CN112871164A - 一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用 - Google Patents
一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN112871164A CN112871164A CN201911198761.1A CN201911198761A CN112871164A CN 112871164 A CN112871164 A CN 112871164A CN 201911198761 A CN201911198761 A CN 201911198761A CN 112871164 A CN112871164 A CN 112871164A
- Authority
- CN
- China
- Prior art keywords
- carrier
- catalyst
- hours
- concentration
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 30
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003057 platinum Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- VBEGUCKCABFDDF-UHFFFAOYSA-N hydroxylamine platinum Chemical compound [Pt].NO VBEGUCKCABFDDF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 10
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 41
- 239000007789 gas Substances 0.000 description 31
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002245 particle Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- 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 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical class [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000009495 sugar coating Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- -1 triphenyl compound Chemical class 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8973—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony or bismuth
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- 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
本发明专利涉及一种催化燃烧治理环境领域,尤其是一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用。催化剂由活性组分、助剂和载体组成;其中活性组分为贵金属铂,铂的含量为载体重量的0.01%~0.2%;助剂为非贵金属,非贵金属的含量为载体重量的0.5%~5%。本发明公开的催化剂具有良好的耐硫性、催化活性和稳定性,能够耐受10‑1000ppm有机硫或者H2S,并将硫化物转化为毒性较小、易于处理的SO2;同时将挥发性有机化合物转化为无毒无害的CO2和H2O,处理后的气体可达标排放。
Description
技术领域
本发明专利涉及一种催化燃烧治理环境领域,尤其是一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用。
背景技术
