CN108211813B - Has GO/TiO2PPS microporous membrane of additive and low-temperature denitration catalytic membrane - Google Patents
Has GO/TiO2PPS microporous membrane of additive and low-temperature denitration catalytic membrane Download PDFInfo
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- CN108211813B CN108211813B CN201810146873.1A CN201810146873A CN108211813B CN 108211813 B CN108211813 B CN 108211813B CN 201810146873 A CN201810146873 A CN 201810146873A CN 108211813 B CN108211813 B CN 108211813B
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- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 239000000654 additive Substances 0.000 title claims abstract description 80
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 61
- 230000000996 additive effect Effects 0.000 title claims abstract description 60
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 41
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 55
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 50
- 239000011593 sulfur Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 239000003085 diluting agent Substances 0.000 claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 101
- 238000002360 preparation method Methods 0.000 claims description 47
- 230000002209 hydrophobic effect Effects 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 11
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- 238000003490 calendering Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001826 dimethylphthalate Drugs 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910016978 MnOx Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- FHESUNXRPBHDQM-UHFFFAOYSA-N diphenyl benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OC=2C=CC=CC=2)=CC=1C(=O)OC1=CC=CC=C1 FHESUNXRPBHDQM-UHFFFAOYSA-N 0.000 claims description 3
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001462 antimony Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004108 freeze drying Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 5
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 238000002791 soaking Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 7
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000004690 nonahydrates Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- 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
- Y02P20/30—Improvements relating to adipic acid or caprolactam production
Abstract
The invention provides a catalyst with GO/TiO2The PPS microporous membrane comprises, by mass, 10-60% of polyphenylene sulfide, 30-80% of a composite diluent and 0.1-20% of GO/TiO, and is a low-temperature denitration catalytic membrane of an additive2And (3) an additive. The problem of poisoning and inactivation of the existing low-temperature SCR catalyst is solved, and the catalytic membrane with the water-resistant and sulfur-resistant functions is prepared. The combination of water vapor and the catalyst can be effectively limited through the high porosity, the high specific surface area, the good solvent resistance, the environmental resistance and the hydrophobicity of the polyphenylene sulfide film, a high-performance carrier is provided for the catalyst, and TiO is loaded2The graphene oxide modifies a matrix, SO that the matrix has good sulfur resistance, and a multifunctional catalytic membrane capable of effectively inhibiting the generation of ammonium sulfate and ammonium bisulfate on the surface of the catalyst is obtained, and further the multifunctional catalytic membrane can resist SO2The activity of the catalyst is damaged, and the service life of the catalyst is prolonged.
Description
Technical Field
The invention belongs to the technical field of preparation of catalytic membranes, and particularly relates to a catalyst containing GO/TiO2PPS microporous membrane of additive and low-temp. denitration catalytic membrane.
Background
At present, the energy structure of China is mainly based onCoal energy is the main energy, and the combustion of a large amount of coal can generate nitrogen oxides which mainly comprise NO and NO2、N2O, etc. can cause acid rain and acid mist, can form photochemical smog by combining with hydrocarbon, damage the atmospheric ozone layer, aggravate the eutrophication of the water body through the effect of dry and wet sedimentation, and simultaneously can influence the respiratory system of the human body. In recent years, the total amount of NOx discharged in China is huge and is in a continuous increasing situation, so that the development of a safe, green, efficient and stable treatment method for nitrogen oxides is particularly important, wherein a Selective Catalytic Reduction (SCR) technology has high denitration efficiency, is mature in technology and free of secondary pollution, and is increasingly applied in China.
In the selective catalytic reduction technology, the catalyst is the key of catalytic efficiency, however, in the current commercial catalyst, the activity of the catalyst can be generally exerted above 350 ℃, and for the power station boiler, the denitration reaction is carried out at the temperature, the denitration device must be arranged in front of the dust remover, and the position has high concentration of dust and SO2Easily cause catalyst poisoning, greatly reduced the efficiency and the life of denitration to need preheating treatment, make energy consumption and equipment economic cost improve. On the other hand, the activity of the catalyst is an important factor affecting the performance of the catalyst, and there are many factors affecting the activity thereof, among which water vapor and SO2Is prone to compete with NOx and catalyst binding renders the catalyst inactive.
