TWI647010B - 金屬汞之氧化反應及氮氧化物之還原反應用觸媒、以及排氣之淨化方法 - Google Patents
金屬汞之氧化反應及氮氧化物之還原反應用觸媒、以及排氣之淨化方法 Download PDFInfo
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- TWI647010B TWI647010B TW106106894A TW106106894A TWI647010B TW I647010 B TWI647010 B TW I647010B TW 106106894 A TW106106894 A TW 106106894A TW 106106894 A TW106106894 A TW 106106894A TW I647010 B TWI647010 B TW I647010B
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- Prior art keywords
- catalyst
- gypsum
- oxide
- nitrogen oxides
- exhaust gas
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 11
- 238000000746 purification Methods 0.000 title claims description 6
- 229910052753 mercury Inorganic materials 0.000 title abstract description 12
- 229910052751 metal Inorganic materials 0.000 title abstract description 12
- 239000002184 metal Substances 0.000 title abstract description 12
- 230000003647 oxidation Effects 0.000 title description 13
- 239000010440 gypsum Substances 0.000 claims abstract description 52
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 52
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 24
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 5
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 5
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 24
- 229940008718 metallic mercury Drugs 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001868 water Inorganic materials 0.000 abstract description 6
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 abstract description 3
- 229940010552 ammonium molybdate Drugs 0.000 abstract description 3
- 235000018660 ammonium molybdate Nutrition 0.000 abstract description 3
