JP2017119271A - ギ酸の処理方法及びギ酸の処理装置 - Google Patents
ギ酸の処理方法及びギ酸の処理装置 Download PDFInfo
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- JP2017119271A JP2017119271A JP2016230852A JP2016230852A JP2017119271A JP 2017119271 A JP2017119271 A JP 2017119271A JP 2016230852 A JP2016230852 A JP 2016230852A JP 2016230852 A JP2016230852 A JP 2016230852A JP 2017119271 A JP2017119271 A JP 2017119271A
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- formic acid
- treatment
- gas
- activated carbon
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- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound 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OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 151
- 229930001995 Formic acid Natural products 0.000 title claims abstract description 150
- 239000011900 formic acid Substances 0.000 title claims abstract description 150
- 239000007789 gases Substances 0.000 claims abstract description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000003463 adsorbents Substances 0.000 claims abstract description 40
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound 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OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 34
- 235000015450 Tilia cordata Nutrition 0.000 claims abstract description 34
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 34
- 239000004571 lime Substances 0.000 claims abstract description 34
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 29
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 29
- 239000010457 zeolite Substances 0.000 claims abstract description 25
- 238000010306 acid treatment Methods 0.000 claims description 19
- 239000007793 ph indicators Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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[O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 25
- 235000011116 calcium hydroxide Nutrition 0.000 description 24
- 238000000034 methods Methods 0.000 description 12
- 230000000052 comparative effects Effects 0.000 description 9
- 229910052751 metals Inorganic materials 0.000 description 9
- 239000002184 metals Substances 0.000 description 9
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[H][H].O=C ZSKCOFJBFXSEDP-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular materials Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound 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[He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gases Substances 0.000 description 2
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- 239000000953 sodium hydroxide Substances 0.000 description 2
- 229910001856 sodium hydroxide Inorganic materials 0.000 description 2
