and the composition and the content are detailed in the following table 3. The related component analysis adopts Agilent 7890B type gas chromatography, a four-valve six-column sample injection system, and the test standard is GB/T16088-1995 chloroethylene direct sample injection gas chromatography determination method.
TABLE 2 incineration plant parameters
TABLE 3 composition of chlorine-containing tail gas
| Composition (I) | Vinyl chloride | Water (I) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| The content wt% | 62 | 1.8 | 15 | 6 | 0.2 | 15 |
Example 1
(1) Preparing an active component doped precursor: taking 100g of refined niobium ore, adding 40 wt% hydrofluoric acid solution for dissolving, adding 40 wt% potassium fluoride solution into the solution after reaction, and controlling the niobium concentrate: hydrofluoric acid: reacting for 60min at room temperature with the mass ratio of potassium fluoride of 1:3:0.8 to obtain a doped component precursor K2[NbOF5]And (3) solution.
(2) Preparing a doped active component: 10g of active component MnO is dissolved in 300g of precursor solutionThen adding NH4And (4) fully stirring and mixing OH until the pH value is controlled to be 8 for 20min to obtain the doped active component.
(3) Preparing and modifying a carrier: referring to the general method for preparing ATP powder in patent CN 102794169B example 1 (step 2-3), ATP powder with 200-300 meshes is screened out. Weighing 100g of powder, putting the powder into a water bath containing 1L of a modified solvent (the volume ratio of all substances in the solvent is ethanol: hydrofluoric acid: aluminum nitrate: magnesium nitrate: silane coupling agent is 4:1:2:2: 1; wherein the silane coupling agent is selected and the mass ratio of the silane coupling agent is KH550: KH560 is 1:1), setting the temperature at 45 ℃, magnetically heating and stirring for 30min, then cooling, filtering, washing with deionized water until the washing liquid becomes neutral, putting the washing liquid into a vacuum oven, and drying at 90 ℃ to complete the preparation of the modified carrier.
(4) Loading active components: according to the proportion of 200ml/100g of the doped active component emulsion and the modified carrier, vacuumizing and dipping for 5 hours under the condition of shaking in a water bath at 80 ℃. Taking out, draining, and roasting in a muffle furnace at 550 ℃ for 7 h. Air containing water vapor with the mass concentration of 700ppm is introduced for passivation during roasting. After roasting, the catalyst is naturally cooled, the catalyst is prepared and loaded into a catalytic incineration reactor.
The effect of catalytic incineration tail gas is shown in the following table 4:
TABLE 4 composition of chlorine-containing tail gas
| Content/ingredient | Vinyl chloride | Water (W) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 25ppm | 2％ | 83％ | 0 | 5ppm | 15％ |
Example 2
(1) Preparing an active component doped precursor: controlling the fine niobium ore: hydrofluoric acid: the mass ratio of potassium fluoride was 1:3:1, and the other conditions were the same as in example 1.
(2) Preparing a doped active component: the same as in example 1.
(3) Preparing and modifying a carrier: KH-550 was selected as the silane coupling agent, and the other conditions were the same as in example 1.
(4) Loading active components: the same as in example 1.
The effect of catalytic incineration tail gas is shown in the following table 5:
TABLE 5 composition of chlorine-containing off-gas
| Content/ingredient | Vinyl chloride | Water (I) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 27ppm | 2％ | 83％ | 0 | 8ppm | 15％ |
Example 3
(1) Preparing an active component doped precursor: 100g of the refined niobium ore is taken, added with a hydrofluoric acid solution with the concentration of 40 wt% for dissolution, a potassium fluoride solution with the concentration of 40 wt% is added into the reacted solution, and the niobium concentrate is controlled: hydrogenHydrofluoric acid: the mass ratio of the potassium fluoride is 1:4:1, and the mixture reacts for 60min at room temperature to obtain a doped component precursor K2[NbOF5]And (3) solution.
(2) Preparing a doped active component: 20g of active component MnO is dissolved in 300g of precursor solution, and then excessive NH is added4And (4) fully stirring and mixing OH until the pH value is controlled to be 9 for 20min to obtain the doped active component.
(3) Preparing and modifying a carrier: refer to patent CN 102794169B example 1 (step 2-3) general method for preparing attapulgite powder, prepare 200-300 mesh ATP powder sieve component. Weighing 100g of powder, putting the powder into a water bath containing 1.5L of a modified solvent (the volume ratio of all substances in the solvent is ethanol: hydrofluoric acid: aluminum nitrate: magnesium nitrate: silane coupling agent is 4:1:2:2: 1; the selection and mass ratio of the silane coupling agent is KH550: KH560: LM-N308 is 1:1:1), setting the temperature to be 60 ℃, magnetically heating and stirring for 45min, then cooling, filtering, washing with deionized water until the washing liquid becomes neutral, putting the washing liquid into a vacuum oven, drying at the temperature of 100 ℃, and finishing the preparation of the modified carrier.