- 239000011609 ammonium molybdate Substances 0.000 abstract description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000010936 titanium Substances 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000012784 inorganic fiber Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
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- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 mercury halide Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- 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
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
本發明利用捏合機將二氧化鈦、鉬酸銨、偏釩酸銨、磷酸、生石膏及水進行混練而獲得糊劑，將該糊劑塗佈於金屬格網基材，繼而進行乾燥、焙燒，藉此獲得含有鈦之氧化物、鉬之氧化物、釩之氧化物、磷之氧化物、以及石膏而成之金屬汞之氧化反應及氮氧化物之還原反應用觸媒。
Description
本發明係關於一種金屬汞之氧化反應及氮氧化物之還原反應用觸媒、以及排氣之淨化方法。更詳細而言，本發明係關於一種促進金屬汞之氣相氧化反應與氮氧化物之氣相還原反應，但可抑制二氧化硫之氣相氧化反應之觸媒、以及包括使金屬汞氧化並且使氮氧化物還原之排氣之淨化方法。
自發電站、工廠、汽車等排出之排煙中所含之金屬汞對環境之影響引發人們擔憂。因此，要求去除排煙中之金屬汞，抑制向大氣排放。例如，專利文獻1揭示有一種排氣中之汞處理系統，其特徵在於：於排出來自鍋爐之排氣之煙道內，具備：氯化銨溶液供給機構；還原脫硝裝置，其具有利用氨將排氣中之氮氧化物還原，並且於氯化氫共存下使汞氧化之脫硝觸媒；濕式脫硫裝置，其利用鹼性吸收液去除於該還原脫硝裝置中所氧化之汞；及最終除汞裝置，其設置於上述濕式脫硫裝置之內部或下游側而去除排氣中殘存之汞。 業界提出有各種觸媒作為使汞氧化之脫硝觸媒。例如，專利文獻2揭示有一種排氣處理方法，其於處理含有氮氧化物與金屬汞之排氣時，使用含有選自由矽、鋯、鋁、鎢及鉬所組成之群中之1種或2種與鈦之二元系或三元系複合氧化物之觸媒，進行於鹵化合物之存在下使金屬汞轉化為鹵化汞之反應、及氮氧化物之處理。 專利文獻3揭示有一種排氣淨化用觸媒，其係包含鈦(i)、鉬及/或鎢(ii)、釩(iii)及磷(iv)之各氧化物之組合物，且(i)/(ii)/(iii)之原子比為85～97.5/2～10/0.5～10，並且(iv)/((ii)＋(iii))之原子比為0.5～1.5。 另一方面，眾所周知有調配有石膏之脫硝觸媒。例如，專利文獻4揭示有一種脫硝觸媒之製造方法，其特徵在於：將如下糊狀物塗佈於金屬或無機纖維製之網狀物之後，進行乾燥、焙燒；該糊狀物係於包含氧化鈦或其前驅物、含有選自由鎢(W)、釩(V)、鉬(Mo)、鋁(Al)及鎵(Ga)所組成之群中之觸媒成分之一種以上之可溶性鹽類及水之糊狀物中混合生石膏而得者。 專利文獻5揭示有一種脫硝觸媒，其係將擔載有鈦氧化物中至少包含釩之活性成分之組合物作為第一成分，將不含釩之組合物作為第二成分，將該等混合後，進行成形、乾燥、焙燒者，其特徵在於：使用二氧化矽、比表面積小於第一成分之氧化鈦、或氧化鋁作為第二成分，進而以第三成分相對於第一成分、第二成分及第三成分之總和之比率超過1成為20重量%之方式添加石膏作為第三成分。 專利文獻4或5所記載之調配有石膏之脫硝觸媒可用於不含汞之排氣之淨化處理。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2012-11317號公報 [專利文獻2]日本專利特開2005-125211號公報 [專利文獻3]WO 2009/031234 A1 [專利文獻4]日本專利特開2011-78898號公報 [專利文獻5]日本專利特開2013-116428號公報