化工行业如炼油厂污水处理的隔油池、采油废气、精细化学品在生产中排放的废气等是主要的大气污染物排放源之一,排放废气量占我国工业废气排放总量的10%左右。其组分除了乙烯、甲烷和三苯化合物等之外,同时其释放的H2S浓度通常在数十至数万ppm,而且共存有较高浓度的硫醇、硫醚、羰基硫、二硫化碳等污染物,带来的恶臭味道严重影响厂区及周边居民的生产、生活质量,同时对大气环境造成污染、导致酸雨、温室气体增加等一系列问题,因此,我国《大气污染物综合排放标准》(GB 16297—1996)对有机物的排放作出了严格限制。
有机废气的治理方法包括吸收、吸附、冷凝、直接燃烧、热力燃烧和催化燃烧等。催化燃烧技术是一种常用的脱烃方法,可以在较低的温度下在催化剂上将废气中的可燃组分氧化分解成二氧化碳和水,达到废气净化的要求。但常规的催化燃烧催化剂活性组分为钯,钯在含硫气氛下极易失活,同时在高温下容易流失;氧化铝载体在含硫的气氛中和氧化气氛下容易硫酸盐化引起催化剂的失活,因此使用常规的燃烧催化剂需要根据硫的种类不同选取对应的脱硫剂,预先精脱硫后进入催化燃烧塔,因而增加整个治理装置的投资和操作费用,因此开发耐硫燃烧催化剂十分重要。
CN1049299A公开了一种含硫有机废气焚烧催化剂,以硫酸处理改性天然丝光沸石为载体,V2O5为主要活性组分,添加少量Pt、Pd,另外还含有少量的钴、锰、钼、镍、钾、钠氧化物中的一种或几种作助催化剂。该催化剂对含硫有机物、CO、烃类和含氧衍生物具有明显的净化效果。该专利公开的催化剂载体为天然丝光沸石,天然丝光沸石由硅铝等元素组成,在长期使用过程中,催化剂表面会逐渐硫化而使活性下降;另外,该催化剂所需反应温度高,入口温度在320℃以上才对含硫有机物有处理效果。专利CN102909020A公开了一种耐硫催化燃烧催化剂及其制备方法,催化剂只能耐受微量的H2S(30-50mg/m3)。
上述专利公开的催化剂耐硫性不足、燃烧活性难以满足《石油化学工业污染物排放标准》(GB31571-2015)和石油炼制工业污染物排放标准(GB31570-2015)中对挥发性有机物的排放指标。因而现阶段急需一种催化燃烧活性高,耐硫性强,易于放大生产的的挥发性有机化合物燃烧催化剂。
发明内容
为了克服现有技术的不足,本发明专利一种耐硫挥发性有机化合物燃烧催化剂及其制备方法。
为实现上述目的,本发明采用的技术方案为:
一种耐硫挥发性有机化合物燃烧催化剂,催化剂由活性组分、助剂和载体组成;其中活性组分为贵金属铂,铂的含量为载体重量的0.01%~0.2%;助剂为非贵金属,非贵金属的含量为载体重量的0.5%~5%。
所述非贵金属助剂为铼、铋、锡、钼、铁、钴、钨、铈、银、钾、钡、钙中的一种或几种的混合。
所述载体为二氧化钛、硅藻土、二氧化硅中的一种或两种。
所述活性组分铂选自硝酸钯、氯铂酸或羟氨铂。
所述二氧化钛粒径为200目以下,晶相为锐钛矿,比表面积在30-100m2/g;所述二氧化硅的粒径为200目以下,比表面积在100-300m2/g;硅藻土中二氧化硅的含量≥85%,粒径为200目以下,比表面积在150-300m2/g。
一种权利要求1所述的耐硫挥发性有机化合物燃烧催化剂的制备方法:
(1)载体制备:将载体与胶溶剂、造孔剂和粘结剂充分混均,混匀后制型,制型后在室温下干燥4-8小时,在100-200℃干燥2-8小时,而后在400-650℃下焙烧4-8小时,制得载体;
(2)按比例将可溶铂盐和非贵金属助剂的可溶盐混合,混合后用去离子水溶解配制成混合溶液,或,可溶铂盐和非贵金属助剂的可溶盐分别经去离子水溶解,而后混合得混合溶液;将上述载体浸入至混合溶液中,将混合溶液中倒入上述载体中进行等体积饱和浸渍,于100~200℃下干燥2~8小时,再于400~650℃下焙烧4~8小时,即得催化剂。
所述混合溶液与制得载体等体积混合浸渍。
所述催化剂经硫化后待用;其中,硫化为将所述催化剂在100-1500ppmSO2的氮气、空速500-5000h-1,在300-500℃下处理1-6小时,制得硫化后的催化剂。
所述胶溶剂为硝酸、草酸或柠檬酸;所述造孔剂为田菁粉和/或硬脂酸;所述粘结剂为铝土矿、水泥、赤泥、拟薄粉、钛酸酯、氧化钙、聚乙烯醇、羟甲基纤维素、硅溶胶、钛溶胶中的一种或两种的混合物;
所述硅溶胶和钛溶胶为酸性;其中,硅溶胶中二氧化硅含量在10-30%;钛溶胶中二氧化钛含量在15-30%。
所述非贵金属助剂的可溶盐溶液在载体成型前加入到载体的粉料中,或,在载体成型后加入到载体中。
一种耐硫挥发性有机化合物燃烧催化剂的应用,所述催化剂在含硫气氛下,对硫化物和/或挥发性有机化合物催化净化中的应用。
所述催化剂反应条件为:反应温度200-600℃,空速5000-30000h-1、压力常压~3.0MPa。
