JP6370713B2 - 窒素酸化物を含有するガスストリームを処理する方法および装置 - Google Patents
窒素酸化物を含有するガスストリームを処理する方法および装置 Download PDFInfo
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- JP6370713B2 JP6370713B2 JP2014555382A JP2014555382A JP6370713B2 JP 6370713 B2 JP6370713 B2 JP 6370713B2 JP 2014555382 A JP2014555382 A JP 2014555382A JP 2014555382 A JP2014555382 A JP 2014555382A JP 6370713 B2 JP6370713 B2 JP 6370713B2
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- gas stream
- zeolitic material
- preferred
- nitrogen oxides
- framework structure
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 313
- 238000000034 method Methods 0.000 title claims description 263
- 239000007789 gas Substances 0.000 title claims description 206
- 239000000463 material Substances 0.000 claims description 232
- 239000000203 mixture Substances 0.000 claims description 106
- 229910052723 transition metal Inorganic materials 0.000 claims description 99
- 150000003624 transition metals Chemical class 0.000 claims description 98
- 239000003638 chemical reducing agent Substances 0.000 claims description 86
- 230000008569 process Effects 0.000 claims description 64
- 239000003054 catalyst Substances 0.000 claims description 52
- 239000010457 zeolite Substances 0.000 claims description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- 229910052760 oxygen Inorganic materials 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 29
- 239000002912 waste gas Substances 0.000 claims description 29
- 230000009467 reduction Effects 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 238000002485 combustion reaction Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 3
- 238000011437 continuous method Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 43
- 238000011282 treatment Methods 0.000 description 40
- 238000005342 ion exchange Methods 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 27
- 238000006722 reduction reaction Methods 0.000 description 21
- 239000011734 sodium Substances 0.000 description 21
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000013078 crystal Substances 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 18
- 230000008025 crystallization Effects 0.000 description 18
- -1 for example Substances 0.000 description 18
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 238000001035 drying Methods 0.000 description 17
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 17
- 229910052783 alkali metal Inorganic materials 0.000 description 16
- 238000010531 catalytic reduction reaction Methods 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 14
- 150000001340 alkali metals Chemical class 0.000 description 13
