JP2015164724A - Agent and method for detoxifying metal hydride-containing exhaust gas - Google Patents
Agent and method for detoxifying metal hydride-containing exhaust gas Download PDFInfo
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- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 64
- 150000004681 metal hydrides Chemical class 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 86
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 45
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 238000011282 treatment Methods 0.000 claims description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 150000001412 amines Chemical class 0.000 abstract description 22
- 239000001257 hydrogen Substances 0.000 abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 5
- 238000001784 detoxification Methods 0.000 description 21
- 238000005259 measurement Methods 0.000 description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 description 15
- 150000004692 metal hydroxides Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 229940116318 copper carbonate Drugs 0.000 description 10
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- -1 basic metal carbonate Chemical class 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910000078 germane Inorganic materials 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DLXAZYQCSSNEPD-UHFFFAOYSA-N [O-2].[Mn+2].[Cu]=O Chemical compound [O-2].[Mn+2].[Cu]=O DLXAZYQCSSNEPD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は金属水素化物含有排ガスの除害剤及び除害方法に関し、詳しくは、半導体製造工場、もしくは液晶製造工場などで発生する金属水素化物含有排ガスの除害剤および除害方法に関する。 The present invention relates to a detoxifying agent and detoxification method for metal hydride-containing exhaust gas, and more particularly to a detoxifying agent and detoxification method for metal hydride-containing exhaust gas generated in a semiconductor manufacturing factory or a liquid crystal manufacturing factory.
半導体製造工場では、その製造中に各種金属水素化物ガス、ハロゲン化物ガス類が使用されている。これらのガスは可燃性及び／又は有害性であることから、これらを含有する排ガスを環境保全上、大気中にそのまま放出することはできず、その危険性、有害性をなくするための処理が必要である。 In a semiconductor manufacturing factory, various metal hydride gases and halide gases are used during the manufacturing process. Since these gases are flammable and / or harmful, the exhaust gas containing them cannot be released into the atmosphere as it is for environmental conservation, and there are no treatments to eliminate the danger or harm. is necessary.
排ガス処理には湿式法と乾式法があり、前者は薬液で排ガスを洗浄処理する方法である。一方、後者は、粒状固体処理剤の充填塔に排ガスを流通させ、除害対象ガスと処理剤との化学的作用、即ち、吸着及び／又は化学反応により、危険性、有害性ガスを分離、除害する方法であり、金属水素化物含有排ガス或いはハロゲン化物ガス含有排ガスの処理で多く行われている。 There are a wet method and a dry method for exhaust gas treatment, and the former is a method of cleaning exhaust gas with a chemical solution. On the other hand, in the latter, exhaust gas is circulated through a packed column of a particulate solid processing agent, and the hazardous and harmful gases are separated by chemical action of the gas to be removed and the processing agent, that is, adsorption and / or chemical reaction. It is a detoxifying method and is often performed in the treatment of exhaust gas containing metal hydride or exhaust gas containing halide gas.
金属水素化物含有排ガス処理剤には多くの特許が見られ、例えば、金属水酸化物からなる処理剤は、特開平０７−１３６４５１号公報（特許文献１）および特開平０６−３１９９４５号公報（特許文献２）、固体金属水酸化物、固体金属炭酸塩および固体金属塩基性炭酸塩のいずれかからなる処理剤については特開平０８−１９２０２４号公報（特許文献３）、特開昭６２−１５２５１５号公報（特許文献４）、塩基性金属炭酸塩からなる処理剤については特許第２６０４９９１号公報（特許文献５）等に示されている。 There are many patents for the metal hydride-containing exhaust gas treatment agent. For example, treatment agents comprising metal hydroxides are disclosed in Japanese Patent Application Laid-Open Nos. 07-136451 (Patent Document 1) and Japanese Patent Application Laid-Open No. 06-319945 (Patents). Document 2), a treating agent comprising any one of solid metal hydroxide, solid metal carbonate and solid metal basic carbonate is disclosed in Japanese Patent Application Laid-Open No. 08-192024 (Patent Document 3) and Japanese Patent Application Laid-Open No. 62-152515. Japanese Patent Publication (Patent Document 4), a processing agent comprising a basic metal carbonate is disclosed in Japanese Patent No. 2604991 (Patent Document 5) and the like.
しかしながら、金属水酸化物、金属炭酸塩あるいは金属塩基性炭酸塩からなる処理剤は、単独でも優れた除害能力を有するが、上記排ガスの処理に伴う化学反応はいずれも発熱性である。従って、従来技術では金属化合物類による排ガス処理は温度上昇が必然的であり、高濃度の金属水素化物を含有する排ガス処理や大量の排ガス処理を行う場合は、大幅な温度上昇を生じる可能性がある。そのために、処理剤は高性能であるだけではなく、低発熱性であることが要求される。更に半導体製造工程で金属水素化物ガスを使用する際、水素雰囲気中で使う場合に、処理剤が被処理ガス中の水素と反応する、すなわち金属の還元による非常に高温の発熱反応、いわゆる暴走反応が起こりやすくなる。そのために処理剤の金属が還元される温度をいかに高くするかが安全面で非常に重要であり、望ましい技術である。 However, treatment agents made of metal hydroxide, metal carbonate or metal basic carbonate alone have excellent detoxifying ability, but all chemical reactions associated with the treatment of exhaust gas are exothermic. Therefore, in the prior art, exhaust gas treatment with metal compounds inevitably requires a temperature rise, and when exhaust gas treatment containing a high concentration of metal hydride or a large amount of exhaust gas treatment is performed, there is a possibility that a significant temperature rise will occur. is there. Therefore, the treatment agent is required not only to have high performance but also to have low heat generation. Furthermore, when using metal hydride gas in the semiconductor manufacturing process, when used in a hydrogen atmosphere, the treating agent reacts with hydrogen in the gas to be treated, that is, a very high temperature exothermic reaction due to metal reduction, so-called runaway reaction. Is likely to occur. Therefore, how to raise the temperature at which the metal of the treating agent is reduced is very important in terms of safety and is a desirable technique.
本発明は、半導体製造工程で発生する金属水素化物含有排ガスの除害処理において、高い処理能力を示し、かつ、金属が還元される温度を高くし暴走反応を起こり難くする金属水素化物含有排ガスの除害剤及び除害方法を提供することを目的とする。 The present invention provides a metal hydride-containing exhaust gas that exhibits high treatment capacity in the detoxification treatment of a metal hydride-containing exhaust gas generated in a semiconductor manufacturing process, and that makes it difficult to cause a runaway reaction by increasing the temperature at which the metal is reduced. An object is to provide a pesticide and a pesticide method.
本発明者らは、上記の課題を解決すべく鋭意研究を続けた結果、固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物に酸またはアミン類を添加することにより、高濃度の金属水素化物含有排ガスに対して優れた除害処理能力を有し、しかも従来の金属酸化物系処理剤よりも水素中での金属還元温度が高くなり暴走反応を起こり難くすることを見出した。この知見に基づき、更に詳細に検討することによって本発明を完成した。 As a result of continual research to solve the above problems, the present inventors have found that at least one metal compound of solid metal basic carbonate, solid metal oxide, solid metal hydroxide, and solid metal carbonate has an acid. Or, by adding amines, it has excellent detoxification ability for exhaust gas containing high concentrations of metal hydride, and has a higher metal reduction temperature in hydrogen than conventional metal oxide treatment agents. I found that the runaway reaction is less likely to occur. Based on this knowledge, the present invention was completed by examining in more detail.
すなわち、固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物に酸またはアミン類を添加することを特徴とする金属水素化物含有排ガスの除害剤である。 That is, removal of exhaust gas containing metal hydride, characterized by adding an acid or amines to at least one metal compound of solid metal basic carbonate, solid metal oxide, solid metal hydroxide, solid metal carbonate. It is a harmful agent.
また、添加する酸は、硝酸、硫酸、クエン酸、酢酸から選択されるいずれか一つであることを特徴とする金属水素化物含有排ガスの除害剤である。 Further, the acid to be added is any one selected from nitric acid, sulfuric acid, citric acid, and acetic acid.
更に、添加するアミン類は、１級、２級または３級アミンから選択されるいずれか一つであることを特徴とする金属水素化物含有排ガスの除害剤である。 Furthermore, the amine to be added is any one selected from primary, secondary, and tertiary amines, and is a metal hydride-containing exhaust gas detoxifying agent.
金属化合物に対して０．１〜２０重量％の酸又はアミン類を添加することを特徴とする金属水素化物含有排ガスの除害剤である。 A metal hydride-containing exhaust gas detoxifying agent characterized by adding 0.1 to 20% by weight of an acid or amine to the metal compound.
また、固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物の金属成分が、銅、マンガン、鉄、シリカから選択される１種または２種以上の成分であることを特徴とする金属水素化物含有排ガスの除害剤である。 The metal component of at least one metal compound of solid metal basic carbonate, solid metal oxide, solid metal hydroxide, and solid metal carbonate is selected from copper, manganese, iron, and silica, or one or two It is a metal hydride-containing exhaust gas detoxifier characterized by being a component of more than seeds.
更に、金属化合物に酸またはアミン類を添加後成型されることを特徴とする金属水素化物含有排ガスの除害剤である。 Furthermore, the present invention is a metal hydride-containing exhaust gas detoxifying agent, which is molded after adding an acid or an amine to a metal compound.
また、金属水素化物含有排ガスを請求項１乃至５のいずれか一項に記載の処理剤と接触させることを特徴とする金属水素化物含有排ガスの除害方法である。 Moreover, it is a detoxification method of the metal hydride containing exhaust gas characterized by making a metal hydride containing exhaust gas contact with the processing agent as described in any one of Claims 1 thru | or 5.
本発明の固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物に酸又はアミン類を添加して製造した処理剤は、高濃度の金属水素化物含有排ガスに対して優れた除害処理能力を有し、しかも従来の金属酸化物系 処理剤よりも水素中での金属還元温度が高くなり暴走反応を起こり難くすることができ、また、冷却設備等あるいは監視装置等特別な装置を用いることなく操作上の安全面においても優れている。 The treatment agent produced by adding an acid or an amine to at least one metal compound of the solid metal basic carbonate, solid metal oxide, solid metal hydroxide, and solid metal carbonate of the present invention is a high concentration metal. It has excellent detoxification treatment capacity for hydride-containing exhaust gas, and also has a higher metal reduction temperature in hydrogen than conventional metal oxide treatment agents, making runaway reaction difficult to occur. It is excellent in terms of operational safety without using a special device such as a cooling facility or a monitoring device.
以下に本発明を詳述する。 The present invention is described in detail below.
本発明は、固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物に酸又はアミン類を添加して製造した処理剤に関する発明である。より具体的には、固体塩基性炭酸銅、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物のドライベースで０．１〜２０重量％の酸又はアミン類を添加し金属化合物類の金属の水素による還元が始まる温度を高くし暴走反応を起こり難くすることを特徴とする。より好適には上記金属化合物のドライベースで４〜１０重量％の酸又はアミン類を添加することができる。 The present invention relates to a treatment agent produced by adding an acid or an amine to at least one metal compound of solid metal basic carbonate, solid metal oxide, solid metal hydroxide, and solid metal carbonate. More specifically, 0.1 to 20% by weight of an acid or amine based on a dry base of at least one metal compound of solid basic copper carbonate, solid metal oxide, solid metal hydroxide, and solid metal carbonate. It is characterized by increasing the temperature at which reduction of metal compounds by hydrogen with metal compounds begins to occur, making runaway reaction difficult. More preferably, 4 to 10% by weight of acid or amine can be added on a dry basis of the metal compound.
ここで処理剤の主体をなす金属化合物の金属としては、固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物で安定に存在し得るものであればどのような金属でも使用することができるが、通常容易に入手できしかも安価な銅、鉄、マンガン、コバルト、ニッケル、マンガン、亜鉛、クロム等が有利に用いられる。 Here, the metal of the metal compound forming the main component of the treatment agent is at least one metal compound of solid metal basic carbonate, solid metal oxide, solid metal hydroxide, solid metal carbonate, which can exist stably. Any metal can be used, but copper, iron, manganese, cobalt, nickel, manganese, zinc, chromium, etc., which are usually easily available and inexpensive, are advantageously used.
更に、本発明の金属化合物類は市販の炭酸塩、酸化物、水酸化物、或いは塩基性炭酸塩をそのまま使用することができ、また金属化合物類の前駆体としての金属塩類を水溶液となした後、添加成分化合物類、たとえばアルカリ化合物類水溶液との中和反応によって製造することもできる。この添加成分化合物類、特にアルカリ化合物類としてはナトリウム、カリウムの水酸化物、炭酸塩等を使用するのが好ましい。中和反応によって得られた沈澱物は水洗した後、濾過、乾燥され原料として使用することもできる。 Furthermore, as the metal compounds of the present invention, commercially available carbonates, oxides, hydroxides, or basic carbonates can be used as they are, and metal salts as precursors of metal compounds are made into aqueous solutions. Then, it can also manufacture by neutralization reaction with additive component compounds, for example, alkaline compound aqueous solution. It is preferable to use sodium, potassium hydroxide, carbonate or the like as the additive component compounds, particularly alkali compounds. The precipitate obtained by the neutralization reaction can be washed with water, filtered and dried and used as a raw material.
ここで、金属化合物類は市販のもの、沈澱法によるもの共に単一化合物での使用のみならず、混合物となして使用してもよい。沈殿法による化合物類の場合、混合物としての使用においては化合物を単独で沈澱させたものを混合してもよいが、共沈法によって複数成分を含む沈澱物を得ることによる方が好ましい。 Here, both commercially available and precipitated metal compounds may be used not only as a single compound but also as a mixture. In the case of compounds by the precipitation method, in the case of use as a mixture, a compound obtained by precipitating the compound alone may be mixed, but it is preferable to obtain a precipitate containing a plurality of components by the coprecipitation method.
添加成分化合物類に金属化合物類を担持する場合において、金属化合物類前駆体は、市販品を使用する場合は粉状物、その成型物、或いは成型後破砕した顆粒が使用され、沈澱法によって製造した金属化合物類前駆体の場合も同様に粉状物、その成型物、若しくは成型後の破砕物が使用される。あるいは、沈澱法によって製造した金属化合物類前駆体としての金属塩類水溶液に添加成分化合物類を予め溶解させておき、酸またはアミン類を加えることができる。これらを以下にまとめて表１に示すと次のようになる。 In the case where metal compounds are supported on additive component compounds, the precursors for metal compounds are powdered products, molded products, or crushed granules after molding, and are produced by a precipitation method. Similarly, in the case of the metal compound precursor, a powdery product, a molded product thereof, or a crushed product after molding is used. Alternatively, the additive component compounds can be dissolved in advance in an aqueous metal salt solution as a metal compound precursor produced by a precipitation method, and an acid or an amine can be added. These are summarized below and shown in Table 1 as follows.
なお、金属化合物類による金属水素化物含有排ガスの処理は、開始直後の吸着作用及び／又は化学反応から、時間が経過して処理剤温度が上昇した時点より支配的になる化学反応へと移行し、それ以降は反応中心の定常的除害過程が大部分の金属成分が消費されるまで継続すると考えられる。この定常状態での反応は見方を変えれば金属化合物類の金属水素化物による還元であり、水素による金属化合物類の還元の場合と同様に水酸化物の方が酸化物よりも発熱性は小さく、また塩基性炭酸塩の場合も同様であることが推定される。従って、金属成分の水素による還元が起こる可能性がある還元性排ガス処理においては、有効金属成分としては発熱性が小さい金属水酸化物、金属炭酸塩、塩基性金属炭酸塩、若しくはこれらの混合物であることがより好ましい。 In addition, the treatment of exhaust gas containing metal hydride with metal compounds shifts from the adsorption action and / or chemical reaction immediately after the start to a chemical reaction that becomes dominant from the point in time when the treatment agent temperature has risen. After that, it is considered that the steady detoxification process of the reaction center continues until most of the metal components are consumed. In other words, the reaction in the steady state is a reduction of metal compounds by metal hydride, and the hydroxide is less exothermic than the oxide as in the case of reduction of metal compounds by hydrogen. It is presumed that the same is true for basic carbonates. Therefore, in reducing exhaust gas treatment in which reduction of the metal component with hydrogen may occur, the effective metal component may be a metal hydroxide, metal carbonate, basic metal carbonate, or a mixture thereof having a low exothermic property. More preferably.
添加する酸の種類は硝酸、硫酸、クエン酸、酢酸等の酸から適宜選択される。 The kind of acid to be added is appropriately selected from acids such as nitric acid, sulfuric acid, citric acid and acetic acid.
添加するアミン類の種類は１級、２級または３級アミンから選択され、好適には、重炭安、尿素から選択される。 The kind of amines to be added is selected from primary, secondary or tertiary amines, and preferably selected from heavy coal and urea.
また、酸またはアミン類の添加量は金属化合物類に対して０．１〜２０重量％であり、より好適には、２〜１０重量％である。 Moreover, the addition amount of an acid or amines is 0.1 to 20 weight% with respect to metal compounds, More preferably, it is 2 to 10 weight%.
本発明の除害剤は、先ず酸の添加は混練法で加えられる場合は、粉末状の金属化合物類と添加成分化合物類の混練中または終了後に添加され、更に押出し、或いは打錠によって成型物とされる。その後、成型物を更に乾燥または焼成することによって最終的に除害剤を製造する。なお、成型された除害剤のサイズは主に０．１ｍｍ〜１５ｍｍであることが好ましい。また、成型後に乾燥あるいは焼成する際の温度は、５０℃〜３００℃であることが好ましい。 When the addition of acid is first carried out by the kneading method, the detoxifying agent of the present invention is added during or after the kneading of the powdered metal compounds and additive component compounds, and is further molded by extrusion or tableting. It is said. Thereafter, the molded product is further dried or fired to finally produce a detoxifying agent. In addition, it is preferable that the size of the molded disinfectant is mainly 0.1 mm to 15 mm. Moreover, it is preferable that the temperature at the time of drying or baking after shaping | molding is 50 to 300 degreeC.
また、本発明の除害剤には使用に耐え得る機械的強度を確保するために、必要に応じてシリカ、アルミナ、マグネシア、若しくはその他の強度改善に有効な無機バインダー類を加えることができる。 Moreover, in order to ensure the mechanical strength which can be used, the inorganic chemicals effective for strength improvement can be added to the abatement agent of the present invention as needed.
なお、排ガスの処理方法は、充填塔に詰められた処理剤に処理対象ガスを流通することによるため、成型処理は圧力損失を低減するために必須で、必要に応じてこれら成型物は破砕処理され、顆粒状となして使用してもよい。 In addition, since the treatment method of the exhaust gas is based on circulating the gas to be treated through the treatment agent packed in the packed tower, the molding treatment is indispensable for reducing the pressure loss, and these molded products are crushed as necessary. It may be used in the form of granules.
アミン類の添加も基本的に上述の酸の添加と同様な方法であるがアンモニア除害施設が必要である。 Addition of amines is basically the same method as the above-mentioned acid addition, but an ammonia abatement facility is required.
本発明の除害剤の還元安定性は、理学社製（ＴＨＥＲＭＯＰＬＵＳ、ＴＧ８１２０）の熱重量及び示差走査熱量測定装置（Ｔｈｅｒｍｏ ｇｒａｖｉｍｅｔｒｉｃ ａｎｄ ｄｉｆｆｅｒｅｎｔｉａｌ ｓｃａｎｎｉｎｇ ｃａｌｏｒｉｍｅｔｅｒ（ＴＧ−ＤＴＡ））を使い水素雰囲気中で処理剤の発熱温度を測ることにより実施することができる。測定装置、測定条件、測定操作法は次の通りである。 The reducing stability of the detoxifying agent of the present invention is treated in a hydrogen atmosphere using a thermogravimetric and differential scanning calorimeter (TG-DTA) manufactured by Rigaku Corporation (THERMOPLUS, TG8120). This can be carried out by measuring the exothermic temperature. The measurement apparatus, measurement conditions, and measurement operation method are as follows.
（水素雰囲気中での測定条件）
測定温度範囲：２０℃〜３００℃
増温速度：１０℃／分
水素：３０ｍｌ／分
圧力：常圧
処理剤量：５〜１５ｍｇ
本発明の除害剤における還元安定性の測定結果は表２に示す。
(Measurement conditions in a hydrogen atmosphere)
Measurement temperature range: 20 ° C to 300 ° C
Heating rate: 10 ° C / min
Hydrogen: 30ml / min
Pressure: normal pressure
Treatment agent amount: 5 to 15 mg
Table 2 shows the measurement results of the reduction stability of the detoxifying agent of the present invention.
更に本発明は、固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩の少なくとも一種の金属化合物に酸またはアミン類を添加する除害剤に金属水素化物を含む排ガスを接触させることによる金属水素化物を含む排ガスの除害方法に関するものである。より詳しくは、金属塩基性炭酸塩、金属酸化物、金属水酸化物、金属炭酸塩の少なくとも一種の金属化合物に０．１〜２０重量％の酸又はアミン類を添加成型し、還元安定性を向上させた金属水素化物を含む排ガスの除害方法に関するものである。 The present invention further includes a metal hydride as a detoxifying agent for adding an acid or amines to at least one metal compound of solid metal basic carbonate, solid metal oxide, solid metal hydroxide, solid metal carbonate. The present invention relates to a method for removing exhaust gas containing metal hydride by contacting exhaust gas. More specifically, 0.1 to 20% by weight of acid or amine is added and molded to at least one metal compound of metal basic carbonate, metal oxide, metal hydroxide, and metal carbonate to reduce reduction stability. The present invention relates to a method for removing exhaust gas containing an improved metal hydride.
実際の使用に当たり、本発明の金属塩基性炭酸塩、金属酸化物、金属水酸化物、金属炭酸塩の少なくとも一種の金属化合物に酸又はアミン類を添加したことによって得られた除害剤は、流通式の充填塔に詰められ固定床として使用される。次いで金属水素化物を含有する排ガスはこの充填塔内に流され、除害剤と接触させることによって金属水素化物ガスは除害される。本発明の除害剤によって除害できる金属水素化物ガスとしては、シラン、アルシン、ホスフィン、ジシラン、ジボラン、セレン化水素、ゲルマン、ジクロルシラン等がある。また、本発明の除害方法が適用される金属水素化物ガス類の濃度およびガスの流速に制限はないが、一般に濃度が高い程流速を小さくすることが望ましい。 In actual use, the detoxifying agent obtained by adding an acid or an amine to at least one metal compound of the metal basic carbonate, metal oxide, metal hydroxide, metal carbonate of the present invention, Packed in a flow-type packed tower and used as a fixed bed. The exhaust gas containing the metal hydride is then allowed to flow into the packed tower and the metal hydride gas is detoxified by contact with a detoxifying agent. Examples of the metal hydride gas that can be removed by the remover of the present invention include silane, arsine, phosphine, disilane, diborane, hydrogen selenide, germane, and dichlorosilane. Moreover, although there is no restriction | limiting in the density | concentration of metal hydride gas and gas flow velocity to which the removal method of this invention is applied, it is generally desirable to make a flow velocity small, so that a density | concentration is high.
また、金属水素化物ガスと除害剤との接触温度は１００℃以下が好ましいが、通常は常温ないし室温でよく、特に加熱や冷却をする必要はない。また、金属水素化物ガスの圧力についても、常圧、減圧、加圧のいずれでもよい。 Further, the contact temperature between the metal hydride gas and the detoxifying agent is preferably 100 ° C. or lower, but it is usually normal temperature to room temperature, and it is not necessary to perform heating or cooling. Further, the pressure of the metal hydride gas may be any of normal pressure, reduced pressure, and increased pressure.
本発明においては、具体的には、本発明で得られた除害剤をステンレス製流通式反応装置に充填し、金属水素化物ガスとして、シラン、ホスフィン、ゲルマンを含有する還元性ガスを反応器に流通させ、除害剤層の温度測定を行いつつ、出口ガス中の金属水素化物ガス漏洩量をブレークモニター（日本バイオニクス社製）によって測定、監視することによって、常温における金属水素化物含有ガスの除害性能測定試験を行った。 In the present invention, specifically, the detoxifying agent obtained in the present invention is filled into a stainless steel flow reactor, and a reducing gas containing silane, phosphine, and germane is used as a metal hydride gas in the reactor. Gas hydride-containing gas at room temperature by measuring and monitoring the amount of metal hydride gas leakage in the exit gas with a break monitor (manufactured by Nippon Bionics) while measuring the temperature of the pesticide layer A detoxification performance measurement test was conducted.
その結果、従来の酸化物系処理剤の場合は試験開始後、暴走反応による処理剤層の温度上昇が著しかったが、本発明の除害剤においては充填層の温度上昇があったものの激しい発熱は起こらなかった。更に、その性能に関しては、酸又はアミン類添加による金属水素化物の処理性能に悪い影響は与えず、処理性能は維持して還元安定性が向上することを確認して本発明を完成した。 As a result, in the case of the conventional oxide-based treatment agent, the temperature rise of the treatment agent layer due to the runaway reaction was remarkable after the start of the test, but in the remover of the present invention, although the temperature of the packed bed was raised, intense heat generation Did not happen. Further, regarding the performance, the present invention was completed by confirming that the addition of acid or amines did not adversely affect the processing performance of the metal hydride and that the processing performance was maintained and the reduction stability was improved.
以下、本発明の内容を実施例によって更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although the content of the present invention is explained still in detail by an example, the present invention is not limited to these.
本発明処理剤の性能評価は窒素ガス中に含まれる金属水素化物ガスの除害性能を測定することによって行った。測定は常圧流通式の反応装置によって行い、その測定装置、測定条件、測定操作法は次の通りである。 The performance evaluation of the treating agent of the present invention was performed by measuring the detoxifying performance of the metal hydride gas contained in the nitrogen gas. The measurement is performed by a normal pressure flow type reaction apparatus, and the measurement apparatus, measurement conditions, and measurement operation method are as follows.
（金属水素化物ガスの除害性能測定装置、及び測定条件）
除害性能測定装置：常圧流通式反応装置
反応管のサイズ ：内径２８ｍｍ、長さ７００ｍｍ
測定条件
使用処理剤量：６０ｃｃ（充填高さ１００ｍｍ）
ＧＨＳＶ ：３００ｈｒ−１
圧力 ：常圧
反応温度 ：常温
反応ガス組成：ＳｉＨ４（シラン）、又はＰＨ３（ホスフィン）、Ｎ２ バランス
(Metal hydride gas abatement performance measuring device and measurement conditions)
Detoxification performance measuring device: Normal pressure flow reactor Reaction tube size: Inner diameter 28mm, Length 700mm
Measurement condition
Amount of processing agent used: 60 cc (filling height 100 mm)
GHSV: 300 hr-1
Pressure: Normal pressure
Reaction temperature: normal temperature
Reaction gas composition: SiH 4 (silane) or PH 3 (phosphine), N 2 balance
（金属水素化物ガスの除害性能測定操作方法及び除害性能計算法）
除害剤６０ｃｃを充填高が１００ｍｍになるように反応管内に詰めて測定装置に設置し、次いで窒素（純度９９．９９％）で希釈した金属水素化物ガスを除害剤充填層に流通させた。ガス流通開始後、除害剤層の温度測定を行いつつ、反応管出口ガス中への金属水素化物ガス漏洩をブレークモニター（日本バイオニクス製）で測定、監視し、その出口濃度が５ｐｐｍに達するまでに流入したシラン、ホスフィン、ゲルマンの積算量を求め、その量を処理剤１ｋｇ当りに換算した。具体的には測定結果から次の式によって金属水素化物ガスの除害性能は計算された。
(Metallic hydride gas abatement performance measurement operation method and abatement performance calculation method)
60 cc of the detoxifying agent was packed in the reaction tube so that the filling height was 100 mm and installed in the measuring device, and then metal hydride gas diluted with nitrogen (purity 99.99%) was circulated through the packed bed of detoxifying agent. . After starting gas flow, while measuring the temperature of the detoxifying agent layer, the metal hydride gas leakage into the reaction tube outlet gas is measured and monitored with a break monitor (manufactured by Nippon Bionics), and the outlet concentration reaches 5 ppm. The total amount of silane, phosphine, and germane that had flowed up to this point was determined, and the amount was converted per 1 kg of the treatment agent. Specifically, the detoxification performance of metal hydride gas was calculated from the measurement results by the following formula.
（処理剤の金属水素化物ガス除害性能計算法）
除害性能（Ｌ／ｋｇ）＝Ａ×（Ｂ／１００）×（Ｃ／Ｅ）
ここで、Ａ：測定ガス流量（Ｌ／ｍｉｎ．）
Ｂ：金属水素化物ガス濃度（容積％）
Ｃ：金属水素化物ガスの出口濃度が所定の濃度に達するまでの累積ガス流通時間（ｍｉｎ．）
Ｅ：処理剤充填量（ｋｇ）
［実施例１］
(Calculation method for metal hydride gas removal performance of treatment agents)
Detoxification performance (L / kg) = A × (B / 100) × (C / E)
Here, A: Measurement gas flow rate (L / min.)
B: Metal hydride gas concentration (volume%)
C: Cumulative gas circulation time (min.) Until the outlet concentration of the metal hydride gas reaches a predetermined concentration
E: Treatment agent filling amount (kg)
[Example 1]
金属化合物として市販の塩基性炭酸銅を用い、ニーダーの中で酢酸を市販塩基性炭酸銅に対して２重量％酢酸と適量の純水と充分混合した後、直径１．５ｍｍまたは３ｍｍのサイズに押出し成型し、１００℃で乾燥した。次いで１００℃で乾燥したものを除害剤とした。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。
［実施例２］
Using commercially available basic copper carbonate as a metal compound, acetic acid in a kneader is sufficiently mixed with 2% by weight acetic acid and an appropriate amount of pure water with respect to the commercially available basic copper carbonate, and then the diameter is 1.5 mm or 3 mm. Extruded and dried at 100 ° C. Subsequently, what was dried at 100 ° C. was used as a remover. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
[Example 2]
実施例１において、酢酸を４重量％にした他は実施例１と全て同様にして除害剤を製造した。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。
［実施例３］
In Example 1, a detoxifying agent was produced in the same manner as in Example 1 except that acetic acid was changed to 4% by weight. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
[Example 3]
実施例１において、酢酸を８重量％にした他は実施例１と全て同様にして除害剤を製造した。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。
［実施例４］
In Example 1, a detoxifying agent was produced in the same manner as in Example 1 except that acetic acid was changed to 8% by weight. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
[Example 4]
実施例１において、金属化合物として市販の塩基性炭酸銅に代え、酸化銅−酸化マンガンを使用し、直径と長さが４．５ｍｍのサイズに打錠成型し、１７０℃または３２０℃で乾燥・焼成して実施例４、５の処理剤を調製した。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。
［実施例５］
In Example 1, instead of commercially available basic copper carbonate as a metal compound, copper oxide-manganese oxide was used, and the tablet was molded into a size having a diameter and length of 4.5 mm, and dried at 170 ° C. or 320 ° C. The treating agents of Examples 4 and 5 were prepared by firing. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
[Example 5]
金属化合物として市販の塩基性炭酸銅を用い、ニーダーの中で尿素を市販塩基性炭酸銅に対して４重量％尿素と適量の純水と充分混合した後、直径１．５ｍｍまたは３ｍｍのサイズに押出し成型し、１１０℃で乾燥した。次いで１１０℃で乾燥したものを除害剤とした。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。