与现有技术相比,本发明的有益效果:
本发明催化剂具有良好的耐硫性、催化活性和稳定性,能够耐受10-1000ppm有机硫或者H2S,并将硫化物转化为毒性较小、易于处理的SO2;同时将挥发性有机化合物转化为无毒无害的CO2和H2O,处理后的气体可达标排放。
1.本发明的耐硫挥发性有机化合物燃烧催化剂,起活温度低,能适应较高的操作空速,且具有良好的催化活性和稳定性;本发明催化剂制备工艺简单、制造成本低、对硫含量的适应性广。
2.本发明的耐硫挥发性有机化合物燃烧催化剂,在进行高效催化有机硫化物转化时其毒性较小、容易处理SO2;本发明催化剂促进挥发性有机化合物转化为无毒无害的CO2和水,处理后的气体可达标排放。
3.本发明的耐硫挥发性有机化合物燃烧催化剂,贵金属使用量少,助剂含量低,因此制造成本低。
附图说明
图1是本发明实施例提供的催化剂测试效果图。
具体实施方式
以下结合实例和附图对本发明的具体实施方式做进一步说明,应当指出的是,此处所描述的具体实施方式只是为了说明和解释本发明,并不局限于本发明。
实施例1
称取9.2g七钼酸铵溶解于15ml去离子水中,制得溶液A。
称取90g二氧化钛、5g铝土矿、5g赤泥(铁含量大于60%)、3ml体积浓度5%稀硝酸溶液、10g羟甲基纤维素钠和上述溶液A充分混捏均匀,将混匀的混合物挤成直径φ3*4mm的条形,室温干燥8小时后在150℃干燥2小时,而后在650℃下焙烧4小时,即制得载体A。
所述二氧化钛粒径为200目以下,晶相为锐钛矿,比表面积在30-100m2/g。
用移液管移取0.3ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml),加入35ml去离子水混合,混合后将上述获得载体A浸渍于其中,而后120℃干燥2小时,650℃焙烧4小时,即制得本发明催化剂。
上述催化剂在实验室小型固定床反应装置上进行预硫化处理,处理气体组成:800ppmSO2、氮气平衡,空速2000h-1,在500℃下处理4小时。
催化剂的活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、甲苯800ppm、乙硫醇浓度800mg/m3、H2S浓度100mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速5000h-1。连续在线测试500小时后出口气体中苯浓度0.43ppm、甲苯浓度1ppm、乙硫醇浓度1ppm;H2S浓度为0。
实施例2
称取90g硅藻土、5g拟薄粉、5g氧化钙,充分混合并粉碎至300目以下,用糖衣机滚制成型,空气中静置干燥8小时后在150℃干燥2小时,而后在350℃下焙烧4小时,即制得载体A。
称取3.54g氯化亚锡和1.5g硝酸钡溶解于35ml去离子水中,再用移液管移取0.65ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml)混合上述水溶液中的混合液;而后将上述载体A浸渍于混合液中,120℃干燥2小时,350℃焙烧4小时,即制得本发明催化剂。
所述硅藻土中二氧化硅的含量≥85%,粒径为200目以下,比表面积在150-300m2/g。
上述催化剂在实验室小型固定床反应装置上进行预硫化处理,硫化气体组成:800ppmSO2、氮气平衡,空速2000h-1,在300下处理4小时。
催化剂的活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、间二甲苯880ppm、乙硫醇浓度80mg/m3、H2S浓度10mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速20000h-1。连续在线测试500小时后出口气体中苯浓度0.35ppm、间二甲苯浓度2ppm、乙硫醇浓度1.2ppm;H2S浓度为0。
实施例3
称取90g二氧化硅、5g钛酸酯、5g水泥、1ml体积浓度5%柠檬酸溶液、2ml体积浓度为10%聚乙烯醇水溶液充分混合均匀,将混匀后混合物用压片机压制成φ3*5mm的片剂,室温干燥8小时后在150℃干燥2小时,而后在600℃下焙烧4小时,即制得载体A。
称取5.1g硝酸铁和1.75g硝酸铋溶解于34ml去离子水中,制得溶液B;用移液管移取1ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml)与溶液B混合后,再将上述载体A浸渍其中,120℃干燥2小时,550℃焙烧4小时,即制得本发明催化剂。