- 229910000679 solders Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste materials Substances 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001614 zinc oxide Inorganic materials 0.000 description 2
- WPDXAMRGYMDTOV-UHFFFAOYSA-N 3-bromo-2-methylphenol Chemical compound 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CC1=C(O)C=CC=C1Br WPDXAMRGYMDTOV-UHFFFAOYSA-N 0.000 description 1
- 229930008671 Acetic acid Natural products 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butanoic acid Chemical compound 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- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound 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CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000001617 acetic acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052783 alkali metals Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metals Inorganic materials 0.000 description 1
- 239000007864 aqueous solutions Substances 0.000 description 1
- 239000006227 byproducts Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound 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[Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous materials Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reactions Methods 0.000 description 1
- 230000002939 deleterious Effects 0.000 description 1
- 238000010586 diagrams Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229910052736 halogens Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011948 hydrogen chloride Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000640 hydroxylating Effects 0.000 description 1
- 238000005805 hydroxylation reactions Methods 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound 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CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000004065 semiconductors Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solids Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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Abstract
Description
本発明は、ギ酸の蒸気を含むガスを、乾式処理により無害化する方法及び装置に関する。
ギ酸は、農業、繊維工業、有機合成化学、半導体デバイス製造業など、幅広い分野で使用されている。近年、真空リフロー半田付け装置において、半田表面の酸化物を還元するために、ギ酸を用いる手法が開発され、急速に発展しつつある。通常、真空リフロー半田付け装置の排気は、1体積%以上のギ酸を含む。しかしながら、ギ酸の蒸気は目や皮膚に対して有害であり、推奨される暴露許容濃度(TLV)は5体積ppmである。したがって、ギ酸の蒸気を含むガスは、大気に排出する前に、無害化処理される必要がある。さらに、ギ酸による配管の腐食の防止や、周辺環境の悪臭の防止には、排気中のギ酸濃度をさらに低くすること、例えば0.5体積ppm以下にすることが求められていた。
これまで、排気中のギ酸の蒸気の処理方法としては、バーナー中に流通させて燃焼除害する方法や、触媒存在下で加熱して熱分解処理する方法や、触媒を用いずに200℃以上に加熱して熱分解処理する方法(特許文献1)があるが、いずれも大型の装置が必要であり、小規模な事業者が真空リフロー半田付け装置を導入することの妨げとなっていた。
また、ギ酸の蒸気の処理方法として、ギ酸の蒸気を含む排ガスを、水やアルコールに接触させてギ酸を溶解させて湿式処理する方法もある(特許文献2)が、大型の装置と廃液処理が必要であり、さらに、水溶液中のギ酸濃度が90質量%を超えると劇物に該当するため、廃液の取り扱いに制限を受ける場合もあり、やはり小規模事業者には向いていない。