［実施例６］
Commercially available basic copper carbonate is used as the metal compound, and urea is mixed in a kneader with 4% by weight urea and an appropriate amount of pure water with respect to the commercially available basic copper carbonate, and then the diameter is 1.5 mm or 3 mm. Extruded and dried at 110 ° C. Subsequently, what was dried at 110 ° C. was used as a detoxifying agent. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
[Example 6]
実施例５において、尿素を１０重量％にした他は実施例５と全て同様にして除害剤を製造した。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。 In Example 5, a detoxifying agent was produced in the same manner as in Example 5 except that urea was changed to 10% by weight. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
実施例１において、除害剤の調製において、塩基性炭酸銅の押出し成型段階に留め、酢酸又は尿素の添加を行わない、すなわち酸又はアミン類を含有しない比較例１として、除害剤を調製した。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。 In Example 1, in the preparation of the detoxifying agent, the detoxifying agent was prepared as Comparative Example 1 in which the addition of acetic acid or urea was not performed, that is, no addition of acetic acid or urea was performed in the extrusion process of basic copper carbonate. did. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
比較例１において、塩基性炭酸銅に代えて水酸化銅を使用した以外は比較例１と全く同様にして比較例２の除害剤を調製した。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。 In Comparative Example 1, a detoxifying agent of Comparative Example 2 was prepared in exactly the same manner as Comparative Example 1 except that copper hydroxide was used instead of basic copper carbonate. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
比較例１において、塩基性炭酸銅に代えて酸化銅と酸化マンガンを使用した以外は比較例１と全く同様にして比較例３の除害剤を調製した。得られた除害剤の金属水素化物の水素中での還元安定性（ＴＧ−ＤＴＡ）結果および除害性能結果を表２に示した。 In Comparative Example 1, a detoxifying agent of Comparative Example 3 was prepared in exactly the same manner as Comparative Example 1 except that copper oxide and manganese oxide were used instead of basic copper carbonate. Table 2 shows the reduction stability (TG-DTA) results and the detoxification performance results of the obtained detoxifying agent in the hydrogen of the metal hydride.
表２の結果より、実施例における金属酸化物、金属水酸化物、金属炭酸塩、塩基性金属炭酸塩系化合物に酸又はアミン類を添加することによって、少なくとも１０℃、高くて９０℃以上金属の還元が始まる温度を高めることができた。一方、金属化合物に酸またはアミンを添加していない比較例１〜３は実施例に比較して還元が始まる温度が高くならず、水素中での金属の還元安定性が低かった。特に、金属化合物の中でも塩基性炭酸銅においては、酸又はアミン類添加の有無に顕著な結果の差があった。 From the results shown in Table 2, at least 10 ° C. and higher than 90 ° C. metal by adding acid or amines to the metal oxide, metal hydroxide, metal carbonate, basic metal carbonate compound in the examples. The temperature at which the reduction starts can be increased. On the other hand, in Comparative Examples 1 to 3 in which no acid or amine was added to the metal compound, the temperature at which the reduction started was not higher than in the Examples, and the reduction stability of the metal in hydrogen was low. In particular, among the metal compounds, basic copper carbonate has a remarkable difference in the presence or absence of addition of acid or amines.
本発明によれば、半導体製造工程で発生する金属水素化物含有ガスを除害する際に、従来の除害剤を使用すると、除害剤と被処理ガス中の水素とが反応する金属の還元反応によって生じていた暴走反応を、本発明の除害剤を使用することで金属の還元開始温度を高めることができるため、暴走反応を抑制することが可能となる。また、金属化合物に酸またはアミン類を添加することで除害剤の性能に対して影響を与えることがないため、除害性能を維持したまま暴走反応をも抑制することができる。従って本発明の除害剤は暴走反応を防止するための特別な装置あるいは制御手段を講じることもなく、簡便で安全なガスの除害が達成できるため、工業的利用に非常に価値が高い。 According to the present invention, when a conventional detoxifying agent is used when detoxifying a metal hydride-containing gas generated in a semiconductor manufacturing process, the reduction of the metal in which the detoxifying agent reacts with hydrogen in the gas to be treated. The runaway reaction caused by the reaction can be suppressed by using the detoxifying agent of the present invention, so that the metal reduction start temperature can be increased. In addition, the addition of an acid or an amine to the metal compound does not affect the performance of the detoxifying agent, so that the runaway reaction can be suppressed while maintaining the detoxifying performance. Therefore, the detoxifying agent of the present invention is very valuable for industrial use because it can achieve simple and safe gas detoxification without taking special equipment or control means for preventing runaway reaction.
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