- 238000001354 calcination Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000002955 isolation Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 239000011877 solvent mixture Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000001294 propane Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 150000004760 silicates Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 150000002506 iron compounds Chemical class 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 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 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 229910000358 iron sulfate Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001423 beryllium ion Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- BWYYVSNVUCFQQN-UHFFFAOYSA-N 1,3-diphenylpropan-2-amine Chemical class C=1C=CC=CC=1CC(N)CC1=CC=CC=C1 BWYYVSNVUCFQQN-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- KBPZVLXARDTGGD-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;iron Chemical compound [Fe].OC(=O)C(O)C(O)C(O)=O KBPZVLXARDTGGD-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XDWURHFOCYSDBT-UHFFFAOYSA-N 3,3-dibenzyl-1,4-diazabicyclo[2.2.2]octane Chemical compound C1N(CC2)CCN2C1(CC=1C=CC=CC=1)CC1=CC=CC=C1 XDWURHFOCYSDBT-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- DKIDFDYBDZCAAU-UHFFFAOYSA-L carbonic acid;iron(2+);carbonate Chemical compound [Fe+2].OC([O-])=O.OC([O-])=O DKIDFDYBDZCAAU-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- MAUZTCHAIPUZJB-OLXYHTOASA-L copper;(2r,3r)-2,3-dihydroxybutanedioate;hydrate Chemical compound O.[Cu+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O MAUZTCHAIPUZJB-OLXYHTOASA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- MELBZJNMLHHZBH-UHFFFAOYSA-L copper;dihydrogen phosphate Chemical compound [Cu+2].OP(O)([O-])=O.OP(O)([O-])=O MELBZJNMLHHZBH-UHFFFAOYSA-L 0.000 description 1
- XNEQAVYOCNWYNZ-UHFFFAOYSA-L copper;dinitrite Chemical compound [Cu+2].[O-]N=O.[O-]N=O XNEQAVYOCNWYNZ-UHFFFAOYSA-L 0.000 description 1
- YMBOSYHCYOYHLF-UHFFFAOYSA-L copper;hydrogen carbonate Chemical compound [Cu+2].OC([O-])=O.OC([O-])=O YMBOSYHCYOYHLF-UHFFFAOYSA-L 0.000 description 1
- CSCNMBQITNFHLH-UHFFFAOYSA-L copper;hydrogen phosphate Chemical compound [Cu+2].OP([O-])([O-])=O CSCNMBQITNFHLH-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- KBRZHSQRYDVNOX-UHFFFAOYSA-L copper;propanedioate Chemical compound [Cu+2].[O-]C(=O)CC([O-])=O KBRZHSQRYDVNOX-UHFFFAOYSA-L 0.000 description 1
- FMWMEQINULDRBI-UHFFFAOYSA-L copper;sulfite Chemical compound [Cu+2].[O-]S([O-])=O FMWMEQINULDRBI-UHFFFAOYSA-L 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- UATXJGCWVXKVBN-UHFFFAOYSA-L dihydrogen phosphate iron(2+) Chemical compound [Fe+2].OP(O)([O-])=O.OP(O)([O-])=O UATXJGCWVXKVBN-UHFFFAOYSA-L 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- AOBAVABSFWTQIX-UHFFFAOYSA-L hydrogen phosphate;iron(2+) Chemical compound [Fe+2].OP([O-])([O-])=O AOBAVABSFWTQIX-UHFFFAOYSA-L 0.000 description 1