所述二氧化硅的粒径为200目以下,比表面积在100-300m2/g。
上述催化剂在实验室小型固定床反应装置上进行预硫化处理,处理气体组成:800ppmSO2、氮气平衡,空速2000h-1,在450℃下处理4小时。
催化剂的活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、苯乙烯1000ppm、甲硫醇浓度670mg/m3、H2S浓度100mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速20000h-1。连续在线测试500小时后出口气体中苯浓度0.23ppm、苯乙烯浓度2.1ppm、甲硫醇浓度0.87ppm;H2S浓度为0。
对比例1
称取5.1g硝酸铁和1.75g硝酸铋溶解于34ml去离子水中,制得溶液B;用移液管移取1ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml)与溶液B混合后,将100gγ-氧化铝浸渍于其中,120℃干燥2小时,550℃焙烧4小时,即制得对比催化剂。
所述γ-氧化铝小球为:比表面积为233.59m2/g,孔容为0.48m3/g,平均孔径为7.5nm,堆比重为0.70g/ml,粒径范围为3~5mm。
对比例催化剂的预硫化条件和活性评价条件同上述实施例3。在线测试10小时后,出口气体中苯浓度123ppm、苯乙烯浓度350ppm、甲硫醇浓度205ppm;H2S浓度为50ppm。
由上述对比例1和实施例3的催化剂活性进行对比可以看出,用γ-氧化铝代替二氧化硅载体后,在相同的催化组分及含量的情况下,VOCs催化燃烧的性能和硫化物的脱除效果显著下降,说明γ-氧化铝不宜作为含硫气氛VOCs燃烧催化剂的载体。
实施例4
称取1.56g高铼酸钾和2.15g硝酸钴溶解于10ml去离子水中,制得溶液A。
称取45g二氧化硅、52g二氧化钛、5g硅溶胶、5ml体积浓度5%稀硝酸溶液、5ml体积浓度为5%聚乙烯醇水溶液和上述溶液A充分混捏均匀,将混匀的混合物挤成直径φ3*4mm的条形,室温干燥8小时后在150℃干燥2小时,而后在600℃下焙烧4小时,即制得载体A。
用移液管移取1.5ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml),加入35ml去离子水中混合后将上述载体A浸渍其中,120℃干燥2小时,550℃焙烧4小时,即制得本发明催化剂。
所述二氧化钛粒径为200目以下,晶相为锐钛矿,比表面积在30-100m2/g;所述二氧化硅的粒径为200目以下,比表面积在100-300m2/g。
上述催化剂在实验室小型固定床反应装置上进行预硫化处理,处理气体组成:800ppmSO2、氮气平衡,空速2000h-1,在400-450℃下处理4小时。
催化剂的活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、间二甲苯880ppm、乙硫醇浓度800mg/m3、H2S浓度100mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速20000h-1。连续在线测试500小时后出口气体中苯浓度0.5ppm、间二甲苯浓度2.2ppm、乙硫醇浓度0.82ppm;H2S浓度为0。
对比例2
称取1.56g高铼酸钾和2.15g硝酸钴溶解于10ml去离子水中,制得溶液A。
取45g二氧化硅、52g二氧化钛、5g硅溶胶、5ml体积浓度5%稀硝酸溶液、5ml体积浓度为5%聚乙烯醇水溶液和上述溶液A充分混捏均匀,将混匀的混合物挤成直径φ3*4mm的条形,室温干燥8小时后在150℃干燥2小时,而后在600℃下焙烧4小时,即制得载体A。
用移液管移取1.5ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml),加入35ml去离子水混合后将上述载体A浸渍其中,120℃干燥2小时,550℃焙烧4小时,即制得对比催化剂。
所述二氧化钛粒径为200目以下,晶相为锐钛矿,比表面积在30-100m2/g;所述二氧化硅的粒径为200目以下,比表面积在100-300m2/g。
对比例催化剂的预硫化条件和活性评价条件同上述实施例4。在线测试50小时后,出口气体中苯浓度12.8ppm、间二甲苯浓度30ppm、乙硫醇浓度15ppm;H2S浓度为5ppm。
由上述对比例2和实施例4制得的催化剂活性进行对比,可以看出,在载体相同和活性组分及含量相同的情况下,无助剂的催化剂VOCs催化燃烧的性能和硫化物的脱除效果明显下降,多元助剂的加入能够大大提高催化剂的耐硫催化活性。