Although research on low temperature SCR catalysts is ongoing, it is always difficult to solve the problem of catalyst life, and therefore, the development of a catalyst having low temperature activity with sulfur-resistant hydrophobicity is the key to improve this technology.
Disclosure of Invention
In view of the above, the present invention is directed to a composition having GO/TiO2The PPS microporous membrane and the low-temperature denitration catalytic membrane of the additive solve the problem of poisoning and inactivation of the existing low-temperature SCR catalyst, and prepare the catalytic membrane with water-resistant and sulfur-resistant functions. The polyphenylene sulfide film has high porosity, high specific surface area, good solvent resistance, environmental resistance and hydrophobicity, and can effectively limit water vapor and catalystBy supporting TiO, a high performance support for the catalyst2The graphene oxide modifies a matrix, SO that the matrix has good sulfur resistance, and a multifunctional catalytic membrane capable of effectively inhibiting the generation of ammonium sulfate and ammonium bisulfate on the surface of the catalyst is obtained, and further the multifunctional catalytic membrane can resist SO2The activity of the catalyst is damaged, and the service life of the catalyst is prolonged.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
has GO/TiO2The PPS microporous membrane of the additive is prepared from the following raw materials, by mass, 10-60 wt% of polyphenylene sulfide, 30-80 wt% of a composite diluent and 0.1-20 wt% of GO/TiO2And (3) an additive.
The invention also provides a method for preparing the GO/TiO composite material2The preparation method of the PPS microporous membrane of the additive comprises the following steps,
1) 10-60 wt% of polyphenylene sulfide, 30-80 wt% of composite diluent and 0.1-20 wt% of GO/TiO2Uniformly mixing the additives;
2) heating the mixed solution obtained in the step 1) to 230-270 ℃ under the protection of inert gas, reacting for 15-60 min, and defoaming to obtain a membrane casting solution;
3) pouring the casting solution obtained in the step 2) into a mold preheated to 230-270 ℃ for calendaring and forming to form a film by the casting solution;
4) after solidification, the solidified film is placed in an extracting agent capable of dissolving the composite diluent to dissolve out the composite diluent, and GO/TiO is prepared2PPS microporous membranes of additives.
Preferably, the TiO is formed by blending, sol-gel, hydrothermal/solvothermal or self-assembled processes2Loading the graphene oxide on the surface of graphene oxide; preferably, the graphene oxide is prepared by a hydrothermal method, and the preparation method comprises the following steps of ultrasonically dispersing a certain mass of graphene oxide in ethanol at room temperature, adding acid, deionized water, ammonium sulfate and tetrabutyl titanate, and stirring for 2-5 hours; the obtained mixed solution is moved into a hydrothermal kettle to react for 10-30 h at a constant temperature of 160-220 ℃; the product was then washed to neutrality with ethanol and deionized waterFreeze drying the prepared sample for 6-24 hours to obtain GO/TiO2An additive;
wherein, 0.02-0.04 ml of tetrabutyl titanate is added into each mg of graphene oxide.
Preferably, the composite diluent is formed by mixing a main diluent and 0-20 wt% of an auxiliary solvent; the main diluent comprises one or more than two of caprolactam, diphenyl sulfone, benzophenone, diphenyl ether, benzoin, diphenyl isophthalate, hydrogenated terphenyl, cyclohexyl pyrrolidone, benzil ketone and the like;
the auxiliary solvent comprises one or more of dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate and dioctyl adipate.
Preferably, in the step 1), the polyphenylene sulfide accounts for 20-30% of the total mass of the mixture of the polyphenylene sulfide and the composite diluent; the extractant in the step 2) comprises one or more than two of methanol, ethanol, glycol, propanol, acetone, distilled water or glycerol; in the step 4), the curing condition is that the curing is carried out in air at room temperature, or the curing is carried out in a water bath at room temperature, or the curing is carried out in an ice-water mixture.