- PIGJJOFBKFPZQG-UHFFFAOYSA-L hydrogen sulfate;iron(2+) Chemical compound [Fe+2].OS([O-])(=O)=O.OS([O-])(=O)=O PIGJJOFBKFPZQG-UHFFFAOYSA-L 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- FPNCFEPWJLGURZ-UHFFFAOYSA-L iron(2+);sulfite Chemical compound [Fe+2].[O-]S([O-])=O FPNCFEPWJLGURZ-UHFFFAOYSA-L 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- PMAOKILDNNXBSR-UHFFFAOYSA-N iron;propanedioic acid Chemical compound [Fe].OC(=O)CC(O)=O PMAOKILDNNXBSR-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012619 stoichiometric conversion Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Images
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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
- B01D53/92—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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
-
- 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
- B01D53/92—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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01D53/92—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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9427—Processes characterised by a specific catalyst for removing nitrous oxide
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
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- B01D2251/202—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/00—Reactants
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- B01D2251/204—Carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/502—Beta zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/402—Dinitrogen oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2258/00—Sources of waste gases
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
-
- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- General Life Sciences & Earth Sciences (AREA)
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- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
(1)1種または複数の窒素酸化物を含有するガスストリームを提供する工程と、
(2)工程(1)で提供されたガスストリームと遷移金属を含有するBEAタイプの骨格構造を有するゼオライト材料とを接触させて、1種または複数の窒素酸化物に反応を起こさせる工程と
を含み、ゼオライト材料が、有機テンプレート不要合成法から得られる、方法に関する。
NO+0.5O2←→NO2
から利用可能であり、したがってガスストリーム中に存在するNOが、反応
N2O+NO→NO2+N2
に従ってN2Oを二酸化窒素および酸素に変換するための共触媒として作用する、本発明の方法の工程(2)におけるこれらの処理は、N2Oの削減が含むことが好ましい。
(I)YO2のための1種または複数の供給源、X2O3のための1種または複数の供給源、およびBEAタイプの骨格構造を有する1種または複数のゼオライト材料を含む種結晶を含む混合物を調製する工程と、
(II)工程(I)で得られた混合物を結晶化する工程と、
(III)工程(II)で得られたBEAタイプの骨格構造を有するゼオライト材料を、1種または複数の遷移金属とのイオン交換の手順にかける工程と
を含む方法によって得られ、
ここで、Yは四価の元素であり、Xは三価の元素であり、
工程(I)で提供され、工程(II)で結晶化された混合物は、構造規定剤として有機テンプレートを含んでいない。
(A)工程(II)で得られたBEAタイプの骨格構造を有するゼオライト材料を、好ましくはろ過によって単離する工程と、
(B)工程(II)で得られたBEAタイプの骨格構造を有するゼオライト材料を、場合によって洗浄する工程、および/または
(C)工程(II)で得られたBEAタイプの骨格構造を有するゼオライト材料を、場合によって乾燥する工程と
をさらに含むことが好ましい。
(IIIa)工程(II)で得られたBEAタイプの骨格構造を有するゼオライト材料に含まれる、1種または複数のイオン性非骨格元素をH+および/もしくはNH4 +、好ましくはH+に場合によって交換する工程、ならびに/または、
(IIIb)工程(II)もしくは(IIIa)で得られた、BEAタイプの骨格構造を有するゼオライト材料を場合によって焼成する工程、ならびに/または
(IIIc)任意の工程(II)、(IIIa)、もしくは(IIIb)で得られた、BEAタイプの骨格構造を有するゼオライト材料に含まれる1種もしくは複数のイオン性非骨格元素を、1種もしくは複数の遷移金属に変換する工程、
の1つまたは複数の工程を含む本発明の実施形態が、さらに好ましい。
(i)処理されるガスストリームと流体接触して提供される触媒床
を備え、触媒床が、遷移金属を含有するBEAタイプの骨格構造を有するゼオライト材料を含み、ゼオライト材料が、有機テンプレート不要の合成法から得られる、装置に関する。
(ii)1種または複数の還元剤をガスストリーム中に噴射するための、触媒床の上流に設けられる1つまたは複数の装置
をさらに備える。