对比例3
称取1.56g高铼酸钾和2.15g硝酸钴溶解于10ml去离子水中,制得溶液A。
称取45g二氧化硅、52g二氧化钛、5g硅溶胶、5ml体积浓度5%稀硝酸溶液、5ml体积浓度为5%聚乙烯醇水溶液和上述溶液A充分混捏均匀,将混匀的混合物挤成直径φ3*4mm的条形,室温干燥8小时后在150℃干燥2小时,而后在600℃下焙烧4小时,即制得载体A。
用移液管移取1.5ml氯化钯溶液(以单质铂计,浓度为0.066g/ml),加入35ml去离子水混合后将上述载体A浸渍其中,120℃干燥2小时,550℃焙烧4小时,即制得对比催化剂。
所述二氧化钛粒径为200目以下,晶相为锐钛矿,比表面积在30-100m2/g;所述二氧化硅的粒径为200目以下,比表面积在100-300m2/g。
对比例催化剂的预硫化条件和活性评价条件同上述实施例4。在线测试50小时后,出口气体中苯浓度418ppm、间二甲苯浓度439ppm、乙硫醇浓度315ppm;H2S浓度为75ppm。
由上述对比例3和实施例4制得的催化剂活性进行对比,可以看出,在载体和助剂相同及含量相同的情况下,以钯作为活性组分的样品催化燃烧VOCs的性能较差,无法实现VOCs的达标排放。说明钯不适宜作为含硫气氛下VOCs燃烧催化剂的活性组分。
实施例5
称取5.57g仲钨酸铵和1.15g硝酸钾溶解于10ml去离子水中,制得溶液A。
称取69g二氧化硅、28g硅藻土、5g硅溶胶、3ml体积浓度10%草酸溶液、5g硬脂酸镁和上述溶液A充分混捏均匀,将混匀的混合物挤成直径φ3*5mm的条形,室温干燥8小时后在150℃干燥2小时,而后在600℃下焙烧4小时,即制得载体A。
称取1.54g硝酸银溶解于15ml去离子水中,用移液管移取0.95ml硝酸铂溶液(以单质铂计,浓度为0.2156g/ml),加入20ml去离子水混合后将上述载体A浸渍其中,120℃干燥2小时,550℃焙烧4小时即制得本发明催化剂。
所述二氧化硅的粒径为200目以下,比表面积在100-300m2/g;硅藻土中二氧化硅的含量≥85%,粒径为200目以下,比表面积在150-300m2/g。
上述催化剂在实验室小型固定床反应装置上进行预硫化处理,处理气体组成:800ppmSO2、氮气平衡,空速2000h-1,在400-450℃下处理4小时。
催化剂的活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、甲苯800ppm、乙硫醇浓度800mg/m3、H2S浓度100mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速30000h-1。连续在线测试500小时后出口气体中苯浓度0.76ppm、甲苯浓度1.1ppm、乙硫醇浓度1.3ppm;H2S浓度为0。
实施例6
称取19g二氧化硅、78g二氧化钛、10g钛溶胶、5ml体积浓度10%柠檬酸溶液、5ml体积浓度为15%聚乙烯醇水溶液充分混捏均匀,将混匀的混合物挤成直径φ3*5mm的条形,室温干燥8小时后在150℃干燥2小时,而后在600℃下焙烧4小时,即制得载体A。
称取1.56g硝酸铈铵和1.15g高铼酸钾溶解于10ml去离子水中,用移液管移取1.5ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml),加入23ml去离子水混合,将两种水溶液混合,混合将上述载体A浸渍其中,120℃干燥2小时,450℃焙烧4小时即制得本发明催化剂。
所述二氧化钛粒径为200目以下,晶相为锐钛矿,比表面积在30-100m2/g;所述二氧化硅的粒径为200目以下,比表面积在100-300m2/g。
上述催化剂在实验室小型固定床反应装置上进行预硫化处理,处理气体组成:800ppmSO2、氮气平衡,空速2000h-1,在400℃下处理4小时。
催化剂的活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、甲苯800ppm、乙硫醇浓度800mg/m3、H2S浓度100mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速20000h-1。连续在线测试500小时后出口气体中苯浓度0.13ppm、甲苯浓度1.1ppm、乙硫醇浓度0.75ppm;H2S浓度为0。
实施例7