The graphene has ultrahigh electron mobility and excellent electric conductivity, and the electron characteristics of the graphene can greatly promote the transfer of electrons in the oxidation-reduction process, so that the activity of the catalyst is effectively improved; TiO22The existence of the catalyst can effectively accelerate electron transfer, thereby limiting the generation of ammonium sulfate and ammonium bisulfate on the surface of the catalyst and improving the sulfur resistance of the catalyst; the polyphenylene sulfide is a hydrophobic material which is resistant to high temperature, solvents and acid and alkali corrosion, and can effectively resist the adsorption and aggregation of water vapor in the pore canal, so that the water resistance of the catalyst is improved.
Adding TiO into the mixture2The catalyst is loaded on graphene oxide, a polyphenylene sulfide microporous membrane matrix is mixed in, and then the SCR composite catalyst is loaded on the inner wall of a microporous membrane pore channel, so that the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane can be prepared
The invention also provides a catalyst containing GO/TiO as described above2PPS microporous membrane with additive or GO/TiO microporous membrane prepared by preparation method2The PPS microporous membrane of the additive is applied to the preparation of a catalytic membrane.
The invention also provides a sulfur-resistant hydrophobic polymer low-temperature denitration catalytic membrane, which comprises the following preparation steps,
1) placing the composite nano SCR catalyst in ethanol, and ultrasonically dispersing to obtain a stable catalyst suspension;
2) the composition of claim 1 having GO/TiO dried by impregnation2PPS microporous membrane with additive or GO/TiO microporous membrane prepared by the preparation method of any one of claims 2-52Soaking the PPS microporous membrane of the additive in the catalyst suspension prepared in the step 1), roasting the soaked membrane in a muffle furnace at the temperature of 150-250 ℃ for 2-12 hours, and quickly cooling after roasting to obtain the sulfur-resistant hydrophobic polymer low-temperature denitration catalytic membrane.
Preferably, the composite nano SCR catalyst consists of a main catalyst and 0-50 wt% of an auxiliary catalyst, wherein the main catalyst is MnOx, and the auxiliary catalyst comprises one or a mixture of several oxides of iron, copper, nickel, cobalt, silver, antimony and cerium in any proportion.
The invention also provides a sulfur-resistant hydrophobic polymer low-temperature denitration catalytic membrane, which comprises the following preparation steps,
1) preparing a manganese salt and a transition metal salt into a mixed solution; preferably, the transition metal salt comprises one or more of transition metal salts such as iron salt, copper salt, nickel salt, cobalt salt, antimony salt, cerium salt and the like;
2) the composition of claim 1 having GO/TiO dried by impregnation or sol-gel process2PPS microporous membrane with additive or GO/TiO microporous membrane prepared by the preparation method of any one of claims 2-52Soaking the PPS microporous membrane of the additive in the mixed solution prepared in the step 1), roasting the soaked membrane in a muffle furnace at the temperature of 150-250 ℃ for 2-12 hours, and cooling after roasting is finished to obtain the sulfur-resistant hydrophobic polymer low-temperature denitration catalytic membrane.
The invention also provides application of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane in removing nitric oxides by SCR.
Compared with the prior art, the invention has GO/TiO2The PPS microporous membrane and the low-temperature denitration catalytic membrane of the additive have the following advantages:
(1) the invention increases the sulfur resistance and water resistance of the catalyst through the catalyst carrier, and prepares the low-temperature SCR denitration catalytic membrane with the characteristics of sulfur resistance and water resistance. The catalytic film has the characteristics of high porosity, large specific surface area, excellent mechanical property, excellent heat resistance and chemical corrosion resistance and the like; by adding the compound of the graphene oxide and the titanium dioxide, the mechanical property, the catalytic activity and the service life of the catalytic membrane are improved.
(2) The high-temperature-resistant, solvent-resistant and acid-alkali corrosion-resistant hydrophobic material polyphenylene sulfide is used as a catalyst carrier, and a TIPS process is adopted to prepare the microporous membrane with uniform pore diameter, high porosity, large specific surface area and good mechanical property, so that the contact surface area and flexibility of the catalyst carrier are improved.