335.1gのNaAlO2を撹拌しながら7,314gのH2Oに溶解し、続いて74.5gのゼオライトベータの種(450℃で5時間の焼成によってH形態に変換された、Zeolyst International製製品番号CP814C、この場合、焼成温度に到達するのに1℃/分の加熱ランプを使用した)を添加した。混合物を20Lオートクレーブに入れ、7,340gのナトリウム水ガラス溶液(26質量%のSiO2および8質量%のNa2O)ならびに1,436gのLudox AS40を添加して、SiO2 1.00:Al2O3 0.0421:Na2O 0.285:H2O 17.48のモル比を有するアルミノケイ酸塩ゲルが得られた。反応混合物を一定の加熱ランプを用いて120℃の温度まで3時間加熱し、この場合、次いで、結晶化のために前記温度を117時間維持した。反応混合物を室温まで冷却させた後、固体をろ過によって分離し、脱イオン水で反復洗浄し、次いで120℃で16時間乾燥して、1,337gの白色結晶性生成物を得た。
実施例1から得られた100.0gのナトリウムの形態の結晶性生成物を、657.8gの脱イオン水中に142.2gの硝酸アンモニウムが溶解された溶液に80℃で添加し、スラリーを80℃で6時間300rpmにおいて撹拌した。次いで固体を適切なろ紙を有するブフナー漏斗上で熱時ろ過をした(追加の冷却なしで)。次いでろ過ケーキを脱イオン水で、洗浄水の導電率が200μScm−1未満になるまで洗浄した。次いでろ過ケーキを120℃で16時間乾燥した。
実施例2から得られたイオン交換されたゼオライト材料を450℃で5時間焼成して、そのH形を得た。化学分析は、この材料は、9.91のSiO2:Al2O3のモル比を有することを示した。焼成された材料のNa2Oとして計算されたナトリウム含量は、0.09質量%であることが分った。
実施例2の手順を反復し、この場合、イオン交換手順を1回だけ反復した。生じたイオン交換されたゼオライト材料は、しかるべく450℃で5時間焼成して、そのH形を得た。化学分析は、この材料は、10.4のSiO2:Al2O3のモル比を示した。焼成された材料のNa2Oとして計算されたナトリウム含量は、0.80質量%であることが分った。
鉄に変換された試料を、以下の表1に示した実施例AおよびBにより調製した。この目的のために、硫酸鉄溶液を、硫酸鉄(II)七水和物を脱イオン水に溶解することによって調製し、この場合、鉄濃度をそれぞれの試料に対して、表1に示したように設定した。それぞれの溶液を80℃まで加熱し、それぞれのゼオライトベータ出発材料を、6.5の溶液対固体の質量比を達成するための量で撹拌下添加し、80℃の温度を2時間維持した。より具体的には、ゼオライト出発材料に関しては、実施例Aに対して、実施例3からのゼオライト材料を出発材料として使用し、一方、実施例Bに対して、実施例4からのゼオライト材料を使用した。
試験のための触媒試料を調製するために、実施例AおよびBからの鉄担持ゼオライトベータ材料と、30質量%(得られる混合物を100質量%として)のPuralSBとを混合し、次いで、混合物を1.5mmのストランドに成形した。成形された混合物を450℃で4時間焼成して、触媒試料CおよびDを得た。
N2Oの削減実験のために、N2O1,000ppmv、酸素3体積%、H2O 0.3体積%を含有し、窒素を用いて100体積%まで混合物を仕上げたガス混合物を使用した。還元剤としてアンモニアおよびプロパンを使用する試験の運転において、最初の混合物に含まれる窒素ガスの対応する部分を、それぞれの還元剤で置き換えた。表2に示すように、選択された試験をそれぞれ350および450℃で、異なる操作において、還元剤を使用しないで、ならびに500および2,000ppmvのプロパンまたはアンモニアを使用して運転した。表に示された「convN2O」という用語は、触媒と接触する前のガスストリーム中の最初のN2O含量および前記窒素酸化物の処理のための触媒試料と接触した後に残るその含量に基づく、ガスストリーム中のN2Oの変換率(%)を示す。
試験1の試験の運転を反復し、この場合、それぞれの試料中のNOxの1,000ppmvの出発濃度を得るために、それぞれのガス混合物に含まれる窒素ガスの対応する部分をNOx(それぞれの混合物中のNOとN2Oの平衡)によって置き換えた。表3に示すように、選択された試験をそれぞれ350および450℃で、異なる操作において、それぞれ還元剤を使用しないで、ならびに2,000ppmvのプロパンおよび500および2,000ppmvのアンモニアを使用して運転した。試験1に関して、表中に示された「convN2O」という用語は、ガスストリーム中のN2Oの変換率(%)を表し、これは、しかるべく、ガスストリーム中のNOxの変換を表す「convNOx」という用語が適用される。
−DE 10112396 A1
−DE 10226461 A1
−DE 102005022650 A1
−WO 03/084646 A1
Claims (36)
- 窒素酸化物を含有するガスストリームを処理するための方法であって、
(1)N2O及びNOxを含有するガスストリームを提供する工程と、
(2)工程(1)で提供されたガスストリームと遷移金属を含有するBEAタイプの骨格構造を有するゼオライト材料とを接触させて、1種または複数の窒素酸化物に反応を起こさせる工程と
を含み、ゼオライト材料が、有機テンプレート不要合成法から得られ、
工程(1)で提供されるガスストリームが、1種または複数の還元剤をさらに含み、
還元剤が、アンモニアまたは尿素を含まない、ことを特徴する方法。 - 工程(1)で提供されるガスストリームが、10から10,000ppmvの範囲に含まれる量でN2Oを含む、請求項1に記載の方法。
- 工程(1)で提供されるガスストリームが、0から5,000ppmvの範囲に含まれる量でNOxを含む、請求項1又は2に記載の方法。
- 工程(1)で提供されるガスストリームが、1:50から5:1の範囲に含まれるNOx:N2Oのモル比でN2OおよびNOxを含む、請求項1から3のいずれかに記載の方法。
- 1種または複数の還元剤が、炭化水素、一酸化炭素、水素、およびこれらの2種以上の組合せからなる群から選択される1種または複数の化合物を含む、請求項1に記載の方法。
- 1種または複数の還元剤対1種または複数の窒素酸化物の化学量論比が、0.05から50の範囲に含まれる、請求項1または5に記載の方法。
- 工程(1)で提供されるガスストリームが、0から10体積%の酸素を含む、請求項1から6のいずれかに記載の方法。
- 工程(1)で提供されるガスストリームが、0から10体積%のH2Oを含む、請求項1から7のいずれかに記載の方法。
- 工程(1)で提供されるガスストリームが、1種または複数の廃ガスを含む、請求項1から8のいずれかに記載の方法。