称取165g硫酸氧钛搅拌溶解于500ml去离子水中,加入62.37g硅溶胶(二氧化硅质量含量28%)搅拌均匀,向混合溶液中滴加浓度为12%的氨水溶液直至pH值为8,继续搅拌30分钟后封上保鲜膜陈化16小时。离心分离并反复用去离子水洗涤沉淀物,得到的滤饼在150℃下干燥10小时,600℃下焙烧4小时留用。破碎筛分后,加入10g钛溶胶、5ml体积浓度10%柠檬酸溶液、5ml体积浓度为15%聚乙烯醇水溶液充分混捏均匀,混合物挤成直径φ3*5mm的条形,室温干燥8小时后在150℃干燥2小时,而后在600℃下焙烧4小时,即制得载体A。
称取1.56g硝酸铈铵和1.15g高铼酸钾溶解于10ml去离子水中,用移液管移取1.5ml氯铂酸溶液(以单质铂计,浓度为0.066g/ml),加入23ml去离子水混合,将两种水溶液混合,混合后将上述载体A浸渍其中,120℃干燥2小时,550℃焙烧4小时,即制得本发明催化剂。
上述催化剂在实验室小型固定床反应装置上进行预硫化处理,处理气体组成:80ppmSO2、氮气平衡,空速2000h-1,在350℃下处理4小时。
催化剂的活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、甲苯800ppm、乙硫醇浓度800mg/m3、H2S浓度100mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速20000h-1。连续在线测试500小时后出口气体中苯浓度0.28ppm、甲苯浓度1.31ppm、乙硫醇浓度0.55ppm;H2S浓度为0。
应用例
采用上述实施例6催化剂进行千小时寿命实验:
采用实施例6中催化剂,先进行预硫化处理,处理气体组成:800ppmSO2、氮气平衡,空速2000h-1,在400℃下处理4小时。
活性评价在固定床反应器内进行。反应器为内径为12mm的不锈钢管,上述预处理的催化剂装填量为10ml,原料气组成为:苯浓度1200ppm、甲苯800ppm、乙硫醇浓度800mg/m3、H2S浓度100mg/m3、氧气浓度10%、余为氮气,反应温度280℃、空速20000h-1。寿命实验结果见图1。
Claims (10)
1.一种耐硫挥发性有机化合物燃烧催化剂,其特征在于:催化剂由活性组分、助剂和载体组成;其中活性组分为贵金属铂,铂的含量为载体重量的0.01%~0.2%;助剂为非贵金属,非贵金属的含量为载体重量的0.5%~5%。
2.按权利要求1所述耐硫挥发性有机化合物燃烧催化剂,其特征在于:所述非贵金属助剂为铼、铋、锡、钼、铁、钴、钨、铈、银、钾、钡、钙中的一种或几种的混合。
3.按权利要求1所述耐硫挥发性有机化合物燃烧催化剂,其特征在于:所述载体为二氧化钛、硅藻土、二氧化硅中的一种或两种。
4.按权利要求1所述耐硫挥发性有机化合物燃烧催化剂,其特征在于:所述活性组分铂选自硝酸钯、氯铂酸或羟氨铂。
5.一种权利要求1所述的耐硫挥发性有机化合物燃烧催化剂的制备方法,其特征在于:
(1)载体制备:将载体与胶溶剂、造孔剂和粘结剂充分混均,混匀后制型,制型后在室温下干燥4-8小时,在100-200℃干燥2-8小时,而后在400-650℃下焙烧4-8小时,制得载体;
(2)按比例将可溶铂盐和非贵金属助剂的可溶盐混合,混合后用去离子水溶解配制成混合溶液,或,可溶铂盐和非贵金属助剂的可溶盐分别经去离子水溶解,而后混合得混合溶液;将上述载体浸入至混合溶液中,将混合溶液中倒入上述载体中进行等体积饱和浸渍,于100~200℃下干燥2~8小时,再于400~650℃下焙烧4~8小时,即得催化剂。
6.按权利要求5所述的耐硫挥发性有机化合物燃烧催化剂的制备方法,其特征在于:所述混合溶液与制得载体等体积混合浸渍。
7.按权利要求5所述的耐硫挥发性有机化合物燃烧催化剂的制备方法,其特征在于:所述催化剂经硫化后待用;其中,硫化为将所述催化剂在100-1500ppmSO2的氮气、空速500-5000h-1,在300-500℃下处理1-6小时,制得硫化后的催化剂。
8.按权利要求5所述的耐硫挥发性有机化合物燃烧催化剂的制备方法,其特征在于:所述胶溶剂为硝酸、草酸或柠檬酸;所述造孔剂为田菁粉和/或硬脂酸;所述粘结剂为铝土矿、水泥、赤泥、拟薄粉、钛酸酯、氧化钙、聚乙烯醇、羟甲基纤维素、硅溶胶、钛溶胶中的一种或两种的混合物;
所述硅溶胶和钛溶胶为酸性;其中,硅溶胶中二氧化硅含量在10-30%;钛溶胶中二氧化钛含量在15-30%。
9.按权利要求5所述的耐硫挥发性有机化合物燃烧催化剂的制备方法,其特征在于:所述非贵金属助剂的可溶盐溶液在载体成型前加入到载体的粉料中,或,在载体成型后加入到载体中。