[發明所欲解決之問題] 本發明之課題在於提供一種促進金屬汞之氣相氧化反應與氮氧化物之氣相還原反應，但可抑制二氧化硫之氣相氧化反應之觸媒、以及包括使金屬汞氧化並且使氮氧化物還原之排氣之淨化方法。 [解決問題之技術手段] 為了解決上述課題而進行了研究，結果完成了包含以下形態之本發明。 [1]一種金屬汞之氧化反應及氮氧化物之還原反應用觸媒，其含有鈦之氧化物、鉬及/或鎢之氧化物、釩之氧化物、磷之氧化物、以及石膏而成。 [2]如[1]所記載之觸媒，其中生石膏之乾燥基準質量相對於鈦之氧化物之質量的比為1/99～40/60。 [3]一種排氣之淨化方法，其包括：使含有金屬汞、氮氧化物及二氧化硫之排氣與含有鈦之氧化物、鉬及/或鎢之氧化物、釩之氧化物、磷之氧化物以及石膏之觸媒接觸，而使金屬汞氧化並且使氮氧化物還原。 [發明之效果] 本發明之觸媒促進金屬汞之氣相氧化反應與氮氧化物之氣相還原反應，但可抑制二氧化硫之氣相氧化反應。 本發明之排氣之淨化方法藉由使含有金屬汞、氮氧化物及二氧化硫之排氣與本發明之觸媒接觸，而使金屬汞氧化並且使氮氧化物還原，但難以使二氧化硫氧化。 本發明之觸媒對於金屬汞之氣相氧化反應、氮氧化物之氣相還原反應及二氧化硫之氣相氧化反應發揮何種作用雖尚不明確，但大概推測原因如下：作為觸媒原料而添加之石膏(生石膏等)於焙燒過程中脫水而多孔化。
本發明之觸媒係含有鈦之氧化物、鉬及/或鎢之氧化物、釩之氧化物、磷之氧化物、以及石膏者。本發明之觸媒用於促進金屬汞之氧化反應及氮氧化物之還原反應。 本發明之觸媒不受其製法之特別限定，例如可藉由將成為構成觸媒之成分之原料之化合物與水一起混合而獲得糊劑，使該糊劑成形或者於基板上塗佈，繼而進行乾燥、焙燒而製造。 作為鈦之氧化物之原料，例如可列舉：二氧化鈦(TiO2
)之粉末、漿料或糊劑；正鈦酸或偏鈦酸(H2
TiO3
)之粉末、漿料或糊劑等。關於可較佳地用作鈦之氧化物之原料之二氧化鈦，其比表面積較佳為20 m2
/g以上，更佳為40～300 m2
/g。二氧化鈦為結晶型，較佳為銳鈦礦型。又，二氧化鈦粉末之藉由電子顯微鏡觀察所測定之數量基準粒度分佈中之50%粒徑較佳為0.001～0.1 μm。 作為鉬及/或鎢之氧化物之原料，可列舉該等元素之氧化物、氧酸或其鹽類。更具體而言，可列舉：三氧化鉬、鉬酸、鉬酸銨等含Mo化合物；三氧化鎢、鎢酸、偏鎢酸銨等含W化合物。關於本發明之觸媒所含之鉬元素與鎢元素之合計量，相對於鈦元素100莫耳，較佳為1.5～13莫耳，更佳為2～12莫耳。 作為釩之氧化物之原料，可列舉：釩之氧化物、氧酸或其鹽類。更具體而言，可列舉：偏釩酸銨、硫酸釩等含V化合物。關於本發明之觸媒所含之釩元素之量，相對於鈦元素之質量100莫耳，較佳為0.1～13莫耳，更佳為0.5～12莫耳。 作為磷之氧化物之原料，可列舉：正磷酸、二磷酸、三磷酸、多磷酸、磷酸銨鹽等。關於本發明之觸媒所含之磷元素之量，相對於鉬元素與鎢元素與釩元素之合計100莫耳，較佳為50～150莫耳，更佳為70～120莫耳。 作為石膏之原料，可列舉：無水石膏(CaSO4
)、燒石膏(CaSO4
1/2H2
O)、生石膏(CaSO4
2H2
O)。再者，認為生石膏於後述焙燒溫度下成為無水物(六方晶體(III型)無水物或斜方晶體(II型)無水物等)。 關於較佳地用於觸媒之製備之生石膏，其形態例如為粉末。生石膏粉末之平均粒徑較佳為15 μm以上，較佳為15～100 μm。再者，生石膏之平均粒徑係藉由雷射繞射法所測定之體積基準粒度分佈中之50%粒徑。若使用平均粒徑未達15 μm之生石膏粉末，則有觸媒之孔隙體積變小之傾向。進而，生石膏粉末之比表面積較佳為1～150 m2