- 工程(1)で提供されるガスストリームが、内燃機関からの1種または複数の廃ガスを含む、請求項1から9のいずれかに記載の方法。
- 工程(1)で提供されるガスストリーム中に含まれる1種または複数の廃ガスが、予めN2Oおよび/またはNOxの削減のための触媒処理手順に供されていない、請求項9または10に記載の方法。
- 工程(2)における、ガスストリームと遷移金属含有ゼオライト材料との接触が、250から550℃の範囲に含まれる温度で実施される、請求項1から11のいずれかに記載の方法。
- 工程(2)における、ガスストリームと遷移金属含有ゼオライト材料との接触が、1から50バールの範囲に含まれる圧力で実施される、請求項1から12のいずれかに記載の方法。
- 前記方法が連続法である、請求項1から13のいずれかに記載の方法。
- N2O及びNOxを含有するガスストリームを処理するための装置であって、
(i)処理されるガスストリームと流体接触して提供される触媒床
を備え、触媒床が、遷移金属を含有するBEAタイプの骨格構造を有するゼオライト材料を含み、ゼオライト材料が、有機テンプレート不要の合成法から得られ、及び
(ii)1種または複数の還元剤をガスストリーム中に投入するための、触媒床の上流に設けられる1つまたは複数の装置
をさらに備え、前記還元剤が、アンモニアまたは尿素を含まない、装置。 - 触媒床が、固定床触媒または流動床触媒である、請求項15に記載の装置。
- ゼオライト材料に含まれる1種または複数の遷移金属が、Co、Ni、Cu、Fe、Ag、Au、Pt、Pd、Rhおよびこれらの2種以上の組合せからなる群から選択される、請求項1から14のいずれかに記載の方法。
- 1種または複数の遷移金属が、ゼオライト材料中に非骨格元素として含まれる、請求項1から14、もしくは17のいずれかに記載の方法。
- ゼオライト材料のBEAタイプの骨格構造が、YO2およびX2O3(式中、Yは四価の元素であり、Xは三価の元素である)を含む、請求項1から14、17もしくは18のいずれかに記載の方法。
- Yが、Si、Sn、Ti、Zr、Ge、およびこれらの2種以上の混合物からなる群から選択される、請求項19に記載の方法。
- Xが、Al、B、In、Ga、およびこれらの2種以上の混合物からなる群から選択される、請求項19もしくは20に記載の方法。
- YO2:X2O3のモル比が、2から100の範囲である、請求項19から21のいずれかに記載の方法。
- BEAタイプの骨格構造中に含まれる、1種または複数の遷移金属対X2O3のモル比が、0.005から10の範囲である、請求項19から22のいずれかに記載の方法。
- BEAタイプの骨格構造を有するゼオライト材料が、ゼオライトベータを含む、請求項1から14、もしくは17から24のいずれかに記載の方法。
- 遷移金属含有ゼオライト材料が、成形品中に含まれる、請求項1から14、もしくは17から25のいずれかに記載の方法。
- ゼオライト材料に含まれる1種または複数の遷移金属が、Co、Ni、Cu、Fe、Ag、Au、Pt、Pd、Rhおよびこれらの2種以上の組合せからなる群から選択される、請求項15又は16に記載の装置。
- 1種または複数の遷移金属が、ゼオライト材料中に非骨格元素として含まれる、請求項15、16、及び27のいずれかに記載の装置。
- ゼオライト材料のBEAタイプの骨格構造が、YO2およびX2O3(式中、Yは四価の元素であり、Xは三価の元素である)を含む、請求項15、16、27、28のいずれかに記載の装置。
- Yが、Si、Sn、Ti、Zr、Ge、およびこれらの2種以上の混合物からなる群から選択される、請求項29に記載の装置。
- Xが、Al、B、In、Ga、およびこれらの2種以上の混合物からなる群から選択される、請求項29もしくは30のいずれかに記載の装置。
- YO2:X2O3のモル比が、2から100の範囲である、請求項29から31のいずれかに記載の装置。
- BEAタイプの骨格構造中に含まれる、1種または複数の遷移金属対X2O3のモル比が、0.005から10の範囲である、請求項29から32のいずれかに記載の装置。
- BEAタイプの骨格構造を有するゼオライト材料が、ゼオライトベータを含む、請求項15、16、27から34のいずれかに記載の装置。
- 遷移金属含有ゼオライト材料が、成形品中に含まれる、請求項15、16、27から35のいずれかに記載の装置。
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JP5879339B2 (ja) * | 2010-06-18 | 2016-03-08 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Lev型構造ゼオライト系材料の製造用の有機テンプレート不使用合成方法 |
US8568677B2 (en) * | 2010-10-12 | 2013-10-29 | Basf Se | P/S-TM-comprising zeolites for decomposition of N2O |
US8375896B2 (en) * | 2010-10-14 | 2013-02-19 | Gaines B. Slade, JR. | Method of use of dicalcium phosphate as an antler scent |
EP2659974B1 (en) * | 2010-12-27 | 2019-06-12 | N.E. Chemcat Corporation | Selective reduction catalyst, and exhaust gas purification device and exhaust gas purification method using same |
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CN104245583B (zh) | 2017-05-03 |
US10792614B2 (en) | 2020-10-06 |
US20150030515A1 (en) | 2015-01-29 |
KR102064625B1 (ko) | 2020-01-09 |
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JP2015506835A (ja) | 2015-03-05 |
EP2812283A4 (en) | 2015-10-28 |
EP3744427A1 (en) | 2020-12-02 |
EP2812283B1 (en) | 2020-09-16 |
US20200368685A1 (en) | 2020-11-26 |
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