10.一种权利要求1所述的耐硫挥发性有机化合物燃烧催化剂的应用,其特征在于:所述催化剂在含硫气氛下,对硫化物和/或挥发性有机化合物催化净化中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911198761.1A CN112871164B (zh) | 2019-11-29 | 2019-11-29 | 一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911198761.1A CN112871164B (zh) | 2019-11-29 | 2019-11-29 | 一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112871164A true CN112871164A (zh) | 2021-06-01 |
CN112871164B CN112871164B (zh) | 2023-08-04 |
Family
ID=76038317
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911198761.1A Active CN112871164B (zh) | 2019-11-29 | 2019-11-29 | 一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112871164B (zh) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6149886A (en) * | 1997-01-06 | 2000-11-21 | Haldor Topsoe A/S | Process for the desulphurization of gaseous substrate |
US20060035780A1 (en) * | 2004-08-14 | 2006-02-16 | Liqiang Xu | Catalyst for purifying diesel engine exhaust emissions |
CN101559376A (zh) * | 2009-05-26 | 2009-10-21 | 清华大学 | 一种硫酸催化分解用催化剂及其制备方法 |
CN104582843A (zh) * | 2012-09-26 | 2015-04-29 | 恩亿凯嘉股份有限公司 | 铂类氧化催化剂以及使用其的废气净化方法 |
CN104874396A (zh) * | 2015-04-03 | 2015-09-02 | 上海华峰新材料研发科技有限公司 | 催化燃烧法脱除低浓度挥发性有机物催化剂及制备方法 |
CN105964254A (zh) * | 2016-06-20 | 2016-09-28 | 西南化工研究设计院有限公司 | 一种用于挥发性有机物催化燃烧的整体式催化剂及其制备方法 |
CN107262147A (zh) * | 2017-06-14 | 2017-10-20 | 昆明理工大学 | 一种耐硫性催化燃烧催化剂及制备方法 |
CN109833883A (zh) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | 一种高活性双金属负载燃烧催化剂及其制备方法 |
-
2019
- 2019-11-29 CN CN201911198761.1A patent/CN112871164B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6149886A (en) * | 1997-01-06 | 2000-11-21 | Haldor Topsoe A/S | Process for the desulphurization of gaseous substrate |
US20060035780A1 (en) * | 2004-08-14 | 2006-02-16 | Liqiang Xu | Catalyst for purifying diesel engine exhaust emissions |
CN101559376A (zh) * | 2009-05-26 | 2009-10-21 | 清华大学 | 一种硫酸催化分解用催化剂及其制备方法 |
CN104582843A (zh) * | 2012-09-26 | 2015-04-29 | 恩亿凯嘉股份有限公司 | 铂类氧化催化剂以及使用其的废气净化方法 |