(3) The graphene oxide with ultrahigh electron mobility and excellent conductivity is compounded with titanium dioxide, so that the activity and the sulfur resistance of the catalytic membrane are improved.
(4) MnOx is used as a main catalyst, and other transition metals are used as auxiliary catalysts, and the auxiliary catalysts are loaded on a modified porous hydrophobic polymer membrane to prepare the low-temperature SCR denitration catalytic membrane with the characteristics of sulfur resistance and water resistance, so that the service life and the catalytic efficiency of the SCR catalyst are effectively improved.
Drawings
FIG. 1 is the GO/TiO melt prepared by hydrothermal method in example 12SEM photograph of additive.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
(1)GO/TiO2Preparation of the additives
Preparation of GO/TiO by hydrothermal method2Adding 150mg of graphite oxide into 40mL of ethanol, performing ultrasonic dispersion for 2 hours, adding 20mL of hydrochloric acid, 10mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate, and stirring for 3 hours; transferring the obtained mixed solution into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃, washing the product to be neutral by using ethanol and deionized water, and finally drying at the temperature of 60 ℃ to obtain GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
6g of caprolactam, 1.5g of dibutyl sebacate, 2.4g of polyphenylene sulfide and 0.1g of the above-mentioned GO/TiO2Adding an additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, reacting at the temperature of 255 ℃, defoaming for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a mold preheated to 260 ℃, calendaring and forming, curing, placing the cured membrane into ethanol to remove a composite diluent, and preparing the GO/TiO composite membrane with the characteristics of high strength, high toughness and low cost2PPS microporous membranes of additives.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
Weighing 0.4mol of manganese acetate tetrahydrate and 0.2mol of ferric nitrate nonahydrate, placing the materials in 40ml of absolute ethyl alcohol, stirring for 1 hour to form a homogeneous mixed solution, and adopting an impregnation method to pre-dry the mixture with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared mixed solution, standing for 1 hour, then placing the soaked membrane in a 200 ℃ muffle furnace for roasting for 5 hours, and cooling after roasting is finished to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the removal efficiency of NO at 150-250 ℃ can reach more than 90 percent, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane can be kept above 85% for a long time.
Example 2
(1)GO/TiO2Preparation of the additives
Preparation of GO/TiO by hydrothermal method2Adding 50mg of graphite oxide into 40mL of ethanol, performing ultrasonic dispersion for 2 hours, adding 20mL of hydrochloric acid, 10mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate, and stirring for 3 hours; transferring the obtained mixed solution into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃, washing the product to be neutral by using ethanol and deionized water, and finally drying at the temperature of 60 ℃ to obtain GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
5.5g of caprolactam, 1.5g of dibutyl sebacate, 2.5g of polyphenylene sulfide and 0.5g of the above-mentioned GO/TiO2Adding an additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, reacting at the temperature of 255 ℃, defoaming for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a mold preheated to 260 ℃, calendaring and forming, curing, placing the cured membrane into ethanol to remove a composite diluent, and preparing the GO/TiO composite membrane with the characteristics of high strength, high toughness and low cost2PPS microporous membranes of additives.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
Weighing 0.4mol of manganese acetate tetrahydrate, 0.1mol of nonahydrate, ferric nitrate and 0.1mol of tetrahydrate and cerium nitrate, placing the materials in 40ml of absolute ethyl alcohol, stirring for 1 hour to form a homogeneous mixed solution, and adopting an impregnation method to pre-dry the mixture with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared mixed solution, standing for 1 hour, then placing the soaked membrane in a 200 ℃ muffle furnace for roasting for 5 hours, and cooling after roasting is finished to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the NO removal efficiency can reach more than 92% at 150-250 ℃, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane can be kept above 88% for a long time.