(4) Loading active components: according to the proportion of the doped active component emulsion to the modified carrier of 270ml/100g, vacuumizing and dipping for 7 hours under the shaking condition of water bath 80 ℃. Taking out, draining, and roasting in a muffle furnace at 600 deg.C for 9 h. Air containing water vapor with the mass concentration of 700ppm is introduced for passivation during roasting. Naturally cooling, finishing the preparation of the catalyst, and loading into a catalytic incineration reactor.
The effect of catalytic incineration tail gas is shown in the following table 6:
TABLE 6 composition of chlorine-containing tail gas
| Content/ingredient | Vinyl chloride | Water (W) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 20ppm | 2％ | 83％ | 0 | 1ppm | 15％ |
Example 4
(1) Preparing an active component doped precursor: taking 100g of refined niobium ore, adding 40 wt% hydrofluoric acid solution for dissolving, adding 40 wt% potassium fluoride solution into the solution after reaction, and controlling the niobium concentrate: hydrofluoric acid: the mass ratio of the potassium fluoride is 1:5:1, and the mixture reacts for 60min at room temperature to obtain a doped component precursor K2[NbOF5]And (3) solution.
(2) Preparing a doped active component: 50g of active component MnO is dissolved in 300g of precursor solution, and then excessive NH is added4OH until pH is controlled to 10, and stirring thoroughlyMixing for 20min to obtain doped active component.
(3) Preparing and modifying a carrier: refer to patent CN 102794169B example 1 (step 2-3) general method for preparing attapulgite powder, prepare 200-300 mesh ATP powder sieve component. Weighing 100g of powder, putting the powder into a water bath containing 2L of a modified solvent (the volume ratio of all substances in the solvent is ethanol: hydrofluoric acid: aluminum nitrate: magnesium nitrate: silane coupling agent is 4:1:2:2: 1; the silane coupling agent is selected and the mass ratio is KH550: KH560: 570: 1:1), setting the temperature to be 75 ℃, magnetically heating and stirring for 60min, then cooling, filtering, washing with deionized water until the washing liquid becomes neutral, putting the washing liquid into a vacuum oven, drying at 110 ℃, and preparing the modified carrier.
(4) Loading active components: according to the proportion of the doped active component emulsion to the modified carrier of 300ml/100g, the vacuum-pumping immersion time is 8h under the condition of shaking in a water bath at 80 ℃. Taking out, draining, and roasting in a muffle furnace at 700 ℃ for 10 h. Air containing water vapor with the mass concentration of 700ppm is introduced for passivation during roasting. Naturally cooling, finishing the preparation of the catalyst, and loading into a catalytic incineration reactor.
The effect of catalytic incineration tail gas is shown in the following table 7:
TABLE 7 composition of chlorine-containing tail gas
| Content/ingredient | Vinyl chloride | Water (W) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 30ppm | 2％ | 83％ | 0 | 10ppm | 15％ |
Example 5
(1) Preparing an active component doped precursor: controlling the fine niobium ore: hydrofluoric acid: the mass ratio of potassium fluoride was 1:5:0.8, and the other conditions were the same as in example 4.
(2) Preparing a doped active component: the same as in example 4.
(3) Preparing and modifying a carrier: the selection and the mass ratio of the silane coupling agent are 570: si-69 is 1:1, other conditions are the same as in example 4.
(4) Loading active components: the same as in example 4.
The effect of catalytic incineration tail gas is shown in the following table 8:
TABLE 8 composition of chlorine-containing tail gas
| Content/ingredient | Vinyl chloride | Water (W) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 41ppm | 2％ | 83％ | 0 | 16ppm | 15％ |
Comparative example 1
(1) Preparing an active component doped precursor: 100g of MnO was added with hydrofluoric acid and potassium fluoride in the proportions described in example 3 to produce a precursor solution containing no Nb component.
(2) Preparing a doped active component: the same as in example 3.
(3) Preparing and modifying a carrier: the same as in example 3.
(4) Loading active components: the same as in example 3.
The catalytic incineration tail gas effect is shown in the following table 9 and is poorer than the effect of the embodiment 1-5 through evaluation of a small test device.
TABLE 9 composition of chlorine-containing off-gas
| Content/ingredient | Vinyl chloride | Water (W) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 235ppm | 2％ | 82.5％ | 2.4％ | 19ppm | 13％ |
Comparative example 2
(1) Preparing an active component doped precursor: the same as in example 3.
(2) Preparing a doped active component: the same as in example 3.
(3) Preparing and modifying a carrier: in the comparative example, the carrier is a 4A molecular sieve of 200-300 meshes, and the other processes are the same as those in example 3.
(4) Loading active components: the same as in example 3.
The catalytic incineration tail gas effect is shown in the following table 10 and is poorer than the effect of the embodiment 1-5 through evaluation of a small test device.