/g，更佳為2～100 m2
/g。 生石膏為天然生石膏、作為化學工業之副產品而生成之化學石膏、脫硝石膏、自廢棄石膏板獲得之石膏等均可。 觸媒所含之石膏之量以生石膏之乾燥基準質量計，相對於鈦之氧化物之質量，較佳為1/99～40/60，更佳為3/97～35/65，進而較佳為5/95～30/70。若石膏之量較少，則有大孔形成之比率下降之傾向。反之，若石膏之量較多，則有觸媒之磨耗強度降低之傾向。 作為用於本發明之觸媒之石膏，較佳為含有Fe元素者。Fe元素之含量並無特別限定，相對於鈦元素100莫耳，較佳為超過0莫耳且為5莫耳以下，更佳為超過0莫耳且為4莫耳以下。推測石膏中所含有之Fe元素於製造過程中轉化為硫酸鐵。本發明中所使用之石膏較佳為不含鈉、鉀等鹼金屬元素；鈣以外之鹼土金屬元素；磷、及砷者。 於本發明之觸媒中，可使用硫酸鋁等含Al化合物等。可期待含Al化合物提高觸媒之耐久性之效果。作為含Al化合物，可列舉硫酸鋁等。 進而，於觸媒之製備中，可使用膠體二氧化矽、矽溶膠等無機粒子；纖維素酯、聚乙烯醇等黏合劑；玻璃纖維等無機纖維。可期待無機微粒子、黏合劑或無機纖維提高觸媒之強度或與基材等之結合力之效果。 糊劑可藉由將上述原料、以及視需要使用之其他無機微粒子、黏合劑及/或無機纖維與水一起進行濕式混練而獲得。混練可使用擠出機、捏合機、行星式攪拌機等周知之混練機構進行。藉由該濕式混練，鈦之氧化物與石膏保持適當之間隙而混合，可製成磨耗強度與觸媒性能得到良好平衡之觸媒。 繼而，使上述糊劑成形。成形可使用擠出成形機、輥壓成形機等進行。作為成形形狀，可列舉：蜂窩狀、柱狀、圓筒狀、板狀、波紋板狀等。又，成形時，可使用用以擔載糊劑之基材。作為基材，可列舉：金屬格網、沖孔金屬、金屬線網、金屬製布等金屬製基板；陶瓷製布、陶瓷製網狀物等陶瓷製基板；玻璃纖維製布等玻璃製基板。 成形後，可裁斷至所需之大小，或賦予所需形狀。例如於成形為板狀之後，可進行切斷、彎折、打孔等加工。又，亦可賦予波型凸條形狀而設置間隔部。 可對以此方式獲得之成形體進行乾燥，繼而進行焙燒。乾燥不受其方式限定，例如可列舉：自然乾燥、熱風乾燥、紅外線乾燥等。焙燒可利用隧道窯等周知之焙燒爐進行。例如，焙燒溫度較佳為400～600℃。焙燒通常於大氣中進行。 本發明之觸媒可使用於含有金屬汞、氮氧化物及二氧化硫之排氣之淨化。具體而言，可於設置於鍋爐等燃燒裝置之後段之脫硝裝置放置本發明之觸媒，使含有金屬汞、氮氧化物及二氧化硫之排氣與該觸媒接觸，同時導入氨與氯化氫或氯化銨等而進行氮氧化物之還原及金屬汞之氧化。由於放置有本發明之觸媒之脫硝裝置中二氧化硫之氧化反應得到抑制，自脫硝裝置排出之氣體中之三氧化硫濃度較低，故而於設置於脫硝裝置之後段之裝置中不會析出酸性硫酸銨而導致壓力損失上升，或不產生機器之腐蝕，亦不會自煙囪排出SO3
之紫煙。 以下，例示具體例對本發明之效果進行說明。 實施例1 將氧化鈦(石原產業公司製造，比表面積170 m2
/g)1276 g、鉬酸銨82 g、偏釩酸銨21.7 g、85%磷酸74 g、矽溶膠(日產化學公司製造，商品名OS溶膠)134 g、生石膏(岸田化學公司製造，比表面積20 m2
/g，水分19.7%)477 g、及水580 g放入捏合機中，混練120分鐘。一面向其中緩慢添加矽鋁系陶瓷纖維(東芝FINELEX)200 g一面混練20分鐘而獲得均勻之糊劑。將所得之糊劑置於對厚度0.2 mm之SUS430J1L製鋼板進行板條加工而成之厚度0.7 mm之金屬格網基材上，將其夾於兩片聚乙烯片材中並使其通過一對加壓輥，以掩蓋金屬格網基材之網狀之方式塗佈糊劑。使其乾燥後，於500℃下焙燒2小時而獲得觸媒1。關於觸媒1，Ti/Mo/V之原子比為96/3/1，生石膏之乾燥基準質量相對於鈦之氧化物之質量的比為23/77。鈦之氧化物之質量＝1276/(1276＋477×(1－19.7/100)＝0.77；生石膏之乾燥基準質量＝477×(1－19.7/100)/(1276＋477×(1－19.7/100)＝0.23。 實施例2 除將生石膏之量自477 g變更為318 g以外，以與實施例1相同之方法獲得觸媒2。關於觸媒2，Ti/Mo/V之原子比為96/3/1，生石膏之乾燥基準質量相對於鈦之氧化物之質量的比為17/83。 實施例3 除將生石膏之量自477 g變更為75 g以外，以與實施例1相同之方法獲得觸媒3。關於觸媒3，Ti/Mo/V之原子比為96/3/1，生石膏之乾燥基準質量相對於鈦之氧化物之質量的比為4/96。 比較例1 除將生石膏變更為熔融二氧化矽(龍森公司製造，商品名FUSELEX E-2，比表面積2 m2
/g，水分0.0%)以外，以與實施例1相同之方法獲得觸媒4。關於觸媒4，Ti/Mo/V之原子比為96/3/1，熔融二氧化矽之質量相對於鈦之氧化物之質量的比為23/77。 比較例2 除將生石膏變更為微粒二氧化矽 (富田製藥公司製造，商品名MICON F，比表面積120 m2
/g，水分5.0%)以外，以與實施例1相同之方法獲得觸媒5。關於觸媒5，Ti/Mo/V之原子比為96/3/1，微粒二氧化矽之乾燥基準質量相對於鈦之氧化物之質量的比為23/77。 比較例3 除將生石膏之量變更為0 g以外，以與實施例1相同之方法獲得觸媒6。觸媒6之Ti/Mo/V之原子比為96/3/1。 比較例4 除將85%磷酸之量變更為0 g以外，以與實施例1相同之方法獲得觸媒7。關於觸媒7，Ti/Mo/V之原子比為96/3/1，生石膏之乾燥基準質量相對於鈦之氧化物之質量的比為23/77。 實驗例 自觸媒1～7分別切出寬度20 mm×長度100 mm之觸媒片。 將1枚觸媒片填充於管型反應器。以表1所示之條件將模擬排氣供給至管型反應器，確定Hg氧化率。Hg氧化率係利用磷酸緩衝液吸收氧化狀態之汞蒸氣，其後藉由依據JIS K-0222之方法分析金屬汞而得之值。 將3枚觸媒片填充於管型反應器。以表2所示之條件將模擬排氣供給至管型反應器，確定脫硝率。脫硝率係基於使用化學發光式NOx分析系統，測定管型反應器之入口及出口處之濃度而得之結果所算出之值。 將3枚觸媒片填充於管型反應器。以表3所示之條件將模擬排氣供給至管型反應器，確定SO2
氧化率。SO2
氧化率係基於使用紅外式SO2
計，測定管型反應器之入口及出口處之濃度而得之結果所算出之值。 [表1]
[表2]
[表3]
[表4]
關於相當於專利文獻3中所記載之觸媒的不含石膏之觸媒6(比較例3)，其脫硝率較高，但Hg氧化率稍低，SO2
氧化率稍高。 含有作為比表面積較小之材料的熔融二氧化矽之觸媒4(比較例1)其脫硝率較低。含有作為比表面積較大之材料的微粒二氧化矽之觸媒5(比較例2)其脫硝率及Hg氧化率均較低。 關於相當於專利文獻4中所記載之觸媒的不含磷之觸媒7(比較例4)，其Hg氧化率及脫硝率較高，但SO2
氧化率較高。 相對於此，關於含有石膏之本發明之觸媒1～3(實施例1～3)，其Hg氧化率較高，為50%以上，脫硝率較高，為64%以上，SO2
氧化率較低，未達1%。 由以上內容可知：本發明之觸媒使金屬汞之氣相氧化反應及氮氧化物之氣相還原反應之促進、與二氧化硫之氣相氧化反應之抑制之平衡性優異。
Claims (2)
- 一種金屬汞之氧化反應及氮氧化物之還原反應用觸媒，其含有鈦之氧化物、選自由鉬之氧化物及鎢之氧化物所組成之群中之至少一種、釩之氧化物、磷之氧化物、以及石膏而成，且生石膏之乾燥基準質量相對於鈦之氧化物之質量的比為1/99~40/60。
- 一種排氣之淨化方法，其包括：使含有金屬汞、氮氧化物及二氧化硫之排氣與觸媒接觸，而使金屬汞氧化並且使氮氧化物還原，上述觸媒含有鈦之氧化物、選自由鉬之氧化物及鎢之氧化物所組成之群中之至少一種、釩之氧化物、磷之氧化物以及石膏，且生石膏之乾燥基準質量相對於鈦之氧化物之質量的比為1/99~40/60。
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