Example 3
(1)GO/TiO2Preparation of the additives
Preparation of GO by hydrothermal method/TiO2Adding 150mg of graphite oxide into 40mL of ethanol, performing ultrasonic dispersion for 2 hours, adding 20mL of hydrochloric acid, 10mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate, and stirring for 3 hours; transferring the obtained mixed solution into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃, washing the product to be neutral by using ethanol and deionized water, and finally drying at the temperature of 60 ℃ to obtain GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
5g of caprolactam, 2.2g of dibutyl sebacate, 2g of polyphenylene sulfide and 0.8g of the above-mentioned GO/TiO2Adding the additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, reacting at the temperature of 255 ℃, defoaming for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a mold preheated to 260 ℃ for calendaring and forming, curing, placing the cured membrane into ethanol, removing the composite diluent, and preparing the PPS microporous membrane with the GO/TiO2 additive.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
MnOx, Fe with a molar ratio of 4:1:12O3、CeO2Placing the composite catalyst with the particle size of 50nm in 40ml of absolute ethyl alcohol for ultrasonic dispersion for 2 hours to form turbid liquid, and adopting an impregnation method to pre-dry the mixed solution with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared suspension, standing for 1 hour, roasting the soaked membrane in a 200-DEG C muffle furnace for 5 hours, and cooling after roasting to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the removal efficiency of NO at 150-250 ℃ can reach more than 93 percent, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane can be kept above 90% for a long time.
Example 4
(1)GO/TiO2Preparation of the additives
Preparation of GO/TiO by hydrothermal method2Adding 100mg of graphite oxide into 40mL of ethanol, ultrasonically dispersing for 2 hours, adding 20mL of hydrochloric acid and 1Stirring for 3 hours after 0mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate; transferring the obtained mixed solution into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃, washing the product to be neutral by using ethanol and deionized water, and finally drying at the temperature of 60 ℃ to obtain GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
6g of caprolactam, 0.4g of dibutyl sebacate, 3.5g of polyphenylene sulfide and 0.1g of the above-mentioned GO/TiO2Adding an additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, reacting at the temperature of 255 ℃, defoaming for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a mold preheated to 260 ℃, calendaring and forming, curing, placing the cured membrane into ethanol to remove a composite diluent, and preparing the GO/TiO composite membrane with the characteristics of high strength, high toughness and low cost2PPS microporous membranes of additives.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
Weighing 0.4mol of manganese acetate tetrahydrate, 0.2mol of nonahydrate and ferric nitrate, placing the mixture in 40ml of absolute ethyl alcohol, stirring for 1 hour to form a homogeneous mixed solution, and adopting an impregnation method to pre-dry the mixture with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared mixed solution, standing for 1 hour, roasting the soaked membrane in a muffle furnace at 250 ℃ for 2 hours, and cooling after roasting to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the removal efficiency of NO at 150-250 ℃ can reach more than 90 percent, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane is kept above 83% for a long time.
Example 5
(1)GO/TiO2Preparation of the additives
Preparation of GO/TiO by hydrothermal method2Adding 150mg of graphite oxide into 40mL of ethanol, performing ultrasonic dispersion for 2 hours, adding 20mL of hydrochloric acid, 10mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate, and stirring for 3 hours; the obtained mixed solution is moved into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃,then washing the product to neutrality by using ethanol and deionized water, and finally drying at 60 ℃ to prepare GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
6g of caprolactam, 1.5g of dimethyl phthalate, 2.4g of polyphenylene sulfide and 0.1g of the above-mentioned GO/TiO2Adding an additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, reacting at the temperature of 255 ℃, defoaming for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a mold preheated to 260 ℃, calendaring and forming, curing, placing the cured membrane into ethanol to remove a composite diluent, and preparing the GO/TiO composite membrane with the characteristics of high strength, high toughness and low cost2PPS microporous membranes of additives.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
Weighing 0.4mol of manganese acetate tetrahydrate, 0.2mol of nonahydrate and ferric nitrate, placing the mixture in 40ml of absolute ethyl alcohol, stirring for 1 hour to form a homogeneous mixed solution, and adopting an impregnation method to pre-dry the mixture with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared mixed solution, standing for 1 hour, then placing the soaked membrane in a muffle furnace at 150 ℃ for roasting for 6 hours, and cooling after roasting is finished to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the removal efficiency of NO at 150-250 ℃ can reach more than 90 percent, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane is kept above 85% for a long time.
