JP2007152263A - Catalyst for nitrous oxide decomposition and method for purifying nitrous oxide-containing gas - Google Patents
Catalyst for nitrous oxide decomposition and method for purifying nitrous oxide-containing gas Download PDFInfo
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- JP2007152263A JP2007152263A JP2005352848A JP2005352848A JP2007152263A JP 2007152263 A JP2007152263 A JP 2007152263A JP 2005352848 A JP2005352848 A JP 2005352848A JP 2005352848 A JP2005352848 A JP 2005352848A JP 2007152263 A JP2007152263 A JP 2007152263A
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000001272 nitrous oxide Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000010948 rhodium Substances 0.000 claims abstract description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 239000010931 gold Substances 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 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 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
- 229910000480 nickel oxide Inorganic materials 0.000 description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910003450 rhodium oxide Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000000306 component Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- -1 etc. Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 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
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Chemical group 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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)
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、亜酸化窒素分解用触媒およびこの触媒を用いた亜酸化窒素含有ガスの浄化方法に関する。 The present invention relates to a nitrous oxide decomposition catalyst and a method for purifying a nitrous oxide-containing gas using the catalyst.
燃焼排ガスや化学プラントなどから排出される各種産業排ガス中に含まれる亜酸化窒素（Ｎ２Ｏ）は、成層圏で分解して一酸化窒素を生成し、また高い温室効果を示すことから、その効率的な分解除去が望まれている。そこで、亜酸化窒素を触媒に接触させて分解除去する方法として、酸化アルミニウムや酸化ジルコニウムのような担体にパラジウム、ニッケル、コバルトなどを担持した触媒を用いる方法（特許文献１）、疎水性アルミナにルテニウムおよび／またはロジウムと酸化ジルコニウムなどとを担持した触媒を用いる方法（特許文献２）、また、酸化ロジウムや酸化コバルトと、マンガン化合物と、アルカリまたはアルカリ土類金属化合物とを含有する触媒を用いる方法（特許文献３）などが提案されている。 Nitrous oxide (N 2 O) contained in various industrial exhaust gas discharged from combustion exhaust gas and chemical plants decomposes in the stratosphere to produce nitric oxide and shows high greenhouse effect. Decomposition and removal are desired. Therefore, as a method for decomposing and removing nitrous oxide by contacting it with a catalyst, a method using a catalyst in which palladium, nickel, cobalt or the like is supported on a carrier such as aluminum oxide or zirconium oxide (Patent Document 1), or hydrophobic alumina. A method using a catalyst supporting ruthenium and / or rhodium and zirconium oxide (Patent Document 2), or using a catalyst containing rhodium oxide or cobalt oxide, a manganese compound, and an alkali or alkaline earth metal compound. A method (Patent Document 3) and the like have been proposed.
本発明の目的は、亜酸化窒素を効率よく分解除去し得る新規な亜酸化窒素分解用触媒、およびこの触媒に亜酸化窒素を含むガスを接触させて亜酸化窒素を効率よく分解除去する亜酸化窒素含有ガスの浄化方法を提供することにある。 An object of the present invention is to provide a novel nitrous oxide decomposition catalyst capable of efficiently decomposing and removing nitrous oxide, and nitrous oxide for efficiently decomposing and removing nitrous oxide by contacting the catalyst with a gas containing nitrous oxide. The object is to provide a method for purifying nitrogen-containing gas.
本発明者らの研究によれば、上記目的は、下記発明により達成できることがわかった。
（１）（Ａ）アルカリ金属、アルカリ土類金属および希土類金属から選ばれる少なくとも１種の元素または化合物と、（Ｂ）ニッケル、コバルト、銅、鉄、マンガン、銀、ルテニウム、ロジウム、白金、金、パラジウムおよびイリジウムから選ばれる少なくとも１種の元素または化合物とを含有し、細孔容積が０．１〜０．６ｍｌ／ｇの範囲にあることを特徴とする亜酸化窒素分解用触媒。
（２）（Ａ）アルカリ土類金属から選ばれる少なくとも１種の元素の化合物と、（Ｂ）ニッケル、コバルト、銅、ルテニウム、ロジウムおよび白金から選ばれる少なくとも１種の元素または化合物とを含有し、細孔容積が０．１〜０．６ｍｌ／ｇの範囲にあることを特徴とする亜酸化窒素分解用触媒。
（３）さらに、（Ｃ）チタン、アルミニウム、ケイ素およびジルコニウムから選ばれる少なくとも１種の元素の酸化物を含む上記（１）または（２）記載の亜酸化窒素分解用触媒。
（４）亜酸化窒素を含有するガスを上記（１）、（２）または（３）の触媒と接触させて亜酸化窒素を分解除去することを特徴とする亜酸化窒素含有ガスの浄化方法。
According to the studies by the present inventors, it has been found that the above object can be achieved by the following invention.
(1) (A) at least one element or compound selected from alkali metals, alkaline earth metals and rare earth metals, and (B) nickel, cobalt, copper, iron, manganese, silver, ruthenium, rhodium, platinum, gold And a catalyst for nitrous oxide decomposition, comprising at least one element or compound selected from palladium and iridium and having a pore volume in the range of 0.1 to 0.6 ml / g.
(2) containing (A) a compound of at least one element selected from alkaline earth metals and (B) at least one element or compound selected from nickel, cobalt, copper, ruthenium, rhodium and platinum. A catalyst for nitrous oxide decomposition, wherein the pore volume is in the range of 0.1 to 0.6 ml / g.
(3) The nitrous oxide decomposition catalyst according to (1) or (2), further comprising (C) an oxide of at least one element selected from titanium, aluminum, silicon and zirconium.
(4) A method for purifying a nitrous oxide-containing gas, wherein a gas containing nitrous oxide is brought into contact with the catalyst of (1), (2) or (3) to decompose and remove nitrous oxide.
本発明の亜酸化窒素分解用触媒は、高性能であって、亜酸化窒素を高い除去率をもって分解除去することができる。したがって、本発明の亜酸化窒素分解用触媒を用いることにより、亜酸化窒素含有ガスを効率よく浄化することができる。 The nitrous oxide decomposition catalyst of the present invention has high performance and can decompose and remove nitrous oxide with a high removal rate. Therefore, the nitrous oxide-containing gas can be efficiently purified by using the nitrous oxide decomposition catalyst of the present invention.
本発明の亜酸化窒素分解用触媒（以下、単に「触媒」ということもある。）は、（Ａ）アルカリ金属、アルカリ土類金属および希土類金属から選ばれる少なくとも１種の元素またはその化合物と、（Ｂ）ニッケル、コバルト、銅、鉄、マンガン、銀、ルテニウム、ロジウム、白金、金、パラジウムおよびイリジウムから選ばれる少なくとも１種の元素または化合物とを必須成分として含有する。なお、成分Ａおよび成分Ｂは各々２種以上の異なる元素または化合物から構成されていてもよいことはいうまでもない。 The nitrous oxide decomposition catalyst of the present invention (hereinafter sometimes simply referred to as “catalyst”) includes (A) at least one element selected from alkali metals, alkaline earth metals, and rare earth metals, or a compound thereof, (B) At least one element or compound selected from nickel, cobalt, copper, iron, manganese, silver, ruthenium, rhodium, platinum, gold, palladium and iridium is contained as an essential component. Needless to say, each of component A and component B may be composed of two or more different elements or compounds.
上記成分Ａのアルカリ金属としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウムなどを、アルカリ土類金属としては、マグネシウム、カルシウム、ストロンチウム、バリウムなどを、また希土類金属としては、スカンジウム、イットリウム、ランタン、セリウムなどを例示することができる。これらのなかでも、アルカリ土類金属、特にカルシウムが好適に用いられる。上記成分（Ｂ）のなかでも、ニッケル、コバルト、銅、ルテニウム、ロジウムおよび白金から選ばれる少なくとも１種が好適に用いられる。 The alkali metal of component A is lithium, sodium, potassium, rubidium, cesium, etc., the alkaline earth metal is magnesium, calcium, strontium, barium, etc., and the rare earth metal is scandium, yttrium, lanthanum, Cerium and the like can be exemplified. Of these, alkaline earth metals, particularly calcium, are preferably used. Among the components (B), at least one selected from nickel, cobalt, copper, ruthenium, rhodium and platinum is preferably used.
したがって、本発明の触媒のなかでも、（Ａ）アルカリ土類金属から選ばれる少なくとも１種の元素の化合物と、（Ｂ）ニッケル、コバルト、銅、ルテニウム、ロジウムおよび白金から選ばれる少なくとも１種の元素または化合物とを必須成分として含有するものが好適に用いられる。 Accordingly, among the catalysts of the present invention, (A) a compound of at least one element selected from alkaline earth metals and (B) at least one selected from nickel, cobalt, copper, ruthenium, rhodium and platinum. What contains an element or a compound as an essential component is used suitably.
本発明の触媒における成分Ａおよび成分Ｂの割合は、特に限定されるものではないが、通常、次のとおりである（触媒全質量基準）。すなわち、成分Ｂがニッケル、コバルト、銅、鉄、マンガンおよび銀の場合、成分Ａ（酸化物換算）は、１〜９９質量％、好ましくは５〜９５質量％であり、成分Ｂ（酸化物換算）は、１〜９９質量％、好ましくは５〜９５質量％である（合計１００質量％）。また、成分Ｂがルテニウム、ロジウム、白金、金、パラジウムおよびイリジウムの場合、成分Ａ（酸化物換算）は、１〜９９．９９質量％、好ましくは５〜９９．９５質量％であり、成分Ｂ（金属換算）は、０．０１〜１０質量％、好ましくは０．０５〜５質量％である（合計１００質量％）。上記のような割合で成分Ａおよび成分Ｂを含むことにより、触媒の亜酸化窒素分解性能が十分に発揮される。 The proportion of component A and component B in the catalyst of the present invention is not particularly limited, but is usually as follows (based on the total mass of the catalyst). That is, when component B is nickel, cobalt, copper, iron, manganese and silver, component A (oxide conversion) is 1 to 99% by mass, preferably 5 to 95% by mass, and component B (oxide conversion) ) Is 1 to 99% by mass, preferably 5 to 95% by mass (total 100% by mass). When component B is ruthenium, rhodium, platinum, gold, palladium and iridium, component A (as oxide) is 1 to 99.99% by mass, preferably 5 to 99.95% by mass. (Metal conversion) is 0.01 to 10% by mass, preferably 0.05 to 5% by mass (total 100% by mass). By including the component A and the component B in the ratio as described above, the nitrous oxide decomposition performance of the catalyst is sufficiently exhibited.
本発明の触媒は、上記成分Ａおよび成分Ｂに加えて、成分Ｃとしてチタン、アルミニウム、ケイ素およびジルコニウムから選ばれる少なくとも１種の元素の酸化物を含有していてもよい。成分Ｃとしては、酸化チタン、酸化アルミニウム、酸化ケイ素、酸化ジルコニウムやこれらの２種以上の混合物、あるいはチタンとアルミニウム、ケイ素およびジルコニウムから選ばれる少なくとも１種との複合酸化物など触媒の担体として一般に用いられている金属酸化物を例示することができる。これらはいずれも触媒の強度に寄与することが知られており、本発明においても、成分Ｃを用いることにより、触媒強度の向上などが期待される。 The catalyst of the present invention may contain an oxide of at least one element selected from titanium, aluminum, silicon and zirconium as component C in addition to component A and component B. Component C is generally used as a catalyst carrier such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide or a mixture of two or more thereof, or a composite oxide of titanium and at least one selected from aluminum, silicon and zirconium. The metal oxide used can be illustrated. These are all known to contribute to the strength of the catalyst, and in the present invention, the use of component C is expected to improve the strength of the catalyst.
本発明の触媒における成分Ａ、成分Ｂおよび成分Ｃの割合は、特に限定されるものではないが、通常、次のとおりである（触媒全質量基準）。すなわち、成分Ｂがニッケル、コバルト、銅、鉄、マンガンおよび銀の場合、成分Ａ（酸化物換算）は、１〜９８質量％、好ましくは５〜９４質量％であり、成分Ｂ（酸化物換算）は、１〜９８質量％、好ましくは５〜９４質量％であり、成分Ｃ（酸化物）は１〜５０質量％、好ましくは１〜４０質量％である（合計１００質量％）。また、成分Ｂがルテニウム、ロジウム、白金、金、パラジウムおよびイリジウムの場合、成分Ａ（酸化物換算）は、１〜９８．９９質量％、好ましくは５〜９８．９５質量％であり、成分Ｂ（金属換算）は、０．０１〜１０質量％、好ましくは０．０５〜５質量％であり、成分Ｃ（酸化物）は１〜５０質量％、好ましくは１〜４０質量％である（合計１００質量％）。上記のような割合で成分Ａ、成分Ｂおよび成分Ｃを含むことにより、触媒の亜酸化窒素分解性能が十分に発揮される。 The proportions of component A, component B, and component C in the catalyst of the present invention are not particularly limited, but are usually as follows (based on the total mass of the catalyst). That is, when component B is nickel, cobalt, copper, iron, manganese, and silver, component A (as oxide) is 1 to 98% by mass, preferably 5 to 94% by mass, and component B (as oxide) ) Is 1 to 98% by mass, preferably 5 to 94% by mass, and component C (oxide) is 1 to 50% by mass, preferably 1 to 40% by mass (total 100% by mass). When component B is ruthenium, rhodium, platinum, gold, palladium and iridium, component A (as oxide) is 1 to 99.99% by mass, preferably 5 to 98.95% by mass. (Metal conversion) is 0.01 to 10% by mass, preferably 0.05 to 5% by mass, and component C (oxide) is 1 to 50% by mass, preferably 1 to 40% by mass (total) 100% by mass). By including component A, component B, and component C in the proportions described above, the nitrous oxide decomposition performance of the catalyst is sufficiently exhibited.
本発明の触媒の細孔容積は０．１〜０．６ｍｌ／ｇであり、好ましくは０．１〜０．５ｍｌ／ｇ、より好ましくは０．１〜０．４ｍｌ／ｇである。細孔容積が０．１ｍｌ／ｇより小さいと、触媒性能（Ｎ２Ｏ除去率）が大幅に低下し、一方、０．６ｍｌ／ｇを超えると触媒が脆くなり、使用に耐え得る触媒強度を維持できなくなる。なお、細孔容積は、水銀圧入法により測定した。 The pore volume of the catalyst of the present invention is 0.1 to 0.6 ml / g, preferably 0.1 to 0.5 ml / g, more preferably 0.1 to 0.4 ml / g. When the pore volume is smaller than 0.1 ml / g, the catalyst performance (N 2 O removal rate) is greatly reduced. It cannot be maintained. The pore volume was measured by a mercury intrusion method.
本発明の、成分Ａおよび成分Ｂ、あるいは成分Ａ、成分Ｂおよび成分Ｃを含有し、細孔容積が０．１〜０．６ｍｌ／ｇの範囲にある触媒は、例えば、次のようにして得られる。 The catalyst of the present invention containing component A and component B, or component A, component B and component C and having a pore volume in the range of 0.1 to 0.6 ml / g is, for example, as follows. can get.
上記成分Ａおよび成分Ｂを含む触媒は、例えば、成分Ａの元素を含む原料化合物と成分Ｂの元素を含む原料化合物とを適量の水と成型助剤などと十分に混合し、所望形状に成型した後、乾燥し、３００〜６００℃、好ましくは３５０〜５５０℃の範囲で焼成することにより調製することができる。また、成分Ａ、成分Ｂおよび成分Ｃを含む触媒は、上記と同様に、成分Ａの元素を含む原料化合物と成分Ｂの元素を含む原料化合物と成分Ｃの金属酸化物とを適量の水と成型助剤などと十分に混合し、所望形状に成型した後、乾燥し、３００〜６００℃、好ましくは３５０〜５５０℃の範囲で焼成することにより調製することができる。そのほか、例えば、成分Ａの原料化合物を水に溶解して、成分Ｂおよび成分Ｃの粉体と混合し、所望形状に成型した後、乾燥し、３００〜６００℃、好ましくは３５０〜５５０℃の範囲で焼成することにより調製することもできる。本発明は上記方法に限定されるものではなく、細孔容積が０．１〜０．６ｍｌ／ｇの範囲にあり、十分な亜酸化窒素分解性能が得られる限り各種方法にしたがって調製することができる。 The catalyst containing the component A and the component B is formed into a desired shape by sufficiently mixing, for example, a raw material compound containing the element A and a raw material compound containing the element B with an appropriate amount of water and a molding aid. Then, it can be prepared by drying and baking in the range of 300 to 600 ° C, preferably 350 to 550 ° C. Similarly to the above, the catalyst containing component A, component B and component C comprises a raw material compound containing the element of component A, a raw material compound containing the element of component B, and a metal oxide of component C with an appropriate amount of water. It can be prepared by thoroughly mixing with a molding aid or the like, molding into a desired shape, drying, and firing at 300 to 600 ° C., preferably 350 to 550 ° C. In addition, for example, the raw material compound of component A is dissolved in water, mixed with the powders of component B and component C, molded into a desired shape, dried, and then dried at 300 to 600 ° C., preferably 350 to 550 ° C. It can also be prepared by firing within a range. The present invention is not limited to the above method, and the pore volume is in the range of 0.1 to 0.6 ml / g, and can be prepared according to various methods as long as sufficient nitrous oxide decomposition performance is obtained. it can.
上記原料化合物としては、各元素を含む、酸化物、水酸化物、炭酸塩、アンモニウム塩、硝酸塩、硫酸塩、リン酸塩、酢酸塩、シュウ酸塩、ハロゲン化合物などを例示することができる。 Examples of the raw material compound include oxides, hydroxides, carbonates, ammonium salts, nitrates, sulfates, phosphates, acetates, oxalates, and halogen compounds containing each element.
成分Ａおよび成分Ｂの形態については、特に限定されるものではないが、金属、または酸化物、炭酸塩、硫酸塩、リン酸塩などの化合物の形態で触媒中に存在する。成分Ａのアルカリ土類金属の場合には、アルカリ土類金属の酸化物や炭酸塩、例えば、酸化カルシウム（ＣａＯ）や炭酸カルシウム（ＣａＣＯ３）の形態で存在する。成分Ｂのニッケル、コバルトおよび銅の場合には、それらの酸化物、例えば、酸化ニッケル（ＮｉＯ）、酸化コバルト（Ｃｏ３Ｏ４）や酸化銅（ＣｕＯ）として、またルテニウム、ロジウムおよび白金の場合には、それぞれ、金属として存在する。成分Ｃは、そのまま、金属酸化物の形態で存在する。 The form of component A and component B is not particularly limited, but is present in the catalyst in the form of a metal or a compound such as an oxide, carbonate, sulfate, phosphate or the like. In the case of the alkaline earth metal of component A, it exists in the form of an oxide or carbonate of an alkaline earth metal, for example, calcium oxide (CaO) or calcium carbonate (CaCO 3 ). In the case of component B nickel, cobalt and copper, their oxides, such as nickel oxide (NiO), cobalt oxide (Co 3 O 4 ) and copper oxide (CuO), and in the case of ruthenium, rhodium and platinum Are each present as a metal. Component C is present as it is in the form of a metal oxide.
本発明の触媒の形状については特に制限はなく、円柱状、円筒状（ペレット状）、球状、板状、ハニカム状、その他一体に成型されたものなど適宜選択することができる。この触媒の成型は一般的な成型方法、例えば打錠成型法、押出成型法などによって行うことができる。球状触媒の場合、その平均粒径は、通常、１〜１０ｍｍである。ハニカム状触媒の場合は、いわゆるモノリス担体と同様であり、押出成型法やシート状素子を巻き固める方法などにより製造される。そのガス通過口（セル形状）の形は６角形、４角形、３角形またはコルゲーション形のいずれであってもよい。セル密度（セル数／単位断面）は、通常、２５〜８００セル／平方インチ（ｘ２．５ｃｍ）である。 The shape of the catalyst of the present invention is not particularly limited, and may be appropriately selected from a columnar shape, a cylindrical shape (pellet shape), a spherical shape, a plate shape, a honeycomb shape, and other integrally molded ones. The catalyst can be molded by a general molding method such as a tableting molding method or an extrusion molding method. In the case of a spherical catalyst, the average particle diameter is usually 1 to 10 mm. In the case of a honeycomb-shaped catalyst, it is the same as a so-called monolithic carrier, and is manufactured by an extrusion molding method or a method of winding and solidifying a sheet-like element. The shape of the gas passage port (cell shape) may be hexagonal, quadrangular, triangular or corrugated. The cell density (number of cells / unit cross section) is usually 25 to 800 cells / in 2 (x2.5 cm).
本発明の亜酸化窒素含有ガスの浄化方法によれば、上記触媒に亜酸化窒素含有ガスを接触させて排ガス中の亜酸化窒素を酸化分解する。本発明の方法は、亜酸化窒素濃度が１〜５００，０００ｐｐｍ、好ましくは１０〜１００，０００ｐｐｍ、より好ましくは１０〜１０，０００ｐｐｍの排ガスの浄化に好適に用いられる。亜酸化窒素含有ガスと本発明の触媒と接触させて亜酸化窒素を分解除去する際の反応温度およびガスの空間速度については特に制限はなく、亜酸化窒素の分解が効率よく進行するように、適宜、決定することができる。具体的には、例えば、反応温度は、１００〜６００℃、好ましくは２００〜６００℃であり、ガスの空間速度（ＳＶ）は、１，０００〜５０，０００ｈｒ−１、好ましくは２，０００〜２０，０００ｈｒ−１である。 According to the method for purifying a nitrous oxide-containing gas of the present invention, the nitrous oxide-containing gas is brought into contact with the catalyst to oxidatively decompose nitrous oxide in the exhaust gas. The method of the present invention is suitably used for purification of exhaust gas having a nitrous oxide concentration of 1 to 500,000 ppm, preferably 10 to 100,000 ppm, more preferably 10 to 10,000 ppm. There are no particular limitations on the reaction temperature and gas space velocity when the nitrous oxide-containing gas is brought into contact with the catalyst of the present invention to decompose and remove the nitrous oxide, so that the decomposition of nitrous oxide proceeds efficiently. It can be determined as appropriate. Specifically, for example, the reaction temperature is 100 to 600 ° C., preferably 200 to 600 ° C., and the gas space velocity (SV) is 1,000 to 50,000 hr −1 , preferably 2,000 to 2,000. 20,000 hr −1 .
本発明の有利な実施態様を示している以下の実施例を挙げて、本発明を更に具体的に説明する。
（実施例１）
炭酸カルシウム８００ｇ、酸化ニッケル（ＮｉＯ）２００ｇに適量の水と成型助剤とを添加しつつニーダーでよく混合した後、押出成型機で直径５ｍｍ、長さ５ｍｍのペレット状に成型した。このペレットを１００℃で１０時間乾燥した後、５００℃で５時間空気雰囲気下で焼成してペレット状の触媒（１）を得た。この触媒の組成は、Ｃａ：Ｎｉ（ＣａＯ：ＮｉＯとして）＝６９．１：３０．９（質量％）であり、その細孔容積は０．２５ｍｌ／ｇであった。
（実施例２〜４）
実施例１の炭酸カルシウムの代わりに、塩基性炭酸マグネシウム、炭酸ストロンチウム、あるいは炭酸バリウムを用いた以外は実施例１と同様にして、表１に示す組成と細孔容積の触媒（２）〜（４）を得た。
（実施例５、６）
実施例１における炭酸カルシウムの代わりに、リン酸三カルシウムまたは硫酸カルシウムを用いた以外は実施例１と同様にして、表１に示す組成と細孔容積の触媒（５）および（６）を得た。
（実施例７、８）
実施例１における酸化ニッケル（ＮｉＯ）の代わりに、酸化コバルト（Ｃｏ３Ｏ４）または酸化銅（ＣｕＯ）を用いた以外は実施例１と同様にして、表１に示す組成と細孔容積の触媒（７）および（８）を得た。
（実施例９）
炭酸カルシウム９９５ｇ、酸化ルテニウム（田中貴金属（株）製、ルテニウムを６５質量％含有）５ｇに適量の水と成型助剤とを添加しつつニーダーでよく混合した後、押出成型機で直径５ｍｍ、長さ５ｍｍのペレット状に成型した。このペレットを１００℃で１０時間乾燥した後、５００℃で５時間空気雰囲気下で焼成してペレット状の触媒（９）を得た。この触媒の組成は、Ｃａ：Ｒｕ（ＣａＯ：Ｒｕとして）＝９９．４：０．６（質量％）であり、その細孔容積は０．２２ｍｌ／ｇであった。
（実施例１０、１１）
実施例９における酸化ルテニウムの代わりに、酸化ロジウムまたは酸化白金を用いた以外は実施例９と同様にして、表１に示す組成と細孔容積の触媒（１０）および（１１）を得た。
（実施例１２、１３）
実施例９における炭酸カルシウムの代わりに、リン酸三カルシウムまたは硫酸カルシウムを用いた以外は実施例９と同様にして、表１に示す組成と細孔容積の触媒（１２）および（１３）を得た。
（実施例１４）
炭酸カルシウム６００ｇ、酸化ニッケル（ＮｉＯ）２００ｇ、酸化アルミニウム（α−Ａｌ２Ｏ３）２００ｇに適量の水と成型助剤とを添加しつつニーダーでよく混合した後、押出成型機で直径５ｍｍ、長さ５ｍｍのペレット状に成型した。このペレットを１００℃で１０時間乾燥した後、５００℃で５時間空気雰囲気下で焼成してペレット状の触媒（１４）を得た。この触媒の組成は、Ｃａ：Ｎｉ：Ａｌ（ＣａＯ：ＮｉＯ：Ａｌ２Ｏ３として）＝４５．７：３０．８：２３．５（質量％）であり、その細孔容積は０．１７ｍｌ／ｇであった。
（実施例１５、１６）
実施例１４における酸化アルミニウム（α−Ａｌ２Ｏ３）の代わりに、酸化チタン（ＴｉＯ２）または酸化ケイ素（ＳｉＯ２）を用いた以外は実施例１４と同様にして、表１に示す組成と細孔容積の触媒（１５）および（１６）を得た。
（比較例１）
実施例１における炭酸カルシウムの代わりに、酸化アルミニウム（α−Ａｌ２Ｏ３）を用いた以外は実施例１と同様にして、表１に示す組成と細孔容積の触媒（比較１）を得た。
（比較例２）
実施例１における酸化ニッケルの代わりに、酸化アルミニウム（α−Ａｌ２Ｏ３）を用いた以外は実施例１と同様にして、表１に示す組成と細孔容積の触媒（比較２）を得た。
（比較例３）
実施例９における炭酸カルシウムの代わりに、酸化アルミニウム（α−Ａｌ２Ｏ３）を用いた以外は実施例９と同様にして、表１に示す組成と細孔容積の触媒（比較３）を得た。
（比較例４）
実施例１における炭酸カルシウムの代わりに硫酸カルシウムを用い、さらに押出成型機内の真空度を高めた以外は実施例１と同様にして、表１に示す組成と細孔容積の触媒（比較４）を得た。
（比較例５）
実施例９における炭酸カルシウムの代わりに硫酸カルシウムを用い、さらに押出成型機内の真空度を高めた以外は実施例９と同様にして、表１に示す組成と細孔容積の触媒（比較５）を得た。
（実施例１７）
触媒（１）〜（１６）および比較触媒（比較１）〜（比較５）の亜酸化窒素分解能を下記の方法により評価した。
（評価方法）
触媒１２０ｍｌを内径３０ｍｍのガラス製反応管に充填した。この触媒層に下記組成の合成ガスを下記条件下に導入した。
＜合成ガス組成＞
亜酸化窒素（Ｎ２Ｏ）：５００ｐｐｍ、酸素（Ｏ２）：５容量％、Ｈ２Ｏ：１０容量％、残り：窒素（Ｎ２）
＜処理条件＞
ガス量：１０ＮＬ／ｍｉｎ、処理温度：４５０℃、空間速度（ＳＶ）：５，０００ｈｒ−１（ＳＴＰ）
上記合成ガスを導入してから１０時間後、上記触媒層の入口および出口における合成ガス中の亜酸化窒素（Ｎ２Ｏ）濃度を非分散赤外線式Ｎ２Ｏ計（日本サーモエレクトロン（株）製、Ｍｏｄｅｌ ４６Ｃ−ＨＬ）により測定し、次式に従ってＮ２Ｏ除去率を算出した。結果を表１に示す。
The invention is further illustrated by the following examples, which illustrate advantageous embodiments of the invention.
Example 1
After adding an appropriate amount of water and a molding aid to 800 g of calcium carbonate and 200 g of nickel oxide (NiO), the mixture was mixed well with a kneader, and then molded into a pellet having a diameter of 5 mm and a length of 5 mm with an extruder. The pellet was dried at 100 ° C. for 10 hours and then calcined at 500 ° C. for 5 hours in an air atmosphere to obtain a pellet-shaped catalyst (1). The composition of this catalyst was Ca: Ni (as CaO: NiO) = 69.1: 30.9 (mass%), and its pore volume was 0.25 ml / g.
(Examples 2 to 4)
Catalysts (2) to (2) to (1) of the compositions and pore volumes shown in Table 1 were used in the same manner as in Example 1 except that basic magnesium carbonate, strontium carbonate, or barium carbonate was used instead of calcium carbonate in Example 1. 4) was obtained.
(Examples 5 and 6)
Catalysts (5) and (6) having the compositions and pore volumes shown in Table 1 were obtained in the same manner as in Example 1 except that tricalcium phosphate or calcium sulfate was used instead of calcium carbonate in Example 1. It was.
(Examples 7 and 8)
In the same manner as in Example 1 except that cobalt oxide (Co 3 O 4 ) or copper oxide (CuO) was used instead of nickel oxide (NiO) in Example 1, the compositions and pore volumes shown in Table 1 were used. Catalysts (7) and (8) were obtained.
Example 9
After mixing 995g of calcium carbonate and 5g of ruthenium oxide (made by Tanaka Kikinzoku Co., Ltd., containing 65% by mass of ruthenium) with a suitable amount of water and a molding aid and mixing well with a kneader, the diameter is 5mm and long with an extruder. It was molded into a 5 mm pellet. The pellet was dried at 100 ° C. for 10 hours and then calcined at 500 ° C. for 5 hours in an air atmosphere to obtain a pellet-shaped catalyst (9). The composition of this catalyst was Ca: Ru (as CaO: Ru) = 99.4: 0.6 (mass%), and the pore volume was 0.22 ml / g.
(Examples 10 and 11)
Catalysts (10) and (11) having the compositions and pore volumes shown in Table 1 were obtained in the same manner as in Example 9, except that rhodium oxide or platinum oxide was used instead of ruthenium oxide in Example 9.
(Examples 12 and 13)
Catalysts (12) and (13) having the compositions and pore volumes shown in Table 1 were obtained in the same manner as in Example 9, except that tricalcium phosphate or calcium sulfate was used instead of calcium carbonate in Example 9. It was.
(Example 14)
A mixture of 600 g of calcium carbonate, 200 g of nickel oxide (NiO), and 200 g of aluminum oxide (α-Al 2 O 3 ) was mixed well with a kneader while adding an appropriate amount of water and a molding aid, and then 5 mm in diameter and long in an extruder. It was molded into a 5 mm pellet. The pellet was dried at 100 ° C. for 10 hours and then calcined at 500 ° C. for 5 hours in an air atmosphere to obtain a pellet-shaped catalyst (14). The composition of this catalyst is Ca: Ni: Al (as CaO: NiO: Al 2 O 3 ) = 45.7: 30.8: 23.5 (mass%), and the pore volume is 0.17 ml / g.
(Examples 15 and 16)
In the same manner as in Example 14 except that titanium oxide (TiO 2 ) or silicon oxide (SiO 2 ) was used instead of aluminum oxide (α-Al 2 O 3 ) in Example 14, the compositions shown in Table 1 were obtained. Pore volume catalysts (15) and (16) were obtained.
(Comparative Example 1)
A catalyst (comparative 1) having the composition and pore volume shown in Table 1 was obtained in the same manner as in Example 1 except that aluminum oxide (α-Al 2 O 3 ) was used instead of calcium carbonate in Example 1. It was.
(Comparative Example 2)
A catalyst (comparative 2) having the composition and pore volume shown in Table 1 was obtained in the same manner as in Example 1 except that aluminum oxide (α-Al 2 O 3 ) was used instead of nickel oxide in Example 1. It was.
(Comparative Example 3)
A catalyst (comparative 3) having the composition and pore volume shown in Table 1 was obtained in the same manner as in Example 9, except that aluminum oxide (α-Al 2 O 3 ) was used instead of calcium carbonate in Example 9. It was.
(Comparative Example 4)
In the same manner as in Example 1 except that calcium sulfate was used instead of calcium carbonate in Example 1 and the degree of vacuum in the extruder was further increased, a catalyst having a composition and pore volume shown in Table 1 (Comparative 4) was used. Obtained.
(Comparative Example 5)
In the same manner as in Example 9 except that calcium sulfate was used instead of calcium carbonate in Example 9 and the degree of vacuum in the extruder was further increased, a catalyst having a composition and pore volume shown in Table 1 (Comparative 5) was used. Obtained.
(Example 17)
The nitrous oxide resolution of the catalysts (1) to (16) and the comparative catalysts (Comparative 1) to (Comparative 5) was evaluated by the following method.
(Evaluation methods)
120 ml of catalyst was filled in a glass reaction tube having an inner diameter of 30 mm. A synthesis gas having the following composition was introduced into the catalyst layer under the following conditions.
<Syngas composition>
Nitrous oxide (N 2 O): 500 ppm, oxygen (O 2 ): 5% by volume, H 2 O: 10% by volume, remaining: nitrogen (N 2 )
<Processing conditions>
Gas amount: 10 NL / min, treatment temperature: 450 ° C., space velocity (SV): 5,000 hr −1 (STP)
10 hours after the synthesis gas was introduced, the concentration of nitrous oxide (N 2 O) in the synthesis gas at the inlet and outlet of the catalyst layer was measured using a non-dispersive infrared N 2 O meter (manufactured by Nippon Thermo Electron Co., Ltd.). , Model 46C-HL), and the N 2 O removal rate was calculated according to the following formula. The results are shown in Table 1.
Claims (4)
A method for purifying a nitrous oxide-containing gas, comprising bringing a gas containing nitrous oxide into contact with the catalyst of claim 1, 2 or 3 to decompose and remove nitrous oxide.
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| WO2008081799A1 (en) * | 2006-12-26 | 2008-07-10 | Nippon Shokubai Co., Ltd. | Catalyst for decomposition of dinitrogen monoxide and method for processing dinitrogen monoxide-containing gas |
| WO2008142765A1 (en) * | 2007-05-18 | 2008-11-27 | Nippon Shokubai Co., Ltd. | Catalyst for nitrous oxide decomposition and method of purifying gas containing nitrous oxide |
| JP2012034576A (en) * | 2010-08-03 | 2012-02-23 | Kajima Corp | Nitrous oxide decomposition apparatus |
| JP2012050969A (en) * | 2010-09-03 | 2012-03-15 | Nippon Shokubai Co Ltd | Catalyst for decomposing nitrous oxide and method for cleaning nitrous oxide-containing gas by using the same |
| CZ305451B6 (en) * | 2013-12-27 | 2015-09-23 | Vysoká škola chemicko- technologická v Praze | Catalyst for removing N2O from waste gases and process for preparing thereof |
| WO2016087269A1 (en) | 2014-12-03 | 2016-06-09 | Basf Se | Rhodium catalyst for decomposing nitrous oxide, the production thereof, and the use thereof |
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| US10695750B2 (en) | 2014-12-03 | 2020-06-30 | Basf Se | Catalyst for decomposition of nitrous oxide |
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