CN104874396A (zh) * | 2015-04-03 | 2015-09-02 | 上海华峰新材料研发科技有限公司 | 催化燃烧法脱除低浓度挥发性有机物催化剂及制备方法 |
CN105964254A (zh) * | 2016-06-20 | 2016-09-28 | 西南化工研究设计院有限公司 | 一种用于挥发性有机物催化燃烧的整体式催化剂及其制备方法 |
CN107262147A (zh) * | 2017-06-14 | 2017-10-20 | 昆明理工大学 | 一种耐硫性催化燃烧催化剂及制备方法 |
CN109833883A (zh) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | 一种高活性双金属负载燃烧催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN112871164B (zh) | 2023-08-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1115471B1 (en) | Process and catalyst/sorber for treating sulfur compound containing effluent | |
EP0568003B1 (en) | Absorption of hydrogen sulfide and absorbent composition therefor | |
US5281445A (en) | Coating of components of sulfur absorbants | |
WO2012027948A1 (zh) | 含硫气体的处理方法及用于该方法的加氢催化剂 | |
CN102039137B (zh) | 蜂窝状硫回收尾气催化焚烧催化剂及制备方法 | |
CN113117517B (zh) | 一种高浓度含硫有机废气的处理方法 | |
US8236264B2 (en) | Adsorption composition and process for removing CO from material streams | |
US8597407B2 (en) | Method for removing contaminants from gas flows containing water | |
CN101472678A (zh) | 吸收组合物和除汞方法 | |
CN103028363B (zh) | 气体脱硫吸附剂及其制备方法和含硫气体的脱硫方法 | |
CN1410149A (zh) | 气体中硫化氢的焚烧催化剂及制备、使用方法 | |
CN112871164B (zh) | 一种耐硫挥发性有机化合物燃烧催化剂及其制备方法和应用 | |
CN113210010A (zh) | 一种分区域涂覆的voc催化剂及其制备方法 | |
CN102039129A (zh) | 蜂窝状含硫气体催化焚烧催化剂及制备方法 | |
KR100285674B1 (ko) | 예비가황된 포획충으로 통과시키므로써 탄화수소로부터 비소를 제거하는 방법 | |
CN115624973B (zh) | 一种抗硫中毒的整体型催化剂及其制备方法和应用 | |
CN111151123A (zh) | 一种用于丙烯腈装置尾气净化的方法 | |
EP1912721B1 (en) | Process for the removal of heavy metals from gases, and compositions therefor and therewith | |
CN103769043A (zh) | 一种气体脱硫吸附剂、其制备方法及应用 | |
CN111068642B (zh) | 一种脱除天然气中硫醇催化剂及其制备方法 | |
KR20090031553A (ko) | 기체에서 중금속을 제거하는 방법 | |
CN103769044B (zh) | 一种气体脱硫吸附剂及其制备方法和应用 | |
JPH08332384A (ja) | 有害有機化合物含有排ガス分解用触媒及び排ガスの処理方法 | |
KR100522042B1 (ko) | 일산화탄소 산화용 촉매의 제조방법 | |
JP3538984B2 (ja) | 塩素化有機化合物の分解方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |