JP2007117911A - Catalyst for decomposing organic chlorine compound and method for removing organic chlorine compound using the same - Google Patents
Catalyst for decomposing organic chlorine compound and method for removing organic chlorine compound using the same Download PDFInfo
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- JP2007117911A JP2007117911A JP2005314579A JP2005314579A JP2007117911A JP 2007117911 A JP2007117911 A JP 2007117911A JP 2005314579 A JP2005314579 A JP 2005314579A JP 2005314579 A JP2005314579 A JP 2005314579A JP 2007117911 A JP2007117911 A JP 2007117911A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 150000004045 organic chlorine compounds Chemical class 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 40
- 239000010941 cobalt Substances 0.000 claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 239000005749 Copper compound Substances 0.000 claims abstract description 12
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 12
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000354 decomposition reaction Methods 0.000 claims description 18
- 238000004438 BET method Methods 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 229960003750 ethyl chloride Drugs 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 9
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- -1 dichloromethane Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Substances CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 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
- 150000004699 copper complex Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000791 photochemical oxidant Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
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- 239000010944 silver (metal) Substances 0.000 description 1
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- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は、有機塩素化合物を分解するための触媒、特に工場等の排ガスに含有された低濃度の有機塩素化合物を分解するためのものに関する。また、本発明は、この触媒を用いた有機塩素化合物の除去方法に関する。 The present invention relates to a catalyst for decomposing organochlorine compounds, particularly for decomposing low-concentration organochlorine compounds contained in exhaust gas from factories and the like. The present invention also relates to a method for removing an organochlorine compound using this catalyst.
工場等から排出される揮発性有機化合物(VOC)は、浮遊粒子状物質や光化学オキシダントの原因物質とされている。VOCの中でもジクロロメタンやクロロホルム等の有機塩素化合物は、酸性雨の原因物質としても知られており、排出抑制が強く求められている。しかし、有機塩素化合物は、トルエンやキシレン、酢酸エチルのような炭化水素類と異なり、容易に酸化分解することができない。さらに、有機塩素化合物を分解すると、その分解生成物には塩素が含まれる。この塩素は、触媒毒として働くことが良く知られている。つまり、有機塩素化合物を分解することにより生成する塩素が、触媒成分を塩素化して触媒性能を劣化させてしまうのである。例えば、酸化分解触媒であるマンガン触媒は、塩素成分があると、容易に塩素化されて、触媒表面が塩化マンガンとなり、酸化性能が低下してしまう。この様な例は、酸化鉄触媒等、様々な触媒で認められる。塩素による被毒を防ぐには、触媒表面に生成した金属塩化物の分解温度以上の高温の条件を使用する必要がある。したがって、通常使用されている触媒では、塩素による被毒のため、有機塩素化合物の処理は困難とされている。特に、低濃度の有機塩素化合物を含む排ガスは、処理量に対するコストが高価であり、未だに効果的な処理方法が確立しておらず、早急な対応が必要である。 Volatile organic compounds (VOC) discharged from factories and the like are considered as causative substances for suspended particulate matter and photochemical oxidants. Among VOCs, organic chlorine compounds such as dichloromethane and chloroform are known as causative substances of acid rain, and emission suppression is strongly demanded. However, unlike hydrocarbons such as toluene, xylene and ethyl acetate, organochlorine compounds cannot be easily oxidatively decomposed. Further, when the organic chlorine compound is decomposed, the decomposition product contains chlorine. It is well known that this chlorine acts as a catalyst poison. That is, chlorine produced by decomposing an organic chlorine compound chlorinates the catalyst component and degrades the catalyst performance. For example, if a manganese catalyst that is an oxidative decomposition catalyst has a chlorine component, it is easily chlorinated and the surface of the catalyst becomes manganese chloride, resulting in a reduction in oxidation performance. Such an example is observed with various catalysts such as an iron oxide catalyst. In order to prevent poisoning by chlorine, it is necessary to use conditions at a temperature higher than the decomposition temperature of the metal chloride formed on the catalyst surface. Therefore, it is difficult to treat organochlorine compounds with commonly used catalysts because of poisoning by chlorine. In particular, exhaust gas containing low-concentration organochlorine compounds is expensive in terms of the amount of treatment, and an effective treatment method has not yet been established, and prompt action is required.
従来、ジクロロメタン等の有機塩素化合物を除去するためには、活性炭吸着による除去(多孔質体の性質とその応用技術,竹内 雍監修,フジテクノシステム,1999年,P441.(非特許文献1))が行われているが、定期的な活性炭の取り替えや、回収した有機塩素化合物の再処理など、コスト的に安価とはいえない。 Conventionally, in order to remove organic chlorine compounds such as dichloromethane, removal by activated carbon adsorption (properties of porous materials and their application technology, supervised by Takeuchi Takeshi, Fuji Techno System, 1999, P441.) However, it is not cheap in terms of cost, such as periodic replacement of activated carbon and reprocessing of recovered organochlorine compounds.
また、酸化分解法として、500℃以上の温度で貴金属触媒を使った触媒分解や(特開平7−31879(特許文献1))、800℃以上での直接燃焼が行われている(環境技術・装置大事典,産業調査会,2003年,P.1360.(非特許文献2))。しかし、これらは分解処理温度が高いため、低濃度の有機塩素化合物の処理としてはランニングコストが高く実用的でない。
そこで、本発明は、工場等の排ガスに含まれているジクロロメタン等の有機塩素化合物を除去するための触媒であって、かつ低濃度の有機塩素化合物の除去にも適した、低温で高活性な触媒を提供することを目的とする。また、本発明は、この触媒を用いて有機塩素化合物を効果的に除去する方法を提供することを目的とする。 Therefore, the present invention is a catalyst for removing organochlorine compounds such as dichloromethane contained in exhaust gas from factories and the like, and suitable for removing low-concentration organochlorine compounds, and is highly active at low temperatures. An object is to provide a catalyst. Moreover, this invention aims at providing the method of removing an organic chlorine compound effectively using this catalyst.
上記目的を達成するため、本発明の触媒は、コバルト・銅複合酸化物を主体とする。また、本発明の触媒は、コバルト化合物および銅化合物を含む溶液からコバルトおよび銅を含む沈殿物を生成させる工程と、前記沈殿物を焼成する工程とを含む方法により得ることを特徴とする。この触媒を用いれば、低濃度の有機塩素化合物を300℃以下の低温で酸化分解して効果的に除去することができる。 In order to achieve the above object, the catalyst of the present invention is mainly composed of a cobalt / copper composite oxide. The catalyst of the present invention is obtained by a method comprising a step of producing a precipitate containing cobalt and copper from a solution containing a cobalt compound and a copper compound, and a step of firing the precipitate. If this catalyst is used, a low concentration organochlorine compound can be effectively removed by oxidative decomposition at a low temperature of 300 ° C. or lower.
また、本発明の触媒は、コバルト化合物および銅化合物を含む水溶液からコバルトおよび銅を含む沈殿物を生成させる工程において、pHが7〜10で沈殿させることが好ましい。この好ましい例によれば、触媒の比表面積が100m2/g以上となり、触媒性能が向上する。 Moreover, it is preferable to precipitate the catalyst of this invention by pH 7-10 in the process of producing | generating the precipitate containing cobalt and copper from the aqueous solution containing a cobalt compound and a copper compound. According to this preferable example, the specific surface area of the catalyst is 100 m 2 / g or more, and the catalyst performance is improved.
本発明の触媒は、V、Cr、Mn、Fe、Ni、Ga、Nb、Mo、Pd、Ag、Cd、Sn、W、Au、Ru、Pt、Bi,Ir,RhおよびCeからなる群から選ばれる少なくとも一種を助触媒としてさらに含むことが好ましい。ただし、助触媒の含有率は20重量%以下であることが好ましい。 The catalyst of the present invention is selected from the group consisting of V, Cr, Mn, Fe, Ni, Ga, Nb, Mo, Pd, Ag, Cd, Sn, W, Au, Ru, Pt, Bi, Ir, Rh and Ce. It is preferable to further include at least one of the above as a cocatalyst. However, the content of the cocatalyst is preferably 20% by weight or less.
本発明の触媒では、コバルトと銅との合計量に対するコバルトの含有率が10原子%以上90原子%以下であることが好ましい。 In the catalyst of this invention, it is preferable that the content rate of cobalt with respect to the total amount of cobalt and copper is 10 atomic% or more and 90 atomic% or less.
本発明の触媒は、Brunauer−Emmett−Teller(BET)法(比表面積測定法)で測定した比表面積が100m2/g以上であることが好ましい。有機塩素化合物の分解に対する触媒の性能が向上するからである。 The catalyst of the present invention preferably has a specific surface area of 100 m 2 / g or more measured by the Brunauer-Emmett-Teller (BET) method (specific surface area measurement method). This is because the performance of the catalyst for the decomposition of the organic chlorine compound is improved.
さらに、本発明の触媒を100m2/g以上の比表面積を有する担体に担持して使用することもできる。 Furthermore, the catalyst of the present invention can be used by being supported on a carrier having a specific surface area of 100 m 2 / g or more.
本発明の有機塩素化合物の除去方法は、本発明の触媒に、有機塩素化合物を含む気体を接触させる工程を含む。本発明の除去方法では、低濃度の有機塩素化合物を除去することができる。 The method for removing an organic chlorine compound of the present invention includes a step of bringing a gas containing an organic chlorine compound into contact with the catalyst of the present invention. The removal method of the present invention can remove low-concentration organochlorine compounds.
本発明の除去方法では、有機塩素化合物を含む気体を300℃以下で触媒に接触させることが好ましい。従来の触媒では、実用上、500℃を超える高温で気体を接触させる必要があった。しかし、上記除去方法では、従来の触媒に較べて低温での処理が可能である。 In the removal method of the present invention, it is preferable that a gas containing an organic chlorine compound is brought into contact with the catalyst at 300 ° C. or lower. In the conventional catalyst, it was necessary to contact the gas at a high temperature exceeding 500 ° C. in practice. However, the above removal method can be processed at a lower temperature than conventional catalysts.
さらに、本発明の有機塩素化合物の除去方法では、気体は水蒸気をさらに含んでいてもよい。 Furthermore, in the method for removing an organic chlorine compound of the present invention, the gas may further contain water vapor.
本発明の触媒は、工場等の排ガスに含まれているジクロロメタン等の有機塩素化合物を除去するための触媒であり、低濃度の有機塩素化合物の除去が可能である。また、本発明の触媒は、低温で高活性な触媒である。本発明の方法は、低濃度の有機塩素化合物の除去を可能にし、低温で操作することができる。 The catalyst of the present invention is a catalyst for removing organochlorine compounds such as dichloromethane contained in exhaust gas from factories and the like, and can remove organochlorine compounds at a low concentration. The catalyst of the present invention is a catalyst that is highly active at low temperatures. The method of the present invention allows the removal of low concentrations of organochlorine compounds and can be operated at low temperatures.
以下、本発明について説明する。 The present invention will be described below.
本発明の触媒は、コバルト・銅複合酸化物を主体とするコバルトと銅の複合化合物である。本発明の触媒では、コバルトと銅との合計量に対するコバルトの含有率が10原子%以上90原子%以下であることが好ましい。本発明の触媒であるコバルト・銅複合酸化物は、比表面積が100m2/g以上、好ましくは150m2/g以上であることが好ましい。触媒の比表面積が大きくなるほど、有機塩素化合物の分解に高活性を示す。本発明の有機塩素化合物分解用触媒は、助触媒として、V、Cr、Mn、Fe、Ni、Ga、Nb、Mo、Pd、Ag、Cd、Sn、W、Au、Ru、Pt、Bi,Ir,RhおよびCeから選ばれる少なくとも一種の元素を含むことができる。触媒中における助触媒の量は20重量%以下が好ましい。さらに好ましくは、10重量%以下である。本発明の触媒は、比表面積が100m2/g以上の担体に担持させることもできる。さらに、本発明の触媒は、後述する製造方法により製造されるものである。 The catalyst of the present invention is a composite compound of cobalt and copper mainly composed of a cobalt / copper composite oxide. In the catalyst of this invention, it is preferable that the content rate of cobalt with respect to the total amount of cobalt and copper is 10 atomic% or more and 90 atomic% or less. The cobalt / copper composite oxide which is the catalyst of the present invention has a specific surface area of 100 m 2 / g or more, preferably 150 m 2 / g or more. The higher the specific surface area of the catalyst, the higher the activity of decomposing organochlorine compounds. The catalyst for decomposing organochlorine compounds of the present invention includes V, Cr, Mn, Fe, Ni, Ga, Nb, Mo, Pd, Ag, Cd, Sn, W, Au, Ru, Pt, Bi, Ir as promoters. , Rh and Ce may be included. The amount of the promoter in the catalyst is preferably 20% by weight or less. More preferably, it is 10 weight% or less. The catalyst of the present invention can also be supported on a carrier having a specific surface area of 100 m 2 / g or more. Furthermore, the catalyst of this invention is manufactured by the manufacturing method mentioned later.
触媒および担体は、上述の比表面積を有することが好ましいが、比表面積は触媒や担体の作成の仕方しだいで、いくらでも大きな比表面積にすることができる。例えば、コバルト・銅複合酸化物触媒の場合、例えば、400m2/g程度までの比表面積、担体では、例えば3000m2/g程度までの比表面積とすることができる。しかし、本発明ではこれらの上限に限らず、さらに大きな比表面積であってもよい。 The catalyst and the support preferably have the above-mentioned specific surface area, but the specific surface area can be made as large as possible depending on how the catalyst and the support are prepared. For example, in the case of a cobalt / copper composite oxide catalyst, the specific surface area can be, for example, up to about 400 m 2 / g, and in the case of a support, the specific surface area can be up to, for example, about 3000 m 2 / g. However, the present invention is not limited to these upper limits and may have a larger specific surface area.
触媒の形状は、特に制限されず、粒状、円柱状、クローバー型、ハニカム型、ネット状等、様々な形状とすることができる。圧力損失を少なくするためには、ハニカム型やネット状が好ましい。 The shape of the catalyst is not particularly limited, and may be various shapes such as a granular shape, a columnar shape, a clover shape, a honeycomb shape, and a net shape. In order to reduce the pressure loss, a honeycomb type or a net shape is preferable.
また、本発明の触媒は、アモルファスであることが好ましい。 The catalyst of the present invention is preferably amorphous.
酸化コバルトおよび酸化銅は、酸化触媒として知られているが、それぞれ単独では有機塩素化合物の分解触媒として有効ではない。コバルトと銅の複合酸化物になることで、コバルトの酸化還元力と銅の酸化還元力が効果的に作用して、有機塩素化合物の低温分解を可能としていると考えられる。また、本発明のコバルト・銅複合酸化物触媒は、塩素被毒を受けにくいことが特徴である。酸化マンガン等の通常の酸化触媒は、塩素により触媒表面が塩素化されるために、300℃以下の低温では急激に触媒の分解活性が劣化するか、またはその分解性能が発揮できなくなる。しかし、本発明のコバルト・銅複合酸化物触媒では、300℃以下で有機塩素化合物を効果的に分解できることから、触媒表面が塩素化されにくいと考えられる。触媒表面の塩素化を防ぐ機構は、不明ではあるが、おそらく、触媒表面に生成した塩化物が、300℃以下の低温でも水蒸気と反応して、塩酸ガスとして触媒表面から除去されるためと考えられる。 Cobalt oxide and copper oxide are known as oxidation catalysts, but each is not effective as a decomposition catalyst for organochlorine compounds. By becoming a complex oxide of cobalt and copper, it is considered that the oxidation-reduction power of cobalt and the oxidation-reduction power of copper act effectively, and the organic chlorine compound can be decomposed at a low temperature. In addition, the cobalt / copper composite oxide catalyst of the present invention is characterized by being less susceptible to chlorine poisoning. A normal oxidation catalyst such as manganese oxide chlorinates the surface of the catalyst with chlorine. Therefore, the decomposition activity of the catalyst is rapidly deteriorated at a low temperature of 300 ° C. or lower, or the decomposition performance cannot be exhibited. However, since the organochlorine compound can be effectively decomposed at 300 ° C. or less in the cobalt / copper composite oxide catalyst of the present invention, it is considered that the catalyst surface is hardly chlorinated. The mechanism for preventing chlorination of the catalyst surface is unknown, but it is probably because chloride generated on the catalyst surface reacts with water vapor even at a low temperature of 300 ° C. or less and is removed as hydrochloric acid gas from the catalyst surface. It is done.
つぎに、本発明における触媒の製法の一形態について説明する。原料となるコバルト化合物および銅化合物としては、硝酸塩、硫酸塩、塩化物をはじめとする各種の無機金属化合物、酢酸塩、蟻酸塩、アルコキシド金属化合物、アセチルアセテート金属化合物をはじめとする各種の有機金属化合物を使用できる。 Next, an embodiment of a method for producing a catalyst in the present invention will be described. Cobalt compounds and copper compounds used as raw materials include various inorganic metal compounds such as nitrates, sulfates and chlorides, various organic metals including acetates, formates, alkoxide metal compounds, and acetylacetate metal compounds. Compounds can be used.
コバルト化合物と銅化合物とを含む原料は溶媒に添加される。溶媒としては、水、アルコール系溶媒等を使用できる。得られた溶液には、pHを調整するために、さらに沈殿助剤を添加することが好ましい。沈澱助剤としては、アンモニア水、炭酸ナトリウム等の各種のアルカリ性化合物を使用できる。また、分解することによってアルカリ性となる尿素等を用いてもよい。このようにして、溶液のpHは、沈殿物の生成に好ましい値となるように調整される。このpHの値は、好ましくは7〜10、さらに好ましくは8〜10である。 A raw material containing a cobalt compound and a copper compound is added to a solvent. As the solvent, water, an alcohol solvent or the like can be used. In order to adjust pH, it is preferable to add a precipitation aid to the obtained solution. As the precipitation aid, various alkaline compounds such as aqueous ammonia and sodium carbonate can be used. Further, urea or the like that becomes alkaline when decomposed may be used. In this way, the pH of the solution is adjusted to a value that is favorable for the formation of a precipitate. The pH value is preferably 7 to 10, more preferably 8 to 10.
コバルト化合物と銅化合物とは、最終的に得られる触媒において、コバルト:銅の原子比が1:9〜9:1となるように、溶液に添加することが好ましい。
コバルト:銅の原子比は、さらに好ましくは2:8〜8:2、最も好ましくは5:5〜8:2である。
The cobalt compound and the copper compound are preferably added to the solution such that the atomic ratio of cobalt: copper is 1: 9 to 9: 1 in the catalyst finally obtained.
The atomic ratio of cobalt: copper is more preferably 2: 8-8: 2, most preferably 5: 5-8: 2.
この様にして製造したコバルト・銅複合酸化物は、比表面積が100m2/g以上、好ましくは150m2/g以上となり、有機塩素化合物の分解に高活性を示す。 The cobalt / copper composite oxide thus produced has a specific surface area of 100 m 2 / g or more, preferably 150 m 2 / g or more, and exhibits high activity in the decomposition of the organic chlorine compound.
本発明の触媒には、助触媒として、V、Cr、Mn、Fe、Ni、Ga、Nb、Mo、Pd、Ag、Cd、Sn、W、Au、Ru、Pt、Bi,Ir,RhおよびCeから選ばれる少なくとも一種の元素を含むことができる。助触媒を含む有機塩素化合物分解用触媒を製造する場合、助触媒となる元素の化合物をコバルト化合物と銅化合物を含む溶液に添加することが効果的である。これらの助触媒は、上記触媒の酸化力を向上させる作用がある。特に、Mn、Cr、V、Ag、Au、Pd、PtおよびCeは、その酸化物自体が強い酸化作用を有するため、触媒の性能向上に有用である。これらの元素は、通常、イオンまたは酸化物として触媒に含有される。 In the catalyst of the present invention, V, Cr, Mn, Fe, Ni, Ga, Nb, Mo, Pd, Ag, Cd, Sn, W, Au, Ru, Pt, Bi, Ir, Rh and Ce are used as promoters. It can contain at least one element selected from When producing an organic chlorine compound decomposition catalyst containing a cocatalyst, it is effective to add a compound of an element serving as a cocatalyst to a solution containing a cobalt compound and a copper compound. These cocatalysts have the effect of improving the oxidizing power of the catalyst. In particular, Mn, Cr, V, Ag, Au, Pd, Pt, and Ce are useful for improving the performance of the catalyst because the oxide itself has a strong oxidizing action. These elements are usually contained in the catalyst as ions or oxides.
触媒中における助触媒の量は20重量%以下が好ましい。さらに好ましくは、10重量%以下である。 The amount of the promoter in the catalyst is preferably 20% by weight or less. More preferably, it is 10 weight% or less.
こうして得られた沈殿物(例えば、コバルト化合物と銅化合物との共沈物)は、さらに洗浄して、余分な金属イオン等を除去することが好ましい。洗浄は、例えばろ過により行うことができる。洗浄は、洗浄液に余分な塩または金属イオンが残存しなくなるまで実施することが好ましい。洗浄の後、沈殿物は、乾燥して水分を十分に除去した後、焼成される。 The precipitate thus obtained (for example, a coprecipitate of a cobalt compound and a copper compound) is preferably further washed to remove excess metal ions and the like. Washing can be performed, for example, by filtration. The washing is preferably carried out until no excessive salt or metal ion remains in the washing solution. After washing, the precipitate is dried to remove moisture sufficiently and then baked.
焼成は250℃〜350℃の大気中で行うことが好ましい。250℃以下の温度で焼成した場合は、沈殿物は水酸化物が主体であり、酸化力に乏しくなる可能性がある。また、350℃以上の温度で焼成した場合は、沈殿物の比表面積が小さくなり、触媒性能が低下する可能性がある。 Firing is preferably performed in the atmosphere at 250 ° C to 350 ° C. When calcined at a temperature of 250 ° C. or lower, the precipitate is mainly composed of hydroxide, and may have poor oxidizing power. Moreover, when calcined at a temperature of 350 ° C. or higher, the specific surface area of the precipitate becomes small, and the catalyst performance may be lowered.
上記触媒は、比表面積が100m2/g以上の担体に担持させることもできる。担体としては、シリカ、アルミナ、ゼオライト、チタニア、メソポーラスシリカ等の材料を使用することができるが、特に限定されない。また、担持方法は、コバルト化合物および銅化合物を含む溶液に担体を添加してから、沈殿助剤で沈殿物を形成する方法、担体にコバルト化合物および銅化合物を含む溶液を含浸させた後に沈殿助剤でコバルト・銅複合化合物を担体上に形成させる方法などがあるが、特に限定されない。これらの担体に担持した後、250℃〜350℃の大気中で焼成することが好ましい。 The catalyst can be supported on a carrier having a specific surface area of 100 m 2 / g or more. As the carrier, materials such as silica, alumina, zeolite, titania, and mesoporous silica can be used, but are not particularly limited. The loading method is a method in which a carrier is added to a solution containing a cobalt compound and a copper compound, and then a precipitate is formed with a precipitation aid, and after the carrier is impregnated with a solution containing a cobalt compound and a copper compound, the precipitation aid is added. Although there is a method of forming a cobalt / copper composite compound on a carrier with an agent, it is not particularly limited. After being supported on these carriers, it is preferably fired in the atmosphere at 250 ° C to 350 ° C.
本発明の有機塩素化合物の除去方法は、上記のようにして製造された触媒と、有機塩素化合物を含有する気体を接触させる工程を含む。本発明の有機塩素化合物の除去方法では、300℃以下の低温において、本発明の触媒を、例えばジクロロメタンのような有機塩素化合物を含む気体(例えば有機塩素化合物を含む空気)と接触させることにより、有機塩素化合物を除去する。 The method for removing an organic chlorine compound of the present invention includes a step of bringing the catalyst produced as described above into contact with a gas containing an organic chlorine compound. In the method for removing an organic chlorine compound of the present invention, the catalyst of the present invention is brought into contact with a gas containing an organic chlorine compound such as dichloromethane (for example, air containing an organic chlorine compound) at a low temperature of 300 ° C. or lower, Remove organochlorine compounds.
また、気体には、有機塩素化合物と空気以外に、水蒸気を含むことができる。水蒸気はもともと気体に含まれていてもよく、別途気体に添加してもよい。水蒸気は、有機塩素化合物に含まれる塩素と反応して塩酸となる。水蒸気が含まれなければ、酸化反応により塩素ガスが生成し、排ガスのスクラバー洗浄だけでは、容易に塩素ガスを除去できない。しかし、水蒸気を含むことで生成する塩酸ガスは、アルカリ性水溶液と反応性が高く、アルカリ性水溶液を使用したスクラバー洗浄で容易に中和して除去することが可能である。水蒸気の量は、有機塩素化合物に含有される塩素原子のモル数の1倍以上であればよく、好ましくは、2倍以上である。 Further, the gas can contain water vapor in addition to the organic chlorine compound and air. The water vapor may be originally contained in the gas, or may be added to the gas separately. Steam reacts with chlorine contained in the organic chlorine compound to form hydrochloric acid. If water vapor is not contained, chlorine gas is generated by an oxidation reaction, and chlorine gas cannot be easily removed by only scrubber cleaning of exhaust gas. However, the hydrochloric acid gas produced by containing water vapor is highly reactive with an alkaline aqueous solution, and can be easily neutralized and removed by scrubber cleaning using an alkaline aqueous solution. The amount of water vapor may be one or more times the number of moles of chlorine atoms contained in the organic chlorine compound, and preferably two or more times.
なお、特に限定されないが、本発明による触媒による有機塩素化合物の除去は、有機塩素化合物を1〜100ppm程度含む気体を対象とするのに適している。 Although not particularly limited, the removal of the organic chlorine compound by the catalyst according to the present invention is suitable for a gas containing about 1 to 100 ppm of the organic chlorine compound.
また、特に限定されないが、本発明による触媒による有機塩素化合物の除去方法の対象となる有機塩素化合物として、例えばジクロロメタン、クロロメタン、クロロホルム、ジクロロエタン、クロロエタン、クロロエチレン、ジクロロエチレンが適している。 Further, although not particularly limited, for example, dichloromethane, chloromethane, chloroform, dichloroethane, chloroethane, chloroethylene, and dichloroethylene are suitable as the organic chlorine compound that is a target of the method for removing an organic chlorine compound by the catalyst according to the present invention.
低濃度の有機塩素化合物を含む空気と触媒とを接触させる過程は、通常の気相触媒反応に用いられる方式を採用して実施すればよい。最も簡単なのは、触媒、または触媒が固定された坦体を、加熱装置を備えた管または容器に充填して用いる方法である。具体的には、触媒等からなる充填層を形成し、この充填層を貫通するように有機塩素化合物を含む気体を流す方法がある。 The process of bringing the catalyst containing air containing a low-concentration organochlorine compound into contact with the catalyst may be carried out by employing a method used for a normal gas phase catalytic reaction. The simplest is a method in which a catalyst or a carrier on which the catalyst is fixed is filled into a tube or container equipped with a heating device. Specifically, there is a method in which a packed bed made of a catalyst or the like is formed and a gas containing an organic chlorine compound is passed through the packed bed.
コバルト・銅複合酸化物を主体とする上記触媒は、工場等の排ガス設備に組み込んで用いることが好ましい。 It is preferable to use the catalyst mainly composed of cobalt / copper composite oxide by being incorporated in an exhaust gas facility such as a factory.
このように上記触媒を使用すれば、長期間にわたって継続的に有害なジクロロメタン等の有機塩素化合物を排ガス中から除去することができる。 When the catalyst is used in this manner, harmful organic chlorine compounds such as dichloromethane can be removed from the exhaust gas continuously over a long period of time.
以下に、本発明を実施例によりさらに詳細に説明するが、本発明は、以下の実施例により制限されるものではない。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.
(実施例1)
硝酸コバルト・6水和物0.15mol、および硝酸銅・3水和物0.05molを1000mlの純水に溶解した。この水溶液に炭酸ナトリウムの10wt%水溶液を添加してpHを9.3に調整し、コバルトと銅との共沈物を生成させた。この共沈物を濾過し、70℃の純水3リットルで洗浄した。さらに、共沈物を120℃で1晩乾燥させた後、300℃で2時間焼成して、コバルト・銅複合酸化物を得た。このコバルト・銅複合酸化物をBET法により比表面積を測定した結果、159m2/gであった。また、粉末X線回折で結晶構造を確認した結果、明確なピークはなくアモルファスであった。
Example 1
Cobalt nitrate hexahydrate 0.15 mol and copper nitrate trihydrate 0.05 mol were dissolved in 1000 ml of pure water. A 10 wt% aqueous solution of sodium carbonate was added to this aqueous solution to adjust the pH to 9.3, thereby forming a coprecipitate of cobalt and copper. The coprecipitate was filtered and washed with 3 liters of pure water at 70 ° C. Further, the coprecipitate was dried at 120 ° C. overnight and then calcined at 300 ° C. for 2 hours to obtain a cobalt / copper composite oxide. It was 159 m < 2 > / g as a result of measuring the specific surface area of this cobalt * copper complex oxide by BET method. Moreover, as a result of confirming the crystal structure by powder X-ray diffraction, there was no clear peak and it was amorphous.
(実施例2)
硝酸コバルト・6水和物0.15mol、および硝酸銅・3水和物0.05molを1000mlの純水に溶解した。この水溶液に炭酸ナトリウムの10wt%水溶液を添加してpHを8.0に調整し、コバルトと銅との共沈物を生成させた。この共沈物を濾過し、70℃の純水3リットルで洗浄した。さらに、共沈物を120℃で1晩乾燥させた後、300℃で2時間焼成して、コバルト・銅複合酸化物を得た。このコバルト・銅複合酸化物をBET法により比表面積を測定した結果、133m2/gであった。また、粉末X線回折で結晶構造を確認した結果、明確なピークはなくアモルファスであった。
(Example 2)
Cobalt nitrate hexahydrate 0.15 mol and copper nitrate trihydrate 0.05 mol were dissolved in 1000 ml of pure water. A 10 wt% aqueous solution of sodium carbonate was added to this aqueous solution to adjust the pH to 8.0, thereby producing a coprecipitate of cobalt and copper. The coprecipitate was filtered and washed with 3 liters of pure water at 70 ° C. Further, the coprecipitate was dried at 120 ° C. overnight and then calcined at 300 ° C. for 2 hours to obtain a cobalt / copper composite oxide. As a result of measuring the specific surface area of this cobalt-copper composite oxide by the BET method, it was 133 m 2 / g. Moreover, as a result of confirming the crystal structure by powder X-ray diffraction, there was no clear peak and it was amorphous.
(実施例3)
硝酸コバルト・6水和物0.15mol、および硝酸銅・3水和物0.05molを1000mlの純水に溶解した。この水溶液に炭酸ナトリウムの10wt%水溶液を添加してpHを7.5に調整し、コバルトと銅との共沈物を生成させた。この共沈物を濾過し、70℃の純水3リットルで洗浄した。さらに、共沈物を120℃で1晩乾燥させた後、300℃で2時間焼成して、コバルト・銅複合酸化物を得た。このコバルト・銅複合酸化物をBET法により比表面積を測定した結果、128m2/gであった。また、粉末X線回折で結晶構造を確認した結果、CuOおよびCo3O4の弱いピークが認められた。
(Example 3)
Cobalt nitrate hexahydrate 0.15 mol and copper nitrate trihydrate 0.05 mol were dissolved in 1000 ml of pure water. A 10 wt% aqueous solution of sodium carbonate was added to this aqueous solution to adjust the pH to 7.5, thereby forming a coprecipitate of cobalt and copper. The coprecipitate was filtered and washed with 3 liters of pure water at 70 ° C. Further, the coprecipitate was dried at 120 ° C. overnight and then calcined at 300 ° C. for 2 hours to obtain a cobalt / copper composite oxide. As a result of measuring the specific surface area of this cobalt-copper composite oxide by the BET method, it was 128 m 2 / g. Moreover, as a result of confirming the crystal structure by powder X-ray diffraction, weak peaks of CuO and Co 3 O 4 were observed.
(比較例1)
硝酸コバルト・6水和物0.15mol、および硝酸銅・3水和物0.05molを1000mlの純水に溶解した。この水溶液に炭酸ナトリウムの10wt%水溶液を添加してpHを6.5に調整し、コバルトと銅との共沈物を生成させた。この共沈物を濾過し、70℃の純水3リットルで洗浄した。さらに、共沈物を120℃で1晩乾燥させた後、300℃で2時間焼成して、コバルト・銅複合酸化物を得た。このコバルト・銅複合酸化物をBET法により比表面積を測定した結果、39m2/gであった。また、粉末X線回折で結晶構造を確認した結果、CuOおよびCo3O4の大きなピークが認められた。
(Comparative Example 1)
Cobalt nitrate hexahydrate 0.15 mol and copper nitrate trihydrate 0.05 mol were dissolved in 1000 ml of pure water. A 10 wt% aqueous solution of sodium carbonate was added to this aqueous solution to adjust the pH to 6.5, thereby forming a coprecipitate of cobalt and copper. The coprecipitate was filtered and washed with 3 liters of pure water at 70 ° C. Further, the coprecipitate was dried at 120 ° C. overnight and then calcined at 300 ° C. for 2 hours to obtain a cobalt / copper composite oxide. As a result of measuring the specific surface area of this cobalt-copper composite oxide by the BET method, it was 39 m 2 / g. As a result of confirming the crystal structure by powder X-ray diffraction, large peaks of CuO and Co 3 O 4 were observed.
(比較例2)
硝酸コバルト・6水和物0.15mol、および硝酸銅・3水和物0.05molを1000mlの純水に溶解した。この水溶液に炭酸ナトリウムの10wt%水溶液を添加してpHを6.1に調整し、コバルトと銅との共沈物を生成させた。この共沈物を濾過し、70℃の純水3リットルで洗浄した。さらに、共沈物を120℃で1晩乾燥させた後、300℃で2時間焼成して、コバルト・銅複合酸化物を得た。このコバルト・銅複合酸化物をBET法により比表面積を測定した結果、11m2/gであった。また、粉末X線回折で結晶構造を確認した結果、CuOおよびCo3O4の大きなピークが認められた。
(Comparative Example 2)
Cobalt nitrate hexahydrate 0.15 mol and copper nitrate trihydrate 0.05 mol were dissolved in 1000 ml of pure water. A 10 wt% aqueous solution of sodium carbonate was added to this aqueous solution to adjust the pH to 6.1, thereby forming a coprecipitate of cobalt and copper. The coprecipitate was filtered and washed with 3 liters of pure water at 70 ° C. Further, the coprecipitate was dried at 120 ° C. overnight and then calcined at 300 ° C. for 2 hours to obtain a cobalt / copper composite oxide. As a result of measuring the specific surface area of this cobalt-copper composite oxide by the BET method, it was 11 m 2 / g. As a result of confirming the crystal structure by powder X-ray diffraction, large peaks of CuO and Co 3 O 4 were observed.
以上の結果より、比表面積が100m2/g以上とするには、共沈させるpHを7以上することが必要であることがわかる。 From the above results, it can be seen that the coprecipitation pH must be 7 or more in order for the specific surface area to be 100 m 2 / g or more.
(実施例4)
硝酸コバルト・6水和物0.15mol、硝酸銅・3水和物0.05mol、および硝酸ランタン・6水和物1.4gを1000mlの純水に溶解した。この水溶液に炭酸ナトリウムの10wt%水溶液を添加してpHを9.3に調整し、コバルトと銅との共沈物を生成させた。この共沈物を濾過し、70℃の純水3リットルで洗浄した。さらに、共沈物を120℃で1晩乾燥させた後、300℃で2時間焼成して、ランタン含有コバルト・銅複合酸化物を得た。このコバルト・銅複合酸化物をBET法により比表面積を測定した結果、161m2/gであった。
Example 4
Cobalt nitrate hexahydrate 0.15 mol, copper nitrate trihydrate 0.05 mol, and lanthanum nitrate hexahydrate 1.4 g were dissolved in 1000 ml of pure water. A 10 wt% aqueous solution of sodium carbonate was added to this aqueous solution to adjust the pH to 9.3, thereby forming a coprecipitate of cobalt and copper. The coprecipitate was filtered and washed with 3 liters of pure water at 70 ° C. Further, the coprecipitate was dried at 120 ° C. overnight and then calcined at 300 ° C. for 2 hours to obtain a lanthanum-containing cobalt / copper composite oxide. It was 161 m < 2 > / g as a result of measuring a specific surface area by this BET method for this cobalt-copper composite oxide.
(実施例5)
硝酸コバルト・6水和物0.15mol、硝酸銅・3水和物0.05mol、硝酸ランタン・6水和物1.4g、および塩化白金酸・6水和物0.4gを1000mlの純水に溶解した。この水溶液に炭酸ナトリウムの10wt%水溶液を添加してpHを9.3に調整し、コバルトと銅との共沈物を生成させた。この共沈物を濾過し、70℃の純水1リットルで洗浄し、120℃で1晩乾燥させた後、300℃で2時間焼成して、白金・ランタン含有コバルト・銅複合酸化物とした。このコバルト・銅複合酸化物をBET法により比表面積を測定した結果、149m2/gであった。
(Example 5)
1000 ml of pure water containing 0.15 mol of cobalt nitrate hexahydrate, 0.05 mol of copper nitrate trihydrate, 1.4 g of lanthanum nitrate hexahydrate, and 0.4 g of chloroplatinic acid hexahydrate Dissolved in. A 10 wt% aqueous solution of sodium carbonate was added to this aqueous solution to adjust the pH to 9.3, thereby forming a coprecipitate of cobalt and copper. The coprecipitate was filtered, washed with 1 liter of pure water at 70 ° C., dried at 120 ° C. overnight, and then calcined at 300 ° C. for 2 hours to obtain a platinum / lanthanum-containing cobalt / copper composite oxide. . It was 149 m < 2 > / g as a result of measuring a specific surface area by this BET method for this cobalt-copper composite oxide.
(比較例3)
塩化金酸・4水和物0.25g、および硝酸鉄・9水和物24.3gを600mlの蒸留水に溶解させてA液を得た。一方、炭酸ナトリウム10.3gを400mlの蒸留水に溶解させてB液を得た。
(Comparative Example 3)
A liquid A was obtained by dissolving 0.25 g of chloroauric acid tetrahydrate and 24.3 g of iron nitrate nonahydrate in 600 ml of distilled water. On the other hand, 10.3 g of sodium carbonate was dissolved in 400 ml of distilled water to obtain a liquid B.
上記B液中にA液を滴下し、1時間撹拌した後、得られた共沈物を十分に水洗して乾燥し、空気中で400℃で5時間焼成することにより、金微粒子固定化鉄酸化物を得た。 After dripping A liquid in the said B liquid and stirring for 1 hour, the obtained coprecipitate was fully washed with water, dried, and baked at 400 degreeC in the air for 5 hours, gold fine particle fixed iron An oxide was obtained.
(比較例4)
過マンガン酸カリウム15.0gを1000mlの純水に溶解した。この水溶液にシュウ酸22.5gを純水に溶解した300mlの水溶液を添加し、1晩撹拌した。得られた沈殿物を十分に水洗して乾燥し、空気中で300℃で2時間焼成して酸化マンガン触媒を得た。
(Comparative Example 4)
15.0 g of potassium permanganate was dissolved in 1000 ml of pure water. To this aqueous solution, 300 ml of an aqueous solution in which 22.5 g of oxalic acid was dissolved in pure water was added and stirred overnight. The obtained precipitate was sufficiently washed with water, dried, and calcined in air at 300 ° C. for 2 hours to obtain a manganese oxide catalyst.
(実施例6)
ジクロロメタン濃度10ppm、空気500ml/min、水蒸気RH50%の条件で、実施例4、実施例5、比較例3、比較例4、および市販触媒(N−840:ズードケミー触媒(株)製)の触媒5mlを常圧管状流通反応装置にセットして、50℃から200℃でジクロロメタンの分解率を測定した。ジクロロメタンの分解率は、下記の式で計算した。
(Example 6)
A catalyst of Example 4, Example 5, Comparative Example 3, Comparative Example 4, and a commercially available catalyst (N-840: manufactured by Zude Chemie Catalysts Co., Ltd.) under conditions of a dichloromethane concentration of 10 ppm, air of 500 ml / min, and water vapor RH of 50%. Was set in an atmospheric pressure tubular flow reactor, and the decomposition rate of dichloromethane was measured at 50 to 200 ° C. The decomposition rate of dichloromethane was calculated by the following formula.
ジクロロメタン除去率(%)=(入口濃度−出口濃度)×100/入口濃度 Dichloromethane removal rate (%) = (inlet concentration−outlet concentration) × 100 / inlet concentration
表1に、各温度における各触媒のジクロロメタン除去率を示す。 Table 1 shows the dichloromethane removal rate of each catalyst at each temperature.
以上の結果より、本発明の触媒が、他の市販触媒や通常の酸化触媒に較べて、有機塩素化合物の分解性能が非常に高いことがわかる。 From the above results, it can be seen that the catalyst of the present invention has a very high decomposition performance of organochlorine compounds compared to other commercially available catalysts and ordinary oxidation catalysts.
なお、用いた常圧管状流通反応装置の概略を図1に示す。図1に示したように、この反応装置では、触媒充填層102をガラス管104の中間に設置し、このガラス管104の上下に通気管106、108が配置されている。上記濃度でジクロロメタンを含んだ気体110は、一方の通気管106からガラス管104へと供給され、触媒充填層102を通過して他方の通気管108から排出される。また、触媒充填層102の温度を調整できるように、ガラス管104の周囲にはヒータ112が設置されている。
An outline of the atmospheric pressure tubular flow reactor used is shown in FIG. As shown in FIG. 1, in this reaction apparatus, the catalyst packed
102 触媒充填層
104 ガラス管
106、108 通気管
110 気体
112 ヒータ
102 Catalyst packed
Claims (11)
The method for removing an organic chlorine compound according to any one of claims 8 to 10, wherein the organic chlorine compound is dichloromethane, chloromethane, chloroform, dichloroethane, chloroethane, chloroethylene, or dichloroethylene.
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