Example 6
(1)GO/TiO2Preparation of the additives
Preparation of GO/TiO by hydrothermal method2Adding 150mg of graphite oxide into 40mL of ethanol, performing ultrasonic dispersion for 2 hours, adding 20mL of hydrochloric acid, 10mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate, and stirring for 3 hours; transferring the obtained mixed solution into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃, washing the product to be neutral by using ethanol and deionized water, and finally drying at the temperature of 60 ℃ to obtain GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
6g of diphenylsulfone, 1.5g of dimethyl phthalate, 2.4g of polyphenylene sulfide and 0.1g of the above-mentioned GO/TiO2Adding an additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, reacting at the temperature of 255 ℃, defoaming for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a mold preheated to 260 ℃, calendaring and forming, curing, placing the cured membrane into ethanol to remove a composite diluent, and preparing the GO/TiO composite membrane with the characteristics of high strength, high toughness and low cost2PPS microporous membranes of additives.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
Weighing 0.4mol of manganese acetate tetrahydrate and 0.2mol of ferric nitrate nonahydrate, placing the materials in 40ml of absolute ethyl alcohol, stirring for 1 hour to form a homogeneous mixed solution, and adopting an impregnation method to pre-dry the mixture with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared mixed solution, standing for 1 hour, then placing the soaked membrane in a 200 ℃ muffle furnace for roasting for 5 hours, and cooling after roasting is finished to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the removal efficiency of NO at 150-250 ℃ can reach more than 90 percent, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane can be kept above 85% for a long time.
Example 7
(1)GO/TiO2Preparation of the additives
Preparation of GO/TiO by hydrothermal method2Adding 150mg of graphite oxide into 40mL of ethanol, performing ultrasonic dispersion for 2 hours, adding 20mL of hydrochloric acid, 10mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate, and stirring for 3 hours; transferring the obtained mixed solution into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃, washing the product to be neutral by using ethanol and deionized water, and finally drying at the temperature of 60 ℃ to obtain GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
6g of benzophenone and 1.5g of phthalic acid bis (tert-butyl ether)Butyl ester, 2.4g polyphenylene sulfide and 0.1g of the above GO/TiO2Adding an additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, reacting at the temperature of 255 ℃, defoaming for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a mold preheated to 260 ℃, calendaring and forming, curing, placing the cured membrane into ethanol to remove a composite diluent, and preparing the GO/TiO composite membrane with the characteristics of high strength, high toughness and low cost2PPS microporous membranes of additives.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
Weighing 0.4mol of manganese acetate tetrahydrate and 0.2mol of ferric nitrate nonahydrate, placing the materials in 40ml of absolute ethyl alcohol, stirring for 1 hour to form a homogeneous mixed solution, and adopting an impregnation method to pre-dry the mixture with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared mixed solution, standing for 1 hour, then placing the soaked membrane in a 200 ℃ muffle furnace for roasting for 5 hours, and cooling after roasting is finished to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the removal efficiency of NO at 150-250 ℃ can reach more than 90 percent, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane can be kept above 85% for a long time.
Example 8
(1)GO/TiO2Preparation of the additives
Preparation of GO/TiO by hydrothermal method2Adding 150mg of graphite oxide into 40mL of ethanol, performing ultrasonic dispersion for 2 hours, adding 20mL of hydrochloric acid, 10mL of deionized water, 0.36g of ammonium sulfate and 4.3mL of tetrabutyl titanate, and stirring for 3 hours; transferring the obtained mixed solution into a hydrothermal kettle for constant temperature reaction for 24 hours at the reaction temperature of 180 ℃, washing the product to be neutral by using ethanol and deionized water, and finally drying at the temperature of 60 ℃ to obtain GO/TiO2And (3) an additive.
(2) With GO/TiO2Preparation of PPS microporous membrane of additive
6g of diphenyl ether, 1.5g of dioctyl adipate, 2.4g of polyphenylene sulfide and 0.1g of the above-mentioned GO/TiO2Adding the additive into a 100mL flask, heating and stirring for 20 minutes under the protection of nitrogen, and reacting at the temperature of 2Defoaming at 55 ℃ for 10 minutes to obtain a membrane casting solution, pouring the membrane casting solution into a die preheated to 260 ℃ for calendaring and forming, curing, placing the cured membrane in ethanol to remove a composite diluent, and preparing the product with GO/TiO2PPS microporous membranes of additives.
(3) Preparation of sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane
Weighing 0.4mol of manganese acetate tetrahydrate and 0.2mol of ferric nitrate nonahydrate, placing the materials in 40ml of absolute ethyl alcohol, stirring for 1 hour to form a homogeneous mixed solution, and adopting an impregnation method to pre-dry the mixture with GO/TiO2And (3) soaking the PPS microporous membrane of the additive in the prepared mixed solution, standing for 1 hour, then placing the soaked membrane in a 200 ℃ muffle furnace for roasting for 5 hours, and cooling after roasting is finished to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane.
Tests show that the removal efficiency of NO at 150-250 ℃ can reach more than 90 percent, and 300ppm of SO is introduced at 200 DEG C2And 10% of water vapor, the removal rate of NO of the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane can be kept above 85% for a long time.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane is characterized in that: comprises the following preparation steps of the preparation method,
1) placing the composite nano SCR catalyst in ethanol, and ultrasonically dispersing to obtain a stable catalyst suspension;
2) drying the product with GO/TiO by impregnation2Dipping a PPS microporous membrane of the additive into the catalyst suspension prepared in the step 1), roasting the dipped membrane in a muffle furnace at the temperature of 150-250 ℃ for 2-12 hours, and quickly cooling after roasting to obtain the sulfur-resistant hydrophobic polymer low-temperature denitration catalytic membrane;
the catalyst has GO/TiO2The PPS microporous membrane of the additive comprises the following mass fractionsThe composite material is prepared from 10-60 wt% of polyphenylene sulfide, 30-80 wt% of composite diluent and 0.1-20 wt% of GO/TiO2An additive; GO/TiO2In the preparation of the additive, 0.01-0.1 ml of tetrabutyl titanate is added into each mg of graphene oxide; the composite diluent is formed by mixing a main diluent and 0-20 wt% of an auxiliary solvent; the main diluent comprises one or more than two of caprolactam, diphenyl sulfone, benzophenone, diphenyl ether, benzoin, diphenyl isophthalate, hydrogenated terphenyl, cyclohexyl pyrrolidone and benzoin;
the auxiliary solvent comprises one or more of dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate and dioctyl adipate; the polyphenylene sulfide accounts for 20-30% of the total mass of the mixture of the polyphenylene sulfide and the composite diluent.
2. The sulfur-resistant hydrophobic polymeric low-temperature denitration catalytic membrane of claim 1, wherein: the catalyst has GO/TiO2The PPS microporous film of the additive is prepared by the following steps,
a) 10-60 wt% of polyphenylene sulfide, 30-80 wt% of composite diluent and 0.1-20 wt% of GO/TiO2Uniformly mixing the additives;
b) heating the mixed solution obtained in the step a) to 230-270 ℃ under the protection of inert gas, reacting for 15-60 min, and defoaming to obtain a membrane casting solution;
c) pouring the casting solution obtained in the step b) into a mold preheated to 230-270 ℃ for calendaring and forming to form a film by the casting solution;
d) after solidification, the solidified film is placed in an extracting agent capable of dissolving the composite diluent to dissolve out the composite diluent, and GO/TiO is prepared2PPS microporous membranes of additives.
3. The sulfur-resistant hydrophobic polymeric low-temperature denitration catalytic membrane of claim 1, wherein: by blending, sol-gel, hydrothermal/solvothermal or self-assembling the TiO2And loading the graphene oxide on the surface of the graphene oxide.
4. The sulfur-resistant hydrophobic polymeric low-temperature denitration catalytic membrane of claim 1, wherein: TiO22Preparing a load on the surface of graphene oxide by a hydrothermal method, and comprises the following steps of ultrasonically dispersing a certain mass of graphene oxide in ethanol at room temperature, adding acid, deionized water, ammonium sulfate and tetrabutyl titanate, and stirring for 2-5 hours; the obtained mixed solution is moved into a hydrothermal kettle to react for 10-30 h at a constant temperature of 160-220 ℃; then washing the product to be neutral by using ethanol and deionized water, and freeze-drying the prepared sample for 6-24 hours to obtain GO/TiO2An additive;
wherein, 0.02-0.04 ml of tetrabutyl titanate is added into each mg of graphene oxide.
5. The sulfur-resistant hydrophobic polymeric low-temperature denitration catalytic membrane of claim 2, wherein: the extractant in the step d) comprises one or more than two of methanol, ethanol, glycol, propanol, acetone, distilled water or glycerol; in step d), the curing condition is that the curing is carried out in air at room temperature, or the curing is carried out in a water bath at room temperature, or the curing is carried out in an ice-water mixture.
6. The sulfur-resistant hydrophobic polymeric low-temperature denitration catalytic membrane of claim 1, wherein: the composite nano SCR catalyst consists of a main catalyst and 0-50 wt% of an auxiliary catalyst, wherein the main catalyst is MnOx, and the auxiliary catalyst comprises one or a mixture of several oxides of iron, copper, nickel, cobalt, silver, antimony and cerium in any proportion.
7. The sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane is characterized in that: comprises the following preparation steps of the preparation method,
1) preparing a manganese salt and a transition metal salt into a mixed solution; the transition metal salt comprises one or a mixture of more of iron salt, copper salt, nickel salt, cobalt salt, antimony salt and cerium salt;
2) by impregnationDrying with GO/TiO by sol-gel method2Dipping the PPS microporous membrane of the additive into the mixed solution prepared in the step 1), roasting the dipped membrane in a muffle furnace at the temperature of 150-250 ℃ for 2-12 hours, and cooling after roasting to obtain the sulfur-resistant hydrophobic high-molecular low-temperature denitration catalytic membrane;
the catalyst has GO/TiO2The PPS microporous membrane of the additive is prepared from the following raw materials, by mass, 10-60 wt% of polyphenylene sulfide, 30-80 wt% of a composite diluent and 0.1-20 wt% of GO/TiO2An additive; GO/TiO2In the preparation of the additive, 0.01-0.1 ml of tetrabutyl titanate is added into each mg of graphene oxide; the composite diluent is formed by mixing a main diluent and 0-20 wt% of an auxiliary solvent; the main diluent comprises one or more than two of caprolactam, diphenyl sulfone, benzophenone, diphenyl ether, benzoin, diphenyl isophthalate, hydrogenated terphenyl, cyclohexyl pyrrolidone and benzoin;
the auxiliary solvent comprises one or more of dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate and dioctyl adipate; the polyphenylene sulfide accounts for 20-30% of the total mass of the mixture of the polyphenylene sulfide and the composite diluent.
8. The application of the sulfur-resistant hydrophobic polymer low-temperature denitration catalyst film as defined in any one of claims 1 to 7 in removing nitrogen oxides by SCR.
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| CN109301133B (en) * | 2018-10-05 | 2020-09-04 | 中山大学 | Preparation method of diaphragm for high-safety and high-energy-density lithium ion battery |
| CN109224635A (en) * | 2018-10-12 | 2019-01-18 | 东南大学 | A kind of compound cryosar denitration and the PPS filtrate of demercuration function and preparation method thereof |
| CN109248711B (en) * | 2018-10-15 | 2021-08-13 | 天津工业大学 | Loaded TiO (titanium dioxide)2Preparation method of PPS photocatalytic film |
| CN113828278A (en) * | 2021-10-29 | 2021-12-24 | 辽宁基伊能源科技有限公司 | Efficient denitration agent for waste gas treatment and preparation method thereof |
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