TABLE 10 chlorine-containing tail gas composition
| Content/ingredient | Vinyl chloride | Water (W) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 122ppm | 2％ | 82.7％ | 1.2％ | 16ppm | 14％ |
Comparative example 3
(1) Preparing an active component doped precursor: the same as in example 3.
(2) Preparing a doped active component: the same as in example 3.
(3) Preparing and modifying a carrier: the same as in example 3.
(4) Loading active components: the calcination process was not passivated by introducing air containing water vapor, and the other processes were the same as in example 3.
The catalytic incineration tail gas effect is shown in the following table 11 and is poorer than the effect of the examples 1-5 through evaluation of a small test device.
TABLE 11 composition of chlorine-containing tail gas
| Content/ingredient | Vinyl chloride | Water (W) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 368ppm | 2％ | 82.5％ | 2.2％ | 19ppm | 13％ |
Comparative example 4
Referring to CN109107567A example 6, the preparation method of the catalyst adopts MnO as an active component and CuO and CeO2As a dopant, the spherical 4A molecular sieve is used as a carrier, the supported CuO-MnO-CeO2 catalyst is prepared by referring to the process conditions (the molar ratio of Mn to Ce is 1:1, and the molar ratio of Cu to Ce is 1:1), and the tail gas in the invention is used for verifying the catalytic effect.
The effect of the catalytic incineration tail gas is shown in the following table 12 and is poorer than the effect of the catalytic incineration tail gas in the examples 1-5 according to the evaluation of a small test device:
TABLE 12 composition of chlorine-containing tail gas
| Content/ingredient | Vinyl chloride | Water (I) | Carbon dioxide | Carbon monoxide | Methyl chloride | Nitrogen gas |
| Content before treatment (wt) | 62％ | 1.8％ | 15％ | 6％ | 0.2％ | 15％ |
| Content after treatment (wt) | 13％ | 2％ | 69.9％ | 10ppm | 16ppm | 15％ |
It should be noted that the above examples are merely illustrative of representative embodiments of the present invention, and thus are preferred embodiments. And not to limit the scope of the invention, and although the invention has been described in detail with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made, and equivalents may be substituted for elements thereof without departing from the scope of the invention as defined in the claims.
Claims (8)
1. A preparation method of a catalyst for catalyzing and burning vinyl chloride to polymerize wet tail gas is characterized by comprising the following steps:
(1) preparing an active component doped precursor: dissolving mineral containing metal niobium with acid, adding fluorine salt, fluorinating and complexing to generate doped precursor K2[NbOF5]；
(2) Preparing a doped active component: mixing active component MnO with doped precursor K2[NbOF5]Mixing, controlling the pH value, adding alkali for coprecipitation to generate active component emulsion;
(3) preparing and modifying a carrier: modifying the attapulgite with a modifier solution containing a silane coupling agent;
(4) loading active components: vacuum dipping the modified carrier with the active component emulsion, roasting and forming, passivating with steam, cooling;
the attapulgite for modification in the step (3) is a 200-300-mesh sieve component, and the modifier solution comprises ethanol, hydrofluoric acid, aluminum nitrate, magnesium nitrate and a silane coupling agent in a volume ratio of =4:1:2:2: 1; the ratio of the amount of the modifier solution to the attapulgite is (1-2) L:100 g.
2. The method for preparing the catalyst according to claim 1, wherein the metal-containing niobium mineral in the step (1) is refined niobium mineral, the acid is hydrofluoric acid, and the fluorine salt is potassium fluoride, wherein the mass ratio of the refined niobium mineral to the hydrofluoric acid to the potassium fluoride is 1 (3-5) to (0.8-1).
3. The method for preparing a catalyst according to claim 1, wherein the active component MnO of step (2) is mixed with the doped precursor K2[NbOF5]Mixing according to the weight ratio of (10-50) g to 300 g; adding excess NH4Controlling the pH value of OH to be 8-10.
4. The preparation method of the catalyst according to claim 1, wherein the modification process in the step (3) is stirring for 30-60 min at 45-75 ℃, and drying at 90-110 ℃ after modification.
5. The method for preparing a catalyst according to claim 1, wherein the silane coupling agent in the step (3) is one or more of KH550, KH560, KH570, Si-69 and LM-N308.
6. The preparation method of the catalyst according to claim 1, wherein the ratio of the doped active component emulsion to the modified carrier is (200-300) mL:100g, and the soaking time is 5-8 h during the soaking in the step (4).
7. The preparation method of the catalyst according to claim 1, wherein the step (4) is calcined at 550-700 ℃ for 7-10 h, and air containing water vapor is introduced for passivation in the calcination stage, wherein the concentration of the water vapor is less than 800ppm based on the mass of the air containing the water vapor.
8. A catalyst for catalyzing and incinerating wet tail gas generated in vinyl chloride polymerization, which is prepared by the method for preparing the catalyst for catalyzing and incinerating wet tail gas generated in vinyl chloride polymerization according to any one of claims 1 to 7.
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