JP4960580B2 - Hydrocarbon removal catalyst and hydrocarbon removal method thereof - Google Patents
Hydrocarbon removal catalyst and hydrocarbon removal method thereof Download PDFInfo
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- JP4960580B2 JP4960580B2 JP2004063735A JP2004063735A JP4960580B2 JP 4960580 B2 JP4960580 B2 JP 4960580B2 JP 2004063735 A JP2004063735 A JP 2004063735A JP 2004063735 A JP2004063735 A JP 2004063735A JP 4960580 B2 JP4960580 B2 JP 4960580B2
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- 239000003054 catalyst Substances 0.000 title claims description 139
- 238000000034 method Methods 0.000 title claims description 55
- 229930195733 hydrocarbon Natural products 0.000 title description 17
- 150000002430 hydrocarbons Chemical class 0.000 title description 16
- 239000004215 Carbon black (E152) Substances 0.000 title description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 187
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 137
- 239000007789 gas Substances 0.000 claims description 99
- 229910052697 platinum Inorganic materials 0.000 claims description 82
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 46
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 40
- 230000003647 oxidation Effects 0.000 claims description 35
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 40
- 239000011593 sulfur Substances 0.000 description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- -1 ethylene, propylene Chemical group 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 17
- 239000010410 layer Substances 0.000 description 15
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 229930195734 saturated hydrocarbon Natural products 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 150000003058 platinum compounds Chemical class 0.000 description 7
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000009970 fire resistant effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000005595 acetylacetonate group Chemical group 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 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
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
本発明は、ガス（例えば、燃焼機器、特に液化石油ガスや天然ガスなどの軽質燃料を用いる内燃機関から排出される排ガス）中の低級不飽和炭化水素（エチレン、プロピレンなど）の酸化に用いられる触媒（特に排ガス浄化用触媒）およびその炭化水素酸化方法（特に排ガス浄化方法）に関する。 The present invention is used for oxidation of lower unsaturated hydrocarbons (ethylene, propylene, etc.) in gas (for example, exhaust gas discharged from an internal combustion engine using light fuel such as liquefied petroleum gas or natural gas, for example, combustion equipment). The present invention relates to a catalyst (particularly an exhaust gas purification catalyst) and a hydrocarbon oxidation method thereof (particularly an exhaust gas purification method).
内燃機関の排気ガス中には、環境上特に有害である窒素酸化物や健康上問題のある一酸化炭素に加えて、微量の炭化水素が含まれる。炭化水素は、大気中において窒素酸化物と反応して光化学スモッグを引き起こすため、その排出は抑制すべきであると考えられており、特に、自動車の排ガスでは、窒素酸化物、一酸化炭素とともに炭化水素の排出も規制されている。 The exhaust gas of an internal combustion engine contains trace amounts of hydrocarbons in addition to nitrogen oxides that are particularly harmful to the environment and carbon monoxide that is a health problem. Since hydrocarbons react with nitrogen oxides in the atmosphere to cause photochemical smog, it is thought that their emissions should be suppressed, especially in automobile exhaust gas, as well as nitrogen oxides and carbon monoxide. Hydrogen emissions are also regulated.
液化石油ガスなど軽質燃料を燃料とする内燃機関から排出される排ガス中の炭化水素は、低級飽和炭化水素が大部分であるが、ごく微量の不飽和炭化水素も含まれる。軽質燃料を燃料とする内燃機関は、ガソリン機関やディーゼル機関の排ガスと比較すると、その排ガス性状が清浄であるので、都市の中心部などの生活空間に近接した場所での利用が多い。また、このような排ガス（特に、内燃機関から排出されるガス）は、最近、温室内に排ガスを投入するなどの農業用途にも利用されている。一部の不飽和炭化水素（エチレンなど）は、ごく微量であっても植物の生育に影響することが知られており、植物に近接した場所ではこれらを極力低減することが望ましい。さらに、不飽和炭化水素は飽和炭化水素に比べると化学的に活性であるので、窒素酸化物除去などの処理を行う過程において、条件次第では部分酸化反応により含酸素化合物など臭気を伴う化合物に変換されるおそれもある。このような観点からも、排ガス中の不飽和炭化水素は、低減することが望ましい。 The hydrocarbons in the exhaust gas discharged from an internal combustion engine fueled with light fuel such as liquefied petroleum gas are mostly lower saturated hydrocarbons, but also contain very small amounts of unsaturated hydrocarbons. An internal combustion engine that uses light fuel as a fuel is often used in a place close to a living space such as the center of a city because its exhaust gas properties are clean as compared with the exhaust gas of a gasoline engine or a diesel engine. Further, such exhaust gas (especially gas discharged from an internal combustion engine) has recently been used for agricultural purposes such as injecting exhaust gas into a greenhouse. Some unsaturated hydrocarbons (such as ethylene) are known to affect plant growth even in very small amounts, and it is desirable to reduce them as much as possible in a place close to the plant. Furthermore, unsaturated hydrocarbons are chemically more active than saturated hydrocarbons, so in the process of removing nitrogen oxides, depending on the conditions, they are converted into compounds with odors, such as oxygenated compounds, depending on the conditions. There is also a risk. From such a viewpoint, it is desirable to reduce unsaturated hydrocarbons in the exhaust gas.
炭化水素や一酸化炭素などの排ガス中に含まれる可燃性成分の接触酸化に貴金属系触媒が有効である。その中でも、特に白金系触媒が低温活性に優れることも知られている。例えば、一酸化炭素の酸化触媒として、特開平７−２４１４６７号公報（特許文献１）には、ハニカム担体に担持した白金／アルミナ触媒であって、その白金担持量が１．２〜２．５ｇ／Ｌである希薄燃焼ガスエンジン排ガス中の一酸化炭素の酸化用触媒が開示されている。また、特開平７−２４１４６８号公報（特許文献２）には、同用途に対し、白金−パラジウム／アルミナ触媒が開示されている。この文献には、白金−パラジウム／アルミナ触媒が、白金／アルミナ触媒あるいはパラジウム／アルミナ触媒のいずれよりも優れた性能を示すことが記載されている。 A noble metal catalyst is effective for catalytic oxidation of combustible components contained in exhaust gas such as hydrocarbons and carbon monoxide. Among them, it is known that platinum-based catalysts are particularly excellent in low-temperature activity. For example, as an oxidation catalyst for carbon monoxide, Japanese Patent Application Laid-Open No. 7-241467 (Patent Document 1) discloses a platinum / alumina catalyst supported on a honeycomb carrier having a platinum loading of 1.2 to 2.5 g. A catalyst for the oxidation of carbon monoxide in the exhaust gas of a lean combustion gas engine that is / L. JP-A-7-241468 (Patent Document 2) discloses a platinum-palladium / alumina catalyst for the same application. This document describes that the platinum-palladium / alumina catalyst performs better than either the platinum / alumina catalyst or the palladium / alumina catalyst.
また、炭化水素除去用の触媒として、特開平１０−３０９４６２号公報（特許文献３）には、燃焼排ガス中の非メタン炭化水素の酸化触媒であって、白金担持量が０．５〜３．０ｇ／Ｌのハニカム体担持白金／アルミナ触媒が開示されている。しかし、このような触媒では、充分な炭化水素の酸化除去性能が得られない。また、このような触媒では、硫黄酸化物（いわゆるＳＯｘ）を含むガスを使用すると、触媒活性およびその耐久性が低下する虞がある。 Further, as a catalyst for removing hydrocarbons, Japanese Patent Application Laid-Open No. 10-309462 (Patent Document 3) discloses an oxidation catalyst for non-methane hydrocarbons in combustion exhaust gas, having a platinum loading of 0.5 to 3. A 0 g / L honeycomb body supported platinum / alumina catalyst is disclosed. However, with such a catalyst, sufficient hydrocarbon removal performance cannot be obtained. In such a catalyst, if a gas containing sulfur oxide (so-called SOx) is used, the catalytic activity and its durability may be lowered.
一方、アルミナ以外の担体を用いた触媒も知られている。例えば、特開２０００−２５４５００号公報（特許文献４）には、排ガス中の未燃炭化水素酸化触媒として、チタニアあるいはジルコニア担体に、白金及びパラジウムが担持されている触媒が開示されている。この文献の実施例では、前記炭化水素としてメタンのみを含むガスから、前記メタンを酸化除去している。さらに、この文献には、排ガスが硫黄酸化物を含んでいてもよいことが記載されており、実施例では、メタンおよび二酸化硫黄を含むガスを使用して、メタンの酸化性能を時間変化とともに測定することにより、触媒の耐久性を評価している。しかし、この触媒において、不飽和炭化水素に対する酸化活性は不明である。 On the other hand, a catalyst using a support other than alumina is also known. For example, JP 2000-254500 A (Patent Document 4) discloses a catalyst in which platinum and palladium are supported on a titania or zirconia support as an unburned hydrocarbon oxidation catalyst in exhaust gas. In the example of this document, the methane is oxidized and removed from a gas containing only methane as the hydrocarbon. Furthermore, this document states that the exhaust gas may contain sulfur oxides. In the examples, a gas containing methane and sulfur dioxide is used to measure the oxidation performance of methane over time. By doing so, the durability of the catalyst is evaluated. However, in this catalyst, the oxidation activity for unsaturated hydrocarbons is unknown.
以上のように、排ガス中の低級不飽和炭化水素、具体的には、エチレン、プロピレンなどの炭素数２〜５程度の不飽和炭化水素の除去技術は確立されているとは言えないのが実情である。
従って、本発明の目的は、低級不飽和炭化水素（特に、エタン、プロパン）を、高い酸化性能で効率よく酸化除去できる酸化触媒（又は酸化除去触媒）、およびこの触媒を用いた酸化方法（又は酸化除去方法）を提供することにある。 Therefore, an object of the present invention is to provide an oxidation catalyst (or oxidation removal catalyst) capable of efficiently oxidizing and removing lower unsaturated hydrocarbons (particularly ethane and propane) with high oxidation performance, and an oxidation method (or an oxidation method) using this catalyst (or It is to provide an oxidation removal method.
本発明の他の目的は、硫黄酸化物を含むガス（内燃機関から排出される排ガスなど）であっても、触媒活性を低下させることなく、優れた酸化性能［特に低温域（３００℃以下程度）での優れた酸化性能］で効率よく低級不飽和炭化水素を酸化除去できる経済性に優れた酸化触媒（又は酸化除去触媒）、およびこの触媒を用いた酸化方法（又は酸化除去方法）を提供することにある。 Another object of the present invention is to provide excellent oxidation performance [especially in a low temperature range (about 300 ° C. or lower) without reducing the catalytic activity even for a gas containing sulfur oxide (such as exhaust gas discharged from an internal combustion engine). Oxidation catalyst (or oxidation removal catalyst) that can efficiently oxidize and remove lower unsaturated hydrocarbons, and an oxidation method (or oxidation removal method) using this catalyst. There is to do.
本発明者らは前記課題を達成するため鋭意検討した結果、ジルコニアに白金を担持した触媒が、特にエチレン、プロピレンなどの低級不飽和炭化水素に対して高い酸化活性を示すとともに、通常、この種の反応において触媒毒と考えられている硫黄酸化物（ＳＯｘ）に対する耐性又は抵抗性が極めて高いことを見出し、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a catalyst in which platinum is supported on zirconia exhibits a high oxidation activity especially for lower unsaturated hydrocarbons such as ethylene and propylene, and this type is usually used. In this reaction, the present inventors have found that the resistance or resistance to sulfur oxide (SOx), which is considered to be a catalyst poison, is extremely high.
すなわち、本発明の触媒は、酸素の存在下、低級不飽和炭化水素を酸化するための触媒であって、ジルコニア担体に少なくとも白金が担持されている。前記触媒において、触媒を構成する金属成分は、実質的にジルコニウムおよび白金のみで構成されていてもよい。また、前記触媒において、白金の割合は、ジルコニア１００重量部に対して０．５〜２０重量部程度であってもよい。 That is, the catalyst of the present invention is a catalyst for oxidizing a lower unsaturated hydrocarbon in the presence of oxygen, and at least platinum is supported on a zirconia support. In the catalyst, the metal component constituting the catalyst may be substantially composed only of zirconium and platinum. In the catalyst, the ratio of platinum may be about 0.5 to 20 parts by weight with respect to 100 parts by weight of zirconia.
本発明は、前記触媒に、少なくとも酸素及び低級不飽和炭化水素を含む被処理ガスを接触させて、前記低級不飽和炭化水素を酸化する方法も含む。前記触媒は、硫黄酸化物に対する耐性を有しているので、本発明の酸化方法において、前記被処理ガスは、さらに硫黄酸化物を含んでいてもよい。例えば、前記触媒に、酸素、硫黄酸化物、前記低級不飽和炭化水素（特に、エチレンおよびプロピレン）を含む被処理ガスを所定の温度（例えば、温度１７５〜３００℃）で接触させることにより、前記低級不飽和炭化水素を酸化（又は酸化除去）してもよい。 The present invention also includes a method of oxidizing the lower unsaturated hydrocarbon by contacting the catalyst with a gas to be treated containing at least oxygen and a lower unsaturated hydrocarbon. Since the catalyst has resistance to sulfur oxides, in the oxidation method of the present invention, the gas to be treated may further contain sulfur oxides. For example, by contacting the catalyst to be treated with oxygen, sulfur oxide, and the lower unsaturated hydrocarbon (particularly ethylene and propylene) at a predetermined temperature (for example, a temperature of 175 to 300 ° C.), The lower unsaturated hydrocarbon may be oxidized (or oxidized and removed).
本発明の触媒では、低級不飽和炭化水素を、高い酸化性能で効率よく酸化除去できる。また、本発明の触媒は、ジルコニアに白金を担持することにより、硫黄酸化物を含むガス（内燃機関から排出される排ガスなど）であっても、触媒活性を低下させることなく、優れた酸化性能［特に比較的低温域（３００℃以下程度）での優れた酸化性能］で効率よく低級不飽和炭化水素を酸化除去でき、経済性に優れている。 The catalyst of the present invention, a lower unsaturated hydrocarbons, can be efficiently oxidized and removed at a high oxidizing performance. In addition, the catalyst of the present invention has excellent oxidation performance without deteriorating the catalytic activity even if it is a gas containing sulfur oxide (such as exhaust gas discharged from an internal combustion engine) by supporting platinum on zirconia. [Especially excellent oxidation performance in a relatively low temperature range (about 300 ° C. or lower)] can efficiently oxidize and remove lower unsaturated hydrocarbons, and is excellent in economic efficiency.
本発明の触媒は、ジルコニア（ジルコニウム成分）と白金（白金成分）とで構成されている。すなわち、前記触媒において、白金は少なくともジルコニアに含まれていればよく、例えば、ジルコニアに担持されていてもよく、ジルコニア内に均一に又は分散して含有されていてもよい。本発明の触媒は、通常、ジルコニアを担体とし、このジルコニア担体に少なくとも白金が担持されている。 The catalyst of the present invention is composed of zirconia (zirconium component) and platinum (platinum component). That is, in the catalyst, it is sufficient that platinum is contained in at least zirconia. For example, platinum may be supported on zirconia, or may be contained uniformly or dispersed in zirconia. The catalyst of the present invention usually has zirconia as a support, and at least platinum is supported on the zirconia support.
ジルコニアの比表面積は、例えば、１ｍ2／ｇ以上（例えば、１〜２００ｍ2／ｇ程度）であってもよく、通常、２〜１５０ｍ2／ｇ（例えば、２〜１００ｍ2／ｇ）、好ましくは２〜６０ｍ2／ｇ（例えば、２〜５０ｍ2／ｇ）、さらに好ましくは５〜３０ｍ2／ｇ（例えば、１０〜３０ｍ2／ｇ）程度であってもよい。比表面積が小さすぎると白金を高分散に保つことができなくなる一方、比表面積が大きすぎると、不安定となって使用中に担体の焼結が進行するおそれがある。 The specific surface area of zirconia, for example, 1 m 2 / g or more (e.g., 1～200M about 2 / g) may be, usually, 2~150m 2 / g (e.g., 2 to 100 m 2 / g), preferably 2~60m 2 / g (eg, 2~50m 2 / g), more preferably 5 to 30 m 2 / g (e.g., 10~30m 2 / g) may be about. If the specific surface area is too small, platinum cannot be kept highly dispersed. On the other hand, if the specific surface area is too large, the carrier may become unstable and sintering of the carrier may proceed during use.
なお、ジルコニア（ＺｒＯ2）は、酸化物（ジルコニア）の形態で存在するものの、触媒活性を損なわない範囲で、ジルコニウム化合物（例えば、水酸化物、ハロゲン化物、酸素酸塩、有機酸塩）を含んでいてもよい。また、白金を担持する担体は、少なくともジルコニアで構成されていればよく、ジルコニアと他の担体（アルミナ、チタニア、シリカ、活性炭など）と組み合わせてもよいが、通常、ジルコニア単独で構成されている場合が多い。 Although zirconia (ZrO 2 ) exists in the form of an oxide (zirconia), a zirconium compound (for example, a hydroxide, a halide, an oxyacid salt, or an organic acid salt) is used as long as the catalytic activity is not impaired. May be included. Further, the carrier supporting platinum may be at least composed of zirconia, and may be combined with zirconia and other carriers (alumina, titania, silica, activated carbon, etc.), but is usually composed of zirconia alone. There are many cases.
触媒を構成する白金（白金成分）は、触媒活性に影響を与えない範囲で、金属単体Ｐｔとして含有されていてもよく、化合物の形態で含有されていてもよい。例えば、白金（白金成分）は、白金単体、酸化白金（二酸化白金など）、塩（硝酸塩などの無機酸塩、有機酸塩、錯塩など）、錯体などの形態で含まれていてもよく、これらの形態が混合していてもよい。白金成分は、通常、少なくとも酸化白金の形態であってもよい。さらに、白金の価数は特に制限されず、二価の白金Ｐｔ(II)であってもよく、四価の白金Ｐｔ(IV)であってもよい。 Platinum (platinum component) constituting the catalyst may be contained as a simple metal Pt or may be contained in the form of a compound as long as the catalyst activity is not affected. For example, platinum (platinum component) may be contained in the form of platinum alone, platinum oxide (such as platinum dioxide), salt (inorganic acid salt such as nitrate, organic acid salt, complex salt, etc.), complex, etc. These forms may be mixed. The platinum component is usually at least in the form of platinum oxide. Furthermore, the valence of platinum is not particularly limited, and may be divalent platinum Pt (II) or tetravalent platinum Pt (IV).
本発明の触媒において、白金（白金成分）の割合（又は担持量）は、ジルコニア１００重量部に対して、白金の重量換算で、例えば、０．１〜３０重量部の範囲から選択でき、例えば、０．５〜２０重量部、好ましくは１〜１０重量部、さらに好ましくは１〜５重量部程度である。白金の割合が少なすぎると触媒活性が低く、また多すぎると白金の粒径が大きくなり、担持された白金が有効に使われなくなる場合がある。 In the catalyst of the present invention, the ratio (or supported amount) of platinum (platinum component) can be selected from a range of, for example, 0.1 to 30 parts by weight in terms of platinum with respect to 100 parts by weight of zirconia. 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably about 1 to 5 parts by weight. If the proportion of platinum is too small, the catalytic activity is low, and if it is too large, the particle size of platinum becomes large and the supported platinum may not be used effectively.
本発明の触媒は、ジルコニア担体に少なくとも白金が担持されていればよく、白金に加えて、必要に応じてさらに他の金属（又は金属成分）を含んで（又は担持されて）いてもよい。このような金属としては、周期表第８Ａ族、第１Ｂ族、第２Ｂ族金属などが例示でき、特に、貴金属（銀、ルテニウム、ロジウム、パラジウムなど）が挙げられる。他の金属（又は貴金属）の割合は、ジルコニア１００重量部に対して、０．１〜３０重量部、好ましくは０．５〜２０重量部程度であってもよい。また、他の金属の割合は、白金１重量部に対して、０．１〜１５重量部の範囲から選択でき、例えば、１〜１０重量部（例えば、２〜１０重量部）、好ましくは２〜８重量部、さらに好ましくは３〜８重量部程度であってもよい。 The catalyst of the present invention is not limited as long as at least platinum is supported on the zirconia support, and may further contain (or be supported) other metals (or metal components) as necessary in addition to platinum. Examples of such metals include Group 8A, Group 1B, and Group 2B metals of the periodic table, and particularly include noble metals (silver, ruthenium, rhodium, palladium, etc.). The ratio of the other metal (or noble metal) may be about 0.1 to 30 parts by weight, preferably about 0.5 to 20 parts by weight with respect to 100 parts by weight of zirconia. Moreover, the ratio of another metal can be selected from the range of 0.1-15 weight part with respect to 1 weight part of platinum, for example, 1-10 weight part (for example, 2-10 weight part), Preferably it is 2 -8 parts by weight, more preferably about 3-8 parts by weight.
なお、他の金属（貴金属など）は、特定の条件下で触媒活性を低下させる場合がある。例えば、貴金属（パラジウムなど）を添加することにより、白金以外の貴金属（パラジウムなど）の添加量が比較的多量である場合（例えば、白金以外の貴金属の添加量が、白金１００重量部に対して１０重量部を超える場合など）や、低温領域（例えば、２００℃以下程度の領域）などにおける酸化性能が低下する場合がある。 Note that other metals (such as noble metals) may reduce the catalytic activity under specific conditions. For example, when a noble metal (palladium or the like) is added in a relatively large amount of a precious metal (such as palladium) other than platinum (for example, the addition amount of a noble metal other than platinum is 100 parts by weight of platinum). The oxidation performance in a low temperature region (for example, a region of about 200 ° C. or less) may be deteriorated.
そのため、本発明の触媒は、他の金属（又は貴金属、特にパラジウム）を含んでいなくてもよい。すなわち、本発明の触媒（又はその触媒活性物質）を構成する金属（又は金属成分）は、ジルコニウム及び白金以外の金属（貴金属、特にパラジウム）を含んでいなくてもよい。好ましい態様では、本発明の触媒において、触媒（又は触媒活性物質）を構成する金属成分が、実質的にジルコニウムおよび白金のみで構成されていてもよい。本発明の触媒は、他の金属（特にパラジウム）を含まなくても、効率よく触媒活性を向上することができる。 Therefore, the catalyst of the present invention may not contain other metals (or noble metals, particularly palladium). That is, the metal (or metal component) constituting the catalyst of the present invention (or its catalytically active substance) may not contain a metal (noble metal, particularly palladium) other than zirconium and platinum. In a preferred embodiment, in the catalyst of the present invention, the metal component constituting the catalyst (or catalytically active substance) may be substantially composed only of zirconium and platinum. Even if the catalyst of this invention does not contain other metals (especially palladium), it can improve a catalyst activity efficiently.
本発明の触媒は、さらに硫黄成分を含んでいてもよい。硫黄成分は、少なくとも硫黄原子で構成されていればよく、後述する硫黄成分を含有させる方法などに応じて、例えば、硫黄化合物（例えば、二酸化硫黄などの硫黄酸化物など）、硫黄原子を含むイオン［硫酸根（ＳＯ4 2-）など］、塩（硫酸塩など）などの形態で前記触媒に含有されていてもよく、これらの形態が混合して前記触媒に含有されていてもよい。好ましい硫黄成分は、少なくとも硫酸根の形態で存在するようである。 The catalyst of the present invention may further contain a sulfur component. The sulfur component only needs to be composed of at least a sulfur atom. For example, a sulfur compound (for example, a sulfur oxide such as sulfur dioxide) or an ion containing a sulfur atom is used depending on the method for containing the sulfur component described later. [Sulphate radicals (SO 4 2−, etc.)], salts (sulfates, etc.) and the like may be contained in the catalyst, and these forms may be mixed and contained in the catalyst. The preferred sulfur component appears to be present at least in the form of sulfate radicals.
硫黄成分の含有形態は、特に限定されないが、硫黄成分の形態（イオンなど）などに応じて、例えば、配位（金属成分に対する配位）、塩（金属成分との塩形成）、吸着（化学吸着など）などの形態により含有されていてもよい。 The content of the sulfur component is not particularly limited, but for example, depending on the form of the sulfur component (ion, etc.), coordination (coordination with the metal component), salt (salt formation with the metal component), adsorption (chemical) It may be contained in a form such as adsorption).
硫黄成分の含有割合は、後述する硫黄成分の含有方法にもよるが、例えば、硫黄Ｓ換算で、触媒（ジルコニアと担持した白金との総量）１００重量部に対して、０．０５〜１０重量部、好ましくは０．１〜５重量部、さらに好ましくは０．２〜１．５重量部程度であってもよい。また、硫黄成分の含有割合は、硫黄Ｓ換算で、ジルコニア（ＺｒＯ2）１００重量部に対して、０．０５〜１０重量部、好ましくは０．１〜５重量部、さらに好ましくは０．２〜１．５重量部程度であってもよい。特に、硫酸根（ＳＯ4 2-として換算）の含有割合は、ジルコニア（ＺｒＯ2）１００重量部に対して、０．１５〜３０重量部、好ましくは０．３〜１５重量部、さらに好ましくは０．６〜４．５重量部程度であってもよい。 Although the content rate of a sulfur component is based also on the content method of the sulfur component mentioned later, for example, it is 0.05-10 weight with respect to 100 weight part of catalysts (total amount of zirconia and the platinum carry | supported) in conversion of sulfur S. Part, preferably 0.1 to 5 parts by weight, more preferably about 0.2 to 1.5 parts by weight. Further, the content of sulfur component, the sulfur S terms, with respect to zirconia (ZrO 2) 100 parts by weight, 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 About 1.5 parts by weight may be used. In particular, the content of sulfate radical (converted as SO 4 2− ) is 0.15 to 30 parts by weight, preferably 0.3 to 15 parts by weight, more preferably 100 parts by weight of zirconia (ZrO 2 ). About 0.6 to 4.5 parts by weight may be used.
なお、硫黄成分（硫酸根など）は、後述するように、原料や硫黄成分の含有方法などを選択することにより、比較的多量、例えば、触媒（ジルコニアと白金との総量）又はジルコニア１００重量部に対して、硫黄Ｓ換算で、１．５〜１０重量部、好ましくは２〜９重量部、さらに好ましくは３〜８重量部程度の含有割合で前記触媒に含有させることも可能である。 In addition, as described later, the sulfur component (such as sulfate radical) is selected in a relatively large amount by selecting a raw material or a method of containing the sulfur component, for example, a catalyst (total amount of zirconia and platinum) or 100 parts by weight of zirconia. On the other hand, in terms of sulfur S, the catalyst can be contained in a content ratio of about 1.5 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably about 3 to 8 parts by weight.
また、硫黄成分の含有割合は、前記触媒の白金１重量部に対して、硫黄Ｓ換算で、例えば、０．１〜１０重量部、好ましくは０．１〜５重量部、さらに好ましくは０．２〜２重量部程度であってもよい。 Moreover, the content rate of a sulfur component is 0.1-10 weight part in conversion of sulfur S with respect to 1 weight part of platinum of the said catalyst, Preferably it is 0.1-5 weight part, More preferably, it is 0.00. It may be about 2 to 2 parts by weight.
本発明の触媒は、非多孔質であってもよく多孔質であってもよい。触媒のＢＥＴ比表面積は、１ｍ2／ｇ以上（例えば、１〜２００ｍ2／ｇ程度）であってもよく、通常、２〜１５０ｍ2／ｇ（例えば、２〜１００ｍ2／ｇ）、好ましくは２〜６０ｍ2／ｇ（例えば、２〜５０ｍ2／ｇ）、さらに好ましくは５〜３０ｍ2／ｇ（例えば、１０〜３０ｍ2／ｇ）程度であってもよい。 The catalyst of the present invention may be non-porous or porous. BET specific surface area of the catalyst, 1 m 2 / g or more (e.g., 1～200M about 2 / g) may be, usually, 2~150m 2 / g (e.g., 2 to 100 m 2 / g), preferably 2~60m 2 / g (e.g., 2~50m 2 / g), more preferably 5 to 30 m 2 / g (e.g., 10~30m 2 / g) may be about.
触媒の形状としては、例えば、粉粒状、粒状、ペレット状、ハニカム状などが挙げられる。これらの形状のうち、圧力損失を低減する観点からハニカム状が好ましい。ハニカム形状の触媒は、触媒成分（少なくともジルコニアおよび白金）をハニカム状に成形することにより得てもよいが、後述するように、通常、ハニカム上に、ジルコニアと白金とで構成された層（触媒活性層）を形成して製造する場合が多い。このような触媒活性層は、白金（および必要に応じて他の金属）が担持されたジルコニアを含む単一の層であってもよく、ジルコニアで構成された層と、この層に担持され、かつ白金で構成された層とで形成されていてもよい。ハニカムのセル数は、圧力損失の増大を抑制できる範囲で選択でき、例えば、１〜２５０個／ｃｍ2、好ましくは５〜１５０個／ｃｍ2、さらに好ましくは１０〜１００個／ｃｍ2程度であってもよい。ハニカムの開口率は、例えば、３０〜８０％（例えば、５０〜８０％）、好ましくは５０〜７５％程度であってもよい。 Examples of the shape of the catalyst include powder, granule, pellet, and honeycomb. Of these shapes, a honeycomb shape is preferable from the viewpoint of reducing pressure loss. A honeycomb-shaped catalyst may be obtained by forming a catalyst component (at least zirconia and platinum) into a honeycomb shape. However, as will be described later, a layer composed of zirconia and platinum is usually formed on the honeycomb (catalyst). In many cases, the active layer is formed. Such a catalytically active layer may be a single layer comprising zirconia on which platinum (and other metals as needed) is supported, a layer composed of zirconia, supported on this layer, And it may be formed with the layer comprised with platinum. The number of cells of the honeycomb can be selected within a range in which an increase in pressure loss can be suppressed. For example, the number of cells is 1 to 250 cells / cm 2 , preferably 5 to 150 cells / cm 2 , and more preferably about 10 to 100 cells / cm 2 . There may be. The aperture ratio of the honeycomb may be, for example, 30 to 80% (for example, 50 to 80%), preferably about 50 to 75%.
［触媒の製造方法］
本発明の触媒は、通常、ジルコニア（酸化ジルコニウム）に白金を含有（特に担持）させることにより製造でき、通常、ジルコニア（又はジルコニウム成分）に、白金成分（白金イオンなど）添加し、焼成することにより得ることができる。白金を含有させる方法は特に限定されず、含浸法、平衡吸着法などを利用できる。含浸法では、例えば、ジルコニア担体に、白金成分（白金イオンなど）を含む白金金属化合物の溶液（水溶液など）を含浸し、乾燥、焼成することによって前記触媒を得ることができる。
[Method for producing catalyst]
The catalyst of the present invention can be usually produced by containing (particularly supporting) platinum in zirconia (zirconium oxide), and usually adding a platinum component (such as platinum ion) to zirconia (or zirconium component) and calcining. Can be obtained. The method of containing platinum is not particularly limited, and an impregnation method, an equilibrium adsorption method, or the like can be used. In the impregnation method, for example, the catalyst can be obtained by impregnating a zirconia support with a solution (such as an aqueous solution) of a platinum metal compound containing a platinum component (such as platinum ions), drying, and firing.
原料となるジルコニアとしては、市販の触媒担体用ジルコニアを用いてもよく、ジルコニウム成分（又はジルコニウム化合物）［例えば、水酸化ジルコニウム、無機酸塩（硫酸ジルコニウム、硝酸ジルコニウムなど）、ハロゲン化物（塩化ジルコニウムなど）、有機酸塩（酢酸ジルコニウムなど）など、好ましくは水酸化ジルコニウム］を焼成（例えば、６００〜１０００℃程度で焼成）して用いてもよい。なお、ジルコニウム成分（例えば、水酸化ジルコニウム）を、後述する硫酸成分で処理してから焼成して得たジルコニア（硫酸根ジルコニア）は、市販のジルコニアなどに比べて、結晶構造が異なる（市販のジルコニアなどでは単斜晶である）ためか、比較的大きい比表面積を有する場合が多い。そのため、このような方法で得られたジルコニアを使用することにより、後述するように、硫黄成分の含有割合を高めてもよい。 As a raw material zirconia, a commercially available zirconia for a catalyst support may be used, and a zirconium component (or zirconium compound) [for example, zirconium hydroxide, inorganic acid salt (zirconium sulfate, zirconium nitrate, etc.), halide (zirconium chloride). Or an organic acid salt (such as zirconium acetate), preferably zirconium hydroxide] may be fired (for example, fired at about 600 to 1000 ° C.). Zirconia (sulfuric acid zirconia) obtained by treating a zirconium component (for example, zirconium hydroxide) with a sulfuric acid component described later and calcining has a different crystal structure (commercially available zirconia). In many cases, it has a relatively large specific surface area because it is monoclinic in zirconia or the like. Therefore, you may raise the content rate of a sulfur component by using the zirconia obtained by such a method so that it may mention later.
白金化合物としては、特に制限されず、種々の白金含有化合物が使用でき、例えば、無機酸塩（硝酸塩など）、ハロゲン化物（塩化物など）、有機酸塩（酢酸塩など）、錯体又は錯塩（例えば、アセチルアセトナト錯体、カルボニル錯体、アンミン錯体など）が例示できる。特に、塩化物（例えば、塩化白金酸など）、錯体又は錯塩［例えば、ビス（アセチルアセトナト）白金、テトラアンミン白金硝酸塩など］を好適に使用できる。これらの白金化合物は単独で又は二種以上組み合わせて使用できる。含浸に用いる白金化合物の溶液は、水溶液で行う場合には、水溶性の化合物（塩化白金酸、テトラアンミン白金硝酸塩など）を水（純水）に溶解することにより調製できる。また、白金化合物の溶液は、有機金属化合物［ビス（アセチルアセトナト）白金など］を有機溶媒（アセトンなど）に溶解した有機溶媒系であってもよい。さらに、白金化合物の溶液は、必要に応じて水に水溶性の有機溶媒を加えた混合溶媒としてもよい。 The platinum compound is not particularly limited, and various platinum-containing compounds can be used. For example, inorganic acid salts (such as nitrates), halides (such as chlorides), organic acid salts (such as acetates), complexes or complex salts ( For example, an acetylacetonato complex, a carbonyl complex, an ammine complex, etc.) can be illustrated. In particular, a chloride (eg, chloroplatinic acid), a complex or a complex salt [eg, bis (acetylacetonato) platinum, tetraammineplatinum nitrate, etc.] can be preferably used. These platinum compounds can be used alone or in combination of two or more. The solution of the platinum compound used for impregnation can be prepared by dissolving a water-soluble compound (chloroplatinic acid, tetraammineplatinum nitrate, etc.) in water (pure water) when carried out as an aqueous solution. In addition, the platinum compound solution may be an organic solvent system in which an organometallic compound [bis (acetylacetonato) platinum or the like] is dissolved in an organic solvent (acetone or the like). Furthermore, the platinum compound solution may be a mixed solvent in which a water-soluble organic solvent is added to water as necessary.
なお、前記他の金属（例えば、パラジウムなどの白金以外の貴金属）は、前記白金を含有させる方法と同様の方法を利用して含有（担持）させることができる。例えば、含浸法では、白金化合物および他の金属の化合物（貴金属塩など）の両方を溶解する溶液（水溶液など）を用いて一度にジルコニアに含有させて（特に担持させても）よい。他の金属の金属化合物（貴金属塩など）の種類によっては、白金化合物との混合により沈殿を生じる場合があるので、このような場合には、金属（白金および他の金属）を１種類ずつ順番に含有させても（担持させても）よく、例えば、第１の金属（白金など）を含有（担持）させた後、適宜乾燥や仮焼などの工程を経て、第２の金属（パラジウムなど）を含有（担持）させてもよい。 The other metal (for example, a noble metal other than platinum such as palladium) can be contained (supported) using a method similar to the method of containing platinum. For example, in the impregnation method, a solution (such as an aqueous solution) in which both a platinum compound and another metal compound (such as a noble metal salt) are dissolved may be included (particularly supported) in zirconia at a time. Depending on the type of metal compound (noble metal salt, etc.) of other metals, precipitation may occur due to mixing with the platinum compound. In such cases, the metals (platinum and other metals) are ordered one by one. For example, after the first metal (such as platinum) is contained (supported), the second metal (such as palladium) is appropriately subjected to steps such as drying and calcining. ) May be contained (supported).
焼成時に流通するガスは、通常の空気を使用してもよく、空気又は酸素と、窒素などの不活性ガスとを適宜混合したガスを用いてもよい。焼成温度は、安定して高い触媒活性を付与できる範囲であればよく、例えば、４５０〜６５０℃の範囲で選択でき、好ましくは５００〜６００℃程度の範囲であってもよい。焼成温度は高すぎると、担持された金属（白金、前記他の金属）の粒成長が進んで高い活性が得られない場合がある。逆に焼成温度が低すぎても焼成の効果が無く、触媒の使用中に金属（白金、前記他の金属）の粒成長が進んで安定した活性が得られないおそれがある。 As the gas flowing during firing, normal air may be used, or a gas obtained by appropriately mixing air or oxygen and an inert gas such as nitrogen may be used. The calcination temperature may be in a range where high catalytic activity can be stably imparted, and can be selected, for example, in the range of 450 to 650 ° C, and preferably in the range of about 500 to 600 ° C. If the firing temperature is too high, grain growth of the supported metal (platinum or other metal) may progress and high activity may not be obtained. On the other hand, if the calcination temperature is too low, there is no effect of calcination, and there is a possibility that stable activity cannot be obtained due to progress of grain growth of metal (platinum or other metal) during use of the catalyst.
本発明の触媒は、前記のように、ペレット状やハニカム状などの任意の形状に成形できる。例えば、ハニカム状触媒は、耐火性ハニカム（例えば、コージェライト、セラミックなど）を触媒成分（少なくともジルコニア及び白金）で被覆（ウオッシュコートなど）する方法や、触媒成分に必要に応じてバインダーを添加し、ハニカム形状に押出成形する方法などが挙げられる。本発明では、圧力損失を低減するという観点から、好ましくは耐火性ハニカム上に触媒成分を被覆（特に、ウオッシュコート）する方法が好ましい。耐火性ハニカム上に触媒成分を被覆（ウオッシュコート）する場合には、（i）上記の方法で調製した触媒（ジルコニアに白金を含有させた触媒）に必要に応じてジルコニアゾルなどを加えてスラリー状にして、耐火性ハニカム上にウオッシュコートしてもよく、（ii）予めジルコニアを同様の方法で耐火性ハニカム上にウオッシュコートし、必要に応じて焼成したのち、上記の方法にしたがって白金などを担持してもよい。耐火性ハニカム（コージェライトなど）に被覆（ウオッシュコート）する場合の触媒の被覆量（コート量）は、耐火性ハニカム１リットルあたり、ジルコニア５０〜３００ｇ程度、かつ白金（白金Ｐｔ換算）０．５〜５ｇ程度とするのがよく、好ましくはジルコニア１００〜２００ｇ程度、かつ白金（白金Ｐｔ換算）１〜３ｇとしてもよい。 As described above, the catalyst of the present invention can be formed into an arbitrary shape such as a pellet shape or a honeycomb shape. For example, for honeycomb-shaped catalysts, a fire-resistant honeycomb (eg, cordierite, ceramic, etc.) is coated with a catalyst component (at least zirconia and platinum) (washcoat, etc.), and a binder is added to the catalyst component as necessary. And a method of extrusion molding into a honeycomb shape. In the present invention, from the viewpoint of reducing pressure loss, a method of coating (particularly wash coating) a catalyst component on a refractory honeycomb is preferable. When a catalyst component is coated (washcoat) on a fire-resistant honeycomb, (i) a slurry prepared by adding zirconia sol or the like to the catalyst prepared by the above method (a catalyst containing platinum in zirconia) as necessary. (Ii) Wash the zirconia on the refractory honeycomb in the same way and fire it if necessary, and then use platinum in accordance with the above method. May be supported. The coating amount (coating amount) of the catalyst when coating (washcoat) on a fire-resistant honeycomb (such as cordierite) is about 50 to 300 g of zirconia per liter of the fire-resistant honeycomb, and platinum (in terms of platinum Pt) 0.5 ˜5 g, preferably about 100 to 200 g of zirconia, and 1 to 3 g of platinum (in terms of platinum Pt).
なお、触媒の成形は、練合機、成形機（押出成形機や圧縮成形機など）、打錠機、造粒機、粉砕機などを使用して行ってもよい。 The catalyst may be molded using a kneader, a molding machine (such as an extrusion molding machine or a compression molding machine), a tableting machine, a granulator, or a pulverizer.
また、前記硫黄成分を含有させる方法としては、特に限定されず、硫黄成分を含む化合物（硫黄含有化合物）で処理する方法、例えば、（i）上記のような方法により調製した触媒（ジルコニアに白金が担持した触媒）を、硫黄成分を含む化合物（硫黄含有化合物）で処理する方法、（ii）前記触媒の調製過程において硫黄成分を含有させる方法（硫黄成分を含む化合物で処理する方法）などが挙げられる。 In addition, the method of containing the sulfur component is not particularly limited, and is a method of treating with a compound containing a sulfur component (sulfur-containing compound), for example, (i) a catalyst prepared by the above method (platinum on zirconia) And (ii) a method of containing a sulfur component in the process of preparing the catalyst (a method of treating with a compound containing a sulfur component), and the like. Can be mentioned.
硫黄含有化合物で処理する方法（i）において、硫黄含有化合物は、特に限定されないが、常温において気体の硫黄含有化合物、通常、硫黄酸化物を使用できる。硫黄酸化物としては、一酸化二硫黄、一酸化硫黄、三酸化二硫黄、二酸化硫黄、三酸化硫黄などが挙げられる。硫黄酸化物は、単独で又は２種以上組み合わせてもよい。好ましい硫黄酸化物は、二酸化硫黄、三酸化硫黄であり、特に二酸化硫黄が好ましい。 In the method (i) of treating with a sulfur-containing compound, the sulfur-containing compound is not particularly limited, but a gaseous sulfur-containing compound, usually a sulfur oxide, can be used at room temperature. Examples of the sulfur oxide include disulfur monoxide, sulfur monoxide, disulfur trioxide, sulfur dioxide, sulfur trioxide and the like. Sulfur oxides may be used alone or in combination of two or more. Preferred sulfur oxides are sulfur dioxide and sulfur trioxide, and sulfur dioxide is particularly preferred.
硫黄含有化合物で処理する方法としては、例えば、前記触媒（ジルコニアに白金が担持した触媒）に、硫黄含有化合物（特に硫黄酸化物）を接触（又は曝露）させる方法が挙げられる。なお、このような方法では、少なくとも硫黄含有化合物（特に硫黄酸化物）を含有するガスを使用すればよく、硫黄含有化合物のみを含むガスを使用してもよく、硫黄含有化合物と他のガス（例えば、酸素、窒素、炭化水素、二酸化炭素など）を含むガス（例えば、排ガス）を使用してもよい。なお、後述するように、前記低級飽和炭化水素を酸化除去するための被処理ガスとして、酸素と前記低級飽和炭化水素と硫黄酸化物（二酸化硫黄など）とを予め含むガス（特に排ガス）を使用すると、このような処理と前記低級飽和炭化水素の酸化除去とを並行して（又は連続して）行うことができるため、環境的にかつコスト的にも有利である。 Examples of the method of treating with a sulfur-containing compound include a method of contacting (or exposing) a sulfur-containing compound (particularly sulfur oxide) to the catalyst (a catalyst in which platinum is supported on zirconia). In such a method, a gas containing at least a sulfur-containing compound (especially a sulfur oxide) may be used, a gas containing only a sulfur-containing compound may be used, and a sulfur-containing compound and another gas ( For example, a gas (for example, exhaust gas) containing oxygen, nitrogen, hydrocarbon, carbon dioxide, or the like may be used. As will be described later, a gas (particularly exhaust gas) containing oxygen, the lower saturated hydrocarbon and sulfur oxide (such as sulfur dioxide) in advance is used as the gas to be treated for oxidizing and removing the lower saturated hydrocarbon. Then, since such a process and the oxidation removal of the lower saturated hydrocarbon can be performed in parallel (or continuously), it is advantageous in terms of environment and cost.
硫黄含有化合物（特に硫黄酸化物）の処理量（又は接触量又は曝露量）は、前記触媒の白金１モルに対して、硫黄原子Ｓ換算で、例えば、少なくとも１０モル（例えば、１０〜５００モル）、好ましくは１５〜２００モル、さらに好ましくは２０〜１００モル程度であってもよい。なお、処理量が少なすぎると、触媒の活性化が不十分となることがある。 The processing amount (or contact amount or exposure amount) of the sulfur-containing compound (especially sulfur oxide) is, for example, at least 10 mol (for example, 10 to 500 mol) in terms of sulfur atom S with respect to 1 mol of platinum of the catalyst. ), Preferably 15 to 200 mol, more preferably about 20 to 100 mol. In addition, when there is too little processing amount, activation of a catalyst may become inadequate.
硫黄含有化合物による処理は、常温下で行ってもよいが、通常、加温下［例えば、１００℃以上（例えば、１００〜６００℃）、好ましくは２００〜５５０℃、さらに好ましくは２５０〜５００℃程度］で行ってもよい。なお、加温は、触媒（又は触媒活性物質）を加温してもよく、接触させる硫黄含有化合物を加温してもよく、これらを組み合わせて加温してもよい。 The treatment with the sulfur-containing compound may be performed at room temperature, but usually under heating [for example, 100 ° C. or higher (for example, 100 to 600 ° C.), preferably 200 to 550 ° C., more preferably 250 to 500 ° C. Degree]. The heating may be performed by heating the catalyst (or catalytically active substance), by heating the sulfur-containing compound to be contacted, or by combining them.
調製過程で硫黄成分を含有させる方法（ii）としては、硫黄成分を調製過程で含有させる方法、例えば、（１）硫酸成分を含むジルコニウム成分（前記ジルコニウム成分など）を焼成して硫酸根ジルコニアを得る方法、（２）硫酸成分の存在下、ジルコニウム成分と白金成分とを共沈させ、この共沈物を乾燥して焼成する方法、（３）ジルコニウム成分に硫酸成分と白金成分とを担持させ、乾燥、焼成する方法などが例示できる。 As a method (ii) for containing a sulfur component in the preparation process, a method for containing a sulfur component in the preparation process, for example, (1) zirconia sulfate containing a sulfuric acid component (such as the zirconium component) is calcined to obtain sulfate zirconia. (2) A method in which a zirconium component and a platinum component are coprecipitated in the presence of a sulfuric acid component, and this coprecipitate is dried and fired. (3) A sulfuric acid component and a platinum component are supported on the zirconium component. Examples thereof include a method of drying and baking.
硫酸根ジルコニアを得る方法（１）において、硫酸成分としては、硫酸又は硫酸塩（アンモニウム塩、アルカリ又はアルカリ土類金属塩など）などが例示できる。硫酸成分は、通常、水溶液の形態で使用できる。詳細には、硫酸根ジルコニアは、ジルコニウム成分を硫酸成分の存在下で、必要によりアルカリなどによりｐＨ調整して沈殿させ、生成物を乾燥し、焼成して調製してもよい。代表的には、ジルコニウム成分（特に水酸化ジルコニウム）に硫酸成分（硫酸アンモニウムなど）を含有する水溶液を含浸させ、乾燥し、焼成してもよい。焼成温度は、例えば、３００〜７００℃、好ましくは４００〜６５０℃（例えば、５００〜６００℃）程度である。焼成時間は、０．１〜１００時間（例えば、１〜８０時間）程度の範囲から選択できる。焼成は、不活性ガス雰囲気中又は酸化性雰囲気（空気など）中で行ってもよい。そして、前記触媒は、得られた硫酸根ジルコニアに、前記方法などにより白金を含有させる（担持させる）ことにより製造できる。 In the method (1) for obtaining sulfate radical zirconia, examples of the sulfuric acid component include sulfuric acid and sulfate (such as ammonium salt, alkali or alkaline earth metal salt). The sulfuric acid component can usually be used in the form of an aqueous solution. Specifically, sulfate zirconia may be prepared by precipitating a zirconium component in the presence of a sulfuric acid component by adjusting the pH with an alkali or the like, if necessary, and drying and calcining the product. Typically, a zirconium component (particularly zirconium hydroxide) may be impregnated with an aqueous solution containing a sulfuric acid component (such as ammonium sulfate), dried, and fired. A calcination temperature is about 300-700 degreeC, for example, Preferably it is about 400-650 degreeC (for example, 500-600 degreeC). The firing time can be selected from a range of about 0.1 to 100 hours (for example, 1 to 80 hours). Firing may be performed in an inert gas atmosphere or in an oxidizing atmosphere (such as air). And the said catalyst can be manufactured by making platinum obtained zirconia contain (carry | support) platinum by the said method.
前記共沈させる方法（２）では、前記ジルコニウム成分のうち、水溶性化合物（硝酸ジルコニウム、塩化ジルコニウム、酢酸ジルコニウムなど）を使用してもよい。また、共沈は、前記と同様にｐＨ調整して行ってもよい。担持させる方法（３）では、ジルコニウム成分を硫酸成分と白金成分とで処理（浸漬又は含浸処理など）して担持させ、乾燥して焼成してもよい。前記方法（３）では、水不溶性化合物（水酸化ジルコニウムなど）を使用してもよい。また、前記方法（３）において、担持処理は、噴霧などにより行ってもよい。なお、方法（２）及び（３）において、焼成条件などは前記方法（１）と同様である。 In the coprecipitation method (2), among the zirconium components, a water-soluble compound (zirconium nitrate, zirconium chloride, zirconium acetate, etc.) may be used. Further, coprecipitation may be performed by adjusting the pH in the same manner as described above. In the supporting method (3), the zirconium component may be supported (treated by immersion or impregnation) with a sulfuric acid component and a platinum component, dried, and fired. In the method (3), a water-insoluble compound (zirconium hydroxide or the like) may be used. In the method (3), the supporting treatment may be performed by spraying or the like. In the methods (2) and (3), the firing conditions and the like are the same as those in the method (1).
なお、これらの（ii）調製過程において硫黄成分を含有させる方法（例えば、（１）硫酸成分を含むジルコニウム成分（水酸化ジルコニウムなど）を焼成して硫酸根ジルコニアを得る方法など）では、ジルコニアの結晶構造を正方晶に制御できるためか、硫黄成分を比較的高い割合（例えば、触媒又はジルコニア１００重量部に対して、硫黄Ｓ換算で、１．５〜１０重量部程度）で含有させることができる場合が多い。 In addition, in these (ii) methods of containing a sulfur component in the preparation process (for example, (1) a method of obtaining a sulfate radical zirconia by firing a zirconium component (such as zirconium hydroxide) containing a sulfuric acid component), Perhaps because the crystal structure can be controlled to be tetragonal, the sulfur component is contained in a relatively high proportion (for example, about 1.5 to 10 parts by weight in terms of sulfur S with respect to 100 parts by weight of the catalyst or zirconia). There are many cases where this is possible.
［酸化除去方法］
本発明の触媒は、低級不飽和炭化水素（例えば、エチレン、プロピレンなどのＣ2-5不飽和炭化水素、特にＣ2-3不飽和炭化水素）を酸化除去するのに有用である。すなわち、本発明では、前記触媒に、少なくとも酸素及び低級不飽和炭化水素を含む被処理ガスを接触させることにより、前記低級不飽和炭化水素を酸化（又は酸化除去）できる。
[Oxidation removal method]
The catalyst of the present invention is useful for oxidizing and removing lower unsaturated hydrocarbons (for example, C 2-5 unsaturated hydrocarbons such as ethylene and propylene, particularly C 2-3 unsaturated hydrocarbons). That is, in the present invention, the lower unsaturated hydrocarbon can be oxidized (or oxidized and removed) by bringing the gas to be treated containing at least oxygen and lower unsaturated hydrocarbon into contact with the catalyst.
前記ガス（被処理ガス）は、酸素および前記低級不飽和炭化水素のみを含んでいてもよく、酸素と前記低級不飽和炭化水素と他のガス［水蒸気、一酸化炭素、二酸化炭素、硫黄酸化物（いわゆるＳＯｘ）、窒素、窒素酸化物（いわゆるＮＯｘ）、アンモニア、前記低級不飽和炭化水素の範疇に含まれない炭化水素（メタン、エタン、プロパンなどの飽和炭化水素など）など］を含んでいてもよい。これらの他のガスは、単独で又は２種以上組み合わせて前記被処理ガスに含まれていてもよい。被処理ガスは、通常、酸素と低級不飽和炭化水素と他のガスを含む混合ガス［特に、酸素、硫黄酸化物、低級不飽和炭化水素（特にエチレンおよびプロピレン）を含むガス］である場合が多い。このような混合ガスとしては、具体的には、排ガス、例えば、内燃機関から排出される排ガスなどが挙げられる。 The gas (treated gas) may contain only oxygen and the lower unsaturated hydrocarbon, and oxygen, the lower unsaturated hydrocarbon, and other gases [water vapor, carbon monoxide, carbon dioxide, sulfur oxides] (So-called SOx), nitrogen, nitrogen oxides (so-called NOx), ammonia, hydrocarbons not included in the category of the lower unsaturated hydrocarbons (saturated hydrocarbons such as methane, ethane, and propane). Also good. These other gases may be contained in the gas to be treated singly or in combination of two or more. The gas to be treated is usually a mixed gas containing oxygen, lower unsaturated hydrocarbon and other gas [especially gas containing oxygen, sulfur oxide, lower unsaturated hydrocarbon (especially ethylene and propylene)]. Many. Specific examples of such a mixed gas include exhaust gas, for example, exhaust gas discharged from an internal combustion engine.
被処理ガス（排ガスなど）において、前記低級不飽和炭化水素の含有量は、特に限定されず、例えば、０．１ｐｐｍ以上（例えば、０．１〜５０００ｐｐｍ）、好ましくは１ｐｐｍ以上（例えば、１〜３０００ｐｐｍ）、さらに好ましくは１０ｐｐｍ以上（例えば、１０〜１０００ｐｐｍ）程度であってもよい。本発明の触媒は、触媒活性が高いため、前記低級不飽和炭化水素濃度が、比較的高濃度、例えば、５００ｐｐｍ以上（例えば、５００〜３０００ｐｐｍ、好ましくは１０００〜２０００ｐｐｍ程度）であっても、効率よく酸化除去できる。 In the gas to be treated (such as exhaust gas), the content of the lower unsaturated hydrocarbon is not particularly limited, and is, for example, 0.1 ppm or more (for example, 0.1 to 5000 ppm), preferably 1 ppm or more (for example, 1 to 1). 3000 ppm), more preferably about 10 ppm or more (for example, 10 to 1000 ppm). Since the catalyst of the present invention has high catalytic activity, even if the lower unsaturated hydrocarbon concentration is relatively high, for example, 500 ppm or more (for example, about 500 to 3000 ppm, preferably about 1000 to 2000 ppm), the efficiency is high. It can be oxidized and removed well.
また、酸素の含有量は、前記低級不飽和炭化水素を確実に酸化できる範囲であれば特に限定されないが、例えば、被処理ガス中、例えば、１〜３０体積％、好ましくは１〜２０体積％、さらに好ましくは２〜１５体積％程度であってもよい。なお、被処理ガス（排ガス）中の酸素濃度が極端に低い場合には、反応速度（酸化速度）が低下するおそれがある。このような場合には、被処理ガス（排ガス）にあらかじめ所要の量の空気を混ぜてもよい。 Further, the oxygen content is not particularly limited as long as the lower unsaturated hydrocarbon can be reliably oxidized. For example, in the gas to be treated, for example, 1 to 30% by volume, preferably 1 to 20% by volume. More preferably, it may be about 2 to 15% by volume. Note that when the oxygen concentration in the gas to be treated (exhaust gas) is extremely low, the reaction rate (oxidation rate) may decrease. In such a case, a required amount of air may be mixed in advance with the gas to be treated (exhaust gas).
なお、水蒸気の割合は、被処理ガス中、例えば、０．１〜４０体積％、好ましくは１〜３０体積％、さらに好ましくは２〜２０体積％程度であってもよい。また、二酸化炭素の割合は、被処理ガス中、例えば、０．１〜２０体積％、好ましくは０．５〜１５体積％、さらに好ましくは１〜１０体積％程度であってもよい。 In addition, the ratio of water vapor | steam may be about 0.1-40 volume% in a to-be-processed gas, for example, Preferably it is 1-30 volume%, More preferably, about 2-20 volume% may be sufficient. The proportion of carbon dioxide in the gas to be treated may be, for example, about 0.1 to 20% by volume, preferably about 0.5 to 15% by volume, and more preferably about 1 to 10% by volume.
さらに、硫黄酸化物の含有量は、被処理ガス（排ガス）中、例えば、０．１〜１００ｐｐｍ、好ましくは０．２〜７０ｐｐｍ、さらに好ましくは０．３〜３０ｐｐｍ程度であってもよい。排ガス中には、通常、上記範囲（例えば、０．３〜３０ｐｐｍ程度）の硫黄酸化物が含まれる場合が多いが、本発明の触媒では、硫黄酸化物による被毒を受けにくいため、この程度の濃度では、酸化性能への影響は小さく、触媒活性を維持できる。 Further, the sulfur oxide content in the gas to be treated (exhaust gas) may be, for example, about 0.1 to 100 ppm, preferably about 0.2 to 70 ppm, and more preferably about 0.3 to 30 ppm. In many cases, the exhaust gas usually contains sulfur oxide in the above-mentioned range (for example, about 0.3 to 30 ppm), but the catalyst of the present invention is less susceptible to sulfur oxide poisoning. In the case of this concentration, the influence on the oxidation performance is small and the catalytic activity can be maintained.
なお、本発明の触媒は、前記のように、硫黄成分を含んでいてもよい。そのため、本発明では、前述のように、前記触媒を硫黄酸化物で処理した後（例えば、前記触媒の白金１モルに対して少なくとも１０モルの処理量で硫黄酸化物を処理して）、この処理された触媒に前記被処理ガスを接触させて前記低級不飽和炭化水素を酸化除去してもよい。特に、被処理ガスが硫黄酸化物を含む（例えば、０．３〜３０ｐｐｍ程度の硫黄酸化物を含む）場合、前記触媒をこのような被処理ガスで処理したのち、さらに連続して前記触媒に被処理ガスを接触させて酸化除去してもよい。このような方法では、予め触媒を硫黄成分により処理する必要がないため、環境上およびコスト的に有利である。 In addition, the catalyst of this invention may contain the sulfur component as mentioned above. Therefore, in the present invention, as described above, after the catalyst is treated with sulfur oxide (for example, the sulfur oxide is treated with a treatment amount of at least 10 moles per mole of platinum of the catalyst) The lower unsaturated hydrocarbon may be oxidized and removed by contacting the gas to be treated with a treated catalyst. In particular, when the gas to be treated contains sulfur oxide (for example, containing sulfur oxide of about 0.3 to 30 ppm), after the catalyst is treated with such a gas to be treated, the catalyst is continuously added to the catalyst. Oxidation may be removed by bringing a gas to be treated into contact. Such a method is advantageous in terms of environment and cost because it is not necessary to treat the catalyst with a sulfur component in advance.
なお、排ガス中には、一酸化炭素が含まれることがあるが、本発明の触媒は、高い酸化活性を有するので、一酸化炭素の酸化除去にも有効である。また、排ガス中には、飽和炭化水素や窒素酸化物が含まれていることがあるが、このような飽和炭化水素や窒素酸化物が本発明の触媒の活性に大きな影響を及ぼすことはない。 In addition, although carbon monoxide may be contained in exhaust gas, since the catalyst of this invention has high oxidation activity, it is effective also in the oxidation removal of carbon monoxide. The exhaust gas may contain saturated hydrocarbons and nitrogen oxides, but such saturated hydrocarbons and nitrogen oxides do not significantly affect the activity of the catalyst of the present invention.
被処理ガスと前記触媒との温度（接触温度）は、効率よく酸化除去できる範囲であればよく、１５０℃以上（例えば、１５０〜６００℃）の範囲から選択でき、例えば、１６０〜５００℃（例えば、１７０〜４５０℃）、好ましくは１６０〜４００℃（例えば、１７０〜３５０℃）、さらに好ましくは１７５〜３００℃（例えば、１８０〜２８０℃）程度であり、６００℃以下の温度で接触させるのが望ましい。接触温度は、被処理ガスの温度であってもよく、触媒の温度（例えば、触媒層又は触媒活性層の温度）であってもよく、これらの双方の温度であってもよい。 The temperature (contact temperature) between the gas to be treated and the catalyst may be in a range where it can be efficiently oxidized and removed, and can be selected from a range of 150 ° C. or higher (for example, 150 to 600 ° C.), for example, 160 to 500 ° C. ( For example, it is about 170-450 degreeC, Preferably it is 160-400 degreeC (for example, 170-350 degreeC), More preferably, it is about 175-300 degreeC (for example, 180-280 degreeC), and is made to contact at the temperature of 600 degrees C or less. Is desirable. The contact temperature may be the temperature of the gas to be treated, the temperature of the catalyst (for example, the temperature of the catalyst layer or the catalyst active layer), or the temperature of both of them.
特に、本発明では、比較的低温域、例えば、３００℃以下（例えば、１５０〜３００℃）、好ましくは１６０〜２６０℃（例えば、１７０〜２５０℃）、さらに好ましくは１７０〜２２０℃（例えば、１７５〜２１０℃）、特に１８０〜２１０℃（例えば、１８０〜２００℃）程度であっても触媒活性を保持でき、低級不飽和炭化水素（特に、エチレン、プロピレン）を有効に酸化除去できる。特に、本発明の触媒は、硫黄酸化物を含む被処理ガスであっても、比較的低温で前記炭化水素を酸化除去できる。なお、排ガス（熱回収を行った後の排ガス）の温度は、通常、３００℃以下（一般的には２００℃以下）である場合が多い。本発明の触媒は、上記のような低温域においても使用可能であるので、このような排ガスであっても好適に前記炭化水素を酸化除去できる。 In particular, in the present invention, a relatively low temperature range, for example, 300 ° C. or less (for example, 150 to 300 ° C.), preferably 160 to 260 ° C. (for example, 170 to 250 ° C.), more preferably 170 to 220 ° C. (for example, 175 to 210 ° C., particularly about 180 to 210 ° C. (for example, 180 to 200 ° C.), the catalytic activity can be maintained, and lower unsaturated hydrocarbons (particularly ethylene and propylene) can be effectively oxidized and removed. In particular, the catalyst of the present invention can oxidize and remove hydrocarbons at a relatively low temperature even when the gas to be treated contains sulfur oxides. Note that the temperature of exhaust gas (exhaust gas after heat recovery) is usually 300 ° C. or lower (generally 200 ° C. or lower) in many cases. Since the catalyst of the present invention can be used even in the low temperature region as described above, the hydrocarbon can be suitably removed by oxidation even with such an exhaust gas.
なお、本発明の触媒は、高い活性を有するが、あまりに低温では活性が下がり、所望の酸化性能が得られない虞があるので、接触温度（例えば、触媒層の温度）が所定の温度（例えば、１５０℃以上）に保たれるようにするのが好ましい。また、６００℃を超えるような温度での使用では、触媒の耐久性が悪化するおそれがある。さらに、前記炭化水素の濃度が著しく高いときには、触媒層（又は触媒活性層）で急激な反応が起こって、触媒の耐久性に影響を及ぼす場合があるので、触媒層での温度上昇が１５０℃以下となる条件で用いるのが好ましい。なお、被処理ガス（排ガス）の温度が高すぎる場合には、触媒の急速な劣化を引き起こすおそれがある。このような場合には、被処理ガスの温度が前記の好適な温度範囲を下回らないように留意しつつ、被処理ガスにあらかじめ所要の量の空気を混ぜるなどより温度調整してもよい。 Although the catalyst of the present invention has high activity, the activity decreases at a too low temperature and the desired oxidation performance may not be obtained. Therefore, the contact temperature (for example, the temperature of the catalyst layer) is a predetermined temperature (for example, , 150 ° C. or higher). In addition, when used at a temperature exceeding 600 ° C., the durability of the catalyst may be deteriorated. Furthermore, when the concentration of the hydrocarbon is extremely high, a rapid reaction occurs in the catalyst layer (or the catalyst active layer), which may affect the durability of the catalyst. It is preferable to use it under the following conditions. If the temperature of the gas to be treated (exhaust gas) is too high, the catalyst may be rapidly deteriorated. In such a case, the temperature of the gas to be processed may be adjusted by mixing a predetermined amount of air in advance with the gas to be processed while taking care that the temperature of the gas to be processed does not fall below the preferred temperature range.
酸化除去において、使用する前記触媒の量は、少なすぎると有効な酸化性能が得られないので、ガス時間当たり空間速度（ＧＨＳＶ）で、例えば、２００，０００ｈ-1以下［例えば、１０００〜２０００００ｈ-1、好ましくは１０００〜１５００００ｈ-1、さらに好ましくは２０００〜１０００００ｈ-1程度］であってもよい。なお、ガス時間当たり空間速度（ＧＨＳＶ）を低くするほど触媒量が多くなるため、酸化性能は向上するが、比較的低いＧＨＳＶ（例えば、１０００ｈ-1以下）で用いるような場合には、経済性の問題に加えて、触媒層での圧力損失が大きくなる問題が生じるおそれがある。 In the oxidation removal, if the amount of the catalyst used is too small, effective oxidation performance cannot be obtained. Therefore, the space velocity per gas time (GHSV) is, for example, 200,000 h −1 or less [eg, 1000 to 200000 h − 1 , preferably 1000 to 150,000 h −1 , more preferably about 2000 to 100000 h −1 ]. Note that the lower the space velocity per gas time (GHSV), the greater the amount of catalyst, so that the oxidation performance is improved. However, when it is used at a relatively low GHSV (for example, 1000 h -1 or less), it is economical. In addition to the above problem, there may be a problem that the pressure loss in the catalyst layer becomes large.
触媒に対する被処理ガスの線速度（ＬＶ）は、例えば、０．０２〜２０ｍ／秒、好ましくは０．０５〜５ｍ／秒、さらに好ましくは０．３〜３ｍ／秒程度の範囲から選択できる。 The linear velocity (LV) of the gas to be treated with respect to the catalyst can be selected, for example, from a range of about 0.02 to 20 m / second, preferably 0.05 to 5 m / second, and more preferably about 0.3 to 3 m / second.
触媒層の長さは、触媒活性を損なわない範囲で選択でき、例えば、０．０１〜１０ｍ、好ましくは０．０５〜５ｍ、さらに好ましくは０．１〜１ｍ程度であってもよい。 The length of the catalyst layer can be selected within a range not impairing the catalytic activity, and may be, for example, 0.01 to 10 m, preferably 0.05 to 5 m, and more preferably about 0.1 to 1 m.
本発明の触媒は、ガス（例えば、排ガス）中の低級不飽和炭化水素の分解除去に高い性能を有するので、高価な貴金属を大量に用いたり、あるいは性能を確保するためにガス（排ガスなど）を加熱したりする必要がなく、経済的に有利な条件でガス（排ガス）の処理を行うことができる。特に、液化石油ガスや天然ガスなどの軽質燃料を用いる内燃機関から排出される排ガスを本発明の触媒に通じることにより、排ガスを効率よく清浄化できる。このため、本発明の触媒は、燃焼機器、特に天然ガスや液化石油ガスなどの軽質燃料を用いる内燃機関から排出される排ガスの処理に特に有用である。 Since the catalyst of the present invention has high performance for decomposing and removing lower unsaturated hydrocarbons in gas (for example, exhaust gas), a large amount of expensive noble metal is used, or gas (exhaust gas, etc.) is used to ensure performance. The gas (exhaust gas) can be treated under economically advantageous conditions. In particular, exhaust gas discharged from an internal combustion engine using light fuel such as liquefied petroleum gas or natural gas is passed through the catalyst of the present invention, whereby the exhaust gas can be efficiently cleaned. For this reason, the catalyst of the present invention is particularly useful for the treatment of exhaust gas discharged from combustion equipment, particularly an internal combustion engine using light fuel such as natural gas or liquefied petroleum gas.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
実施例１
ジルコニア（日本電工（株）製、「Ｎ−ＰＣ」、比表面積２８ｍ2／ｇ）１００重量部にジルコニアゾル（第一希元素化学工業（株）製、「ジルコゾール」）１００重量部と水８０重量部を加えてボールミルによりスラリーを調製し、コージェライトハニカム（５０ｍｍ角×５０ｍｍ厚、６．４５平方センチメートルあたりのセル数２１０）にコートして、５５０℃で焼成し、ハニカム１リットルあたりジルコニアを１４０ｇコートした担体を作製した。これにテトラアンミン白金硝酸塩溶液（Ｐｔとして３重量％含有）を吸収（吸水）させて、５５０℃で焼成し、ハニカム１リットルあたりＰｔを２ｇ担持したＰｔ／ジルコニア触媒（以下では、Ｐｔ（２）／ジルコニアと記す）を調製した。
Example 1
100 parts by weight of zirconia (manufactured by Nippon Denko Co., Ltd., “N-PC”, specific surface area 28 m 2 / g) and 100 parts by weight of zirconia sol (manufactured by Daiichi Elemental Chemical Co., Ltd., “Zircosol”) and 80 parts by weight of water A slurry was prepared by a ball mill after adding a portion, coated on a cordierite honeycomb (50 mm square × 50 mm thickness, 210 cells per 6.45 square centimeters), fired at 550 ° C., and coated with 140 g of zirconia per liter of honeycomb. The prepared carrier was prepared. A tetraammine platinum nitrate solution (containing 3% by weight as Pt) was absorbed (water absorbed), fired at 550 ° C., and Pt / zirconia catalyst carrying 2 g of Pt per liter of honeycomb (hereinafter referred to as Pt (2) / (Referred to as zirconia).
Ｐｔ（２）／ジルコニアを直径１４ｍｍ、長さ１７ｍｍに切り出し、石英反応管に充填して触媒層とした。触媒層の温度を所定の温度に保って、エチレン１５０ｐｐｍ、プロピレン１５０ｐｐｍ、酸素１０％、水蒸気１０％、残部窒素の反応ガスを毎分２．７リットルの流量で流通して、触媒層前後のガスに含まれるエチレンおよびプロピレン濃度をガスクロマトグラフで測定して、エチレンおよびプロピレンの除去率を計算した。 Pt (2) / zirconia was cut into a diameter of 14 mm and a length of 17 mm, and filled in a quartz reaction tube to form a catalyst layer. While maintaining the temperature of the catalyst layer at a predetermined temperature, a reaction gas of 150 ppm of ethylene, 150 ppm of propylene, 10% of oxygen, 10% of water vapor, and the remaining nitrogen is circulated at a flow rate of 2.7 liters per minute, The ethylene and propylene concentrations contained in were measured with a gas chromatograph, and the removal rate of ethylene and propylene was calculated.
得られた触媒の初期活性の測定は、１７５℃、２００℃、２２５℃、２５０℃で行った。次いで反応ガスに硫黄酸化物（二酸化硫黄）３ｐｐｍを添加して３００℃で２０時間処理し、そのガス組成を保って硫黄酸化物処理後の活性を１７５℃、２００℃、２２５℃、２５０℃で測定した。硫黄酸化物処理前後のプロピレン除去率を表１に、エチレン除去率を表２に示す。Ｐｔ（２）／ジルコニア触媒は、硫黄酸化物を添加しても、１７５℃において一定の活性を維持しており、２００℃以上であればほぼ完全にエチレン、プロピレンを除去できる。 The initial activity of the obtained catalyst was measured at 175 ° C., 200 ° C., 225 ° C., and 250 ° C. Next, 3 ppm of sulfur oxide (sulfur dioxide) was added to the reaction gas and treated at 300 ° C. for 20 hours, and the activity after treatment with sulfur oxide was maintained at 175 ° C., 200 ° C., 225 ° C. and 250 ° C. while maintaining the gas composition. It was measured. Table 1 shows the propylene removal rate before and after the sulfur oxide treatment, and Table 2 shows the ethylene removal rate. The Pt (2) / zirconia catalyst maintains a constant activity at 175 ° C. even when sulfur oxide is added, and can remove ethylene and propylene almost completely at 200 ° C. or higher.
参考例
テトラアンミン白金硝酸塩溶液（Ｐｔとして３重量％含有）の代わりに、テトラアンミン白金硝酸塩とテトラアンミンパラジウム硝酸塩溶液（Ｐｔとして１．５重量％、Ｐｄとして７．５重量％含有）を用いた他は実施例１と同様にしてハニカム１リットルあたりＰｔを１ｇとＰｄを５ｇ担持したＰｔ−Ｐｄ／ジルコニア触媒（以下では、Ｐｔ（１）−Ｐｄ（５）／ジルコニアと記す）を調製し、実施例１と同じ条件で評価した。２００℃以上では、Ｐｔ（２）／ジルコニアと同等かそれ以上の性能を示した。また、この温度域では硫黄酸化物で処理した後の方が性能が向上している。
Reference Example A tetraammineplatinum nitrate solution (containing 1.5 wt% as Pt and containing 7.5 wt% as Pd) was used in place of the tetraammineplatinum nitrate solution (containing 3 wt% as Pt). In the same manner as in Example 1, a Pt-Pd / zirconia catalyst (hereinafter referred to as Pt (1) -Pd (5) / zirconia) carrying 1 g of Pt and 5 g of Pd per liter of honeycomb was prepared. Was evaluated under the same conditions. Above 200 ° C., the performance was equal to or better than Pt (2) / zirconia. In this temperature range, the performance is improved after treatment with sulfur oxide.
比較例１
アルミナ（住友化学工業（株）製、「ＮＫ−１２４」）１００重量部とアルミナゾル（日産化学工業（株）製、「＃５２０」）１００重量部を用いた他は実施例１と同様にして、ハニカム１リットルあたりアルミナを１０５ｇコートした担体を作製した。これを用いて、実施例１と同様にしてハニカム１リットルあたりＰｔを１．５ｇ担持したＰｔ／アルミナ触媒（以下では、Ｐｔ（１．５）／アルミナと記す）を調製し、実施例１と同じ条件で評価した。Ｐｔ量の差異を考慮してもＰｔ（２）／ジルコニアに比べると活性は著しく低く、完全にエチレン、プロピレンを除去するには２２５℃以上の温度を必要とした。
Comparative Example 1
Example 1 was used except that 100 parts by weight of alumina (manufactured by Sumitomo Chemical Co., Ltd., “NK-124”) and 100 parts by weight of alumina sol (manufactured by Nissan Chemical Industries, Ltd., “# 520”) were used. A carrier coated with 105 g of alumina per liter of honeycomb was prepared. Using this, a Pt / alumina catalyst (hereinafter referred to as Pt (1.5) / alumina) carrying 1.5 g of Pt per liter of honeycomb was prepared in the same manner as in Example 1. Evaluation was performed under the same conditions. Considering the difference in the amount of Pt, the activity was remarkably lower than that of Pt (2) / zirconia, and a temperature of 225 ° C. or higher was required to completely remove ethylene and propylene.
比較例２
比較例１と同じ担体を用いて参考例と同様の方法で貴金属を担持し、ハニカム１リットルあたりＰｔを１ｇとＰｄを５ｇ担持したＰｔ／アルミナ触媒（以下では、Ｐｔ（１）−Ｐｄ（５）／アルミナと記す）を調製し、実施例１と同じ条件で評価した。２２５℃以上の温度では硫黄酸化物で処理した後の方が高い性能が得られたが、その性能は実施例の触媒に及ばなかった。
Comparative Example 2
Pt / alumina catalyst (hereinafter referred to as Pt (1) -Pd (5) supporting 1 g of Pt and 5 g of Pd per liter of honeycomb using the same carrier as that of Comparative Example 1 in the same manner as in the Reference Example. ) / Denoted alumina) and evaluated under the same conditions as in Example 1. At a temperature of 225 ° C. or higher, higher performance was obtained after treatment with sulfur oxide, but the performance did not reach that of the catalyst of the example.
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