取り扱いが容易な酸性ガスの除害方法として、固体への吸着を利用する乾式処理方法が知られている。例えば、硫黄酸化物、塩化水素等の酸性ガスの乾式処理方法として、アルカリ金属やアルカリ土類金属の水酸化物が広く用いられており、コストと取り扱いの容易さから、水酸化カルシウムが主に用いられている(特許文献3)。ハロゲン系ガス及び酸性ガスを処理対象とする例としては、消石灰の造粒体からなる吸着剤(特許文献4)や、酸化性ガス及び酸性ガスを処理対象とするソーダライムとゼオライトと活性炭の混合物の造粒体からなる処理剤(特許文献5)等が挙げられる。特許文献5では、実施例と比較例においてギ酸の蒸気を処理しているがTLV以下にまでは処理していない。また、K2CO3を含有する活性炭を用いて、ガス中のギ酸蒸気の濃度を100ppmから10ppmまで処理している(特許文献6)。
乾式処理で使用する固体材料は、ガス中に含まれる酸性ガスを、物理吸着又は化学吸着により固定して、ガス中から除去する。物理吸着は、酸性ガスが固体材料にファンデルワールス力により吸着されている状態で、その結合は比較的弱く、温度や圧力の制御で可逆的に吸着・脱離が生じる。化学吸着は、酸性ガスが固体材料と化学反応にて吸着されている状態で、その結合は強固で、一旦吸着したガスを脱離することは困難である。
しかしながら、本発明者らが、様々な既存の処理剤を検討したところ、排気ガス中のギ酸の処理量が十分でない場合や、排気ガス中のギ酸濃度を0.5体積ppm以下に低減することが難しいという問題点があった。
特許文献3と4に記載のような、水酸化カルシウムのみを排気ガスの処理剤に用いた場合、濃度数体積%の高濃度のギ酸を含有するガスを流通させると、十分にギ酸を吸着せず、吸着材をすぐに破過してしまうという現象が見られた。
さらに、特許文献5に記載のような、活性炭とソーダライムを組み合わせた処理剤を用いた場合、高濃度のギ酸を含有するガスを流通させると、ある程度ギ酸を吸着することができたが、処理後の排気ガス中のギ酸濃度は、0.5体積ppmを超えてしまった。
本発明は、ギ酸の蒸気を含むガスを通しても、従来の処理剤に比べて大量にギ酸を処理できる上に、処理後のギ酸濃度を0.5体積ppm以下まで低減可能なギ酸の乾式処理方法を提供することを目的とする。
本発明者らは上記の課題を解決すべく鋭意研究を重ねた結果、ギ酸の蒸気を含むガスを、炭素質吸着剤と水酸化カルシウムを併用する処理剤で一次処理をした後、多孔質吸着剤を用いて二次処理をすることにより、処理剤の単位体積あたりの処理量を増やすことができ、さらに、ギ酸濃度を0.5体積ppm以下までギ酸を除去できることを見出し、本発明を完成させるに至った。
すなわち、本発明は、ギ酸を含むガスから、ギ酸を除去する処理方法であって、前記ガスに含まれるギ酸を、炭素質吸着剤と水酸化カルシウムを含む第一処理剤を用いて処理する第一処理工程と、前記第一処理工程後のガスを、さらに多孔質吸着剤を用いて処理する第二処理工程と、を有するギ酸の処理方法を提供する。
本発明により、ギ酸の蒸気を含むガスを通しても、従来の処理剤に比べて大量にギ酸を処理できる上に、ギ酸濃度を0.5体積ppm以下まで低減可能なギ酸の乾式処理方法を提供することができる。
以下、本発明の実施の形態を図に基づいて説明する。図1は、本発明に係るギ酸処理装置11を示す図である。ギ酸処理装置11は、ギ酸使用装置17からの排気ガスを処理する第一処理部13と、第一処理部13で処理されたガスをさらに処理する第二処理部15とを有する。第一処理部13と第二処理部15はそれぞれガス入口及びガス出口を有する処理剤充填容器からなる。
なお、ギ酸処理装置11が処理する排ガスに含まれるギ酸濃度は特に限定されないが、通常は少なくともTLVである5体積ppmを超えている。また、ギ酸処理装置11は、ギ酸濃度が1体積%以上のガスにも対処可能である。一方で、ギ酸処理装置11が処理する排ガスに含まれるギ酸濃度は、通常は10体積%以下と考えられる。ただし、本発明の方法によれば、上限は特に限定されず、実用的には20体積%程度でもよい。
ギ酸処理装置11が処理する排ガスは、100%のギ酸蒸気ではなく、所定濃度のギ酸を含むガスである。排ガスを構成するギ酸以外のガスとしては、空気だけでなく、窒素ガスやアルゴンガス、ネオンガス、ヘリウムガスなどの不活性ガスや、水素ガスや一酸化炭素ガスなどの還元性ガスや、それらが混合されたものが考えられる。
第一処理部13では、排気ガスが第一処理剤と接触し、排気ガス中のギ酸が第一処理剤により除去される。例えば、第一処理部13は、内部に第一処理剤が充填された管状反応器などである。なお、第一処理部13内にガスを均一にするような攪拌羽根や邪魔板が設けられていてもよい。
第一処理部と第二処理部は、特に加熱する必要はない。また、第一処理部と第二処理部では、導入される排気ガスの温度が0〜100℃であることが好ましく、通常は常温付近である。
第一処理剤は、炭素質吸着剤と水酸化カルシウムとを含む。炭素質吸着剤としては、多孔質な炭素材料であれば特に限定されないが、そのBET比表面積が500m2/g以上であることが好ましく、1000m2/g以上であることがより好ましく、1500m2/gであることがさらに好ましい。例えば、炭素質吸着剤としては、活性炭を用いることができる。なお、活性炭としては、金属成分を含む活性炭、いわゆる金属添着活性炭を用いることができ、例えば、酸化銅及び酸化亜鉛を添着させた活性炭を用いることができる。金属添着活性炭は、活性炭表面に金属又はその化合物が付着しており、活性炭に対する金属の濃度は、金属換算で1〜10質量%程度である。
第一処理剤は、水酸化カルシウムを含む材料として、ソーダライムを用いることが好ましい。ソーダライムは、ソーダ石灰とも呼ばれ、水酸化カルシウムを主成分とし、アルカリ金属水酸化物と水分を含む材料である。ソーダライムは、水酸化カルシウムを50質量%以上含むことが好ましく、70質量%以上含むことがより好ましい。ソーダライムとしては、粒子径100μm〜5mmで、比表面積1〜100m2/g程度の粉状または粒状のものを使用できる。
第一処理剤は、水酸化カルシウムと炭素質吸着剤の両方を含めば、形態は特に限定されず、水酸化カルシウムと炭素質吸着剤の混合品を用いることができる。第一処理剤に含まれる水酸化カルシウムと炭素質吸着剤の割合は、質量比で、水酸化カルシウム:炭素質吸着剤=1:0.1〜0.5であることが好ましく、1:0.2〜0.4であることがより好ましい。
第一処理工程では、水酸化カルシウムと炭素質吸着剤を併用することで、水酸化カルシウムと炭素質吸着剤をそれぞれ単独で用いるよりも、大量のギ酸を処理できる。水酸化カルシウムは、ギ酸と反応し、ギ酸カルシウムを生成することでギ酸を処理剤に固定することができるが、その反応速度が遅いため、通常の排気ガスの滞留時間では、一部の水酸化カルシウムしか有効に使用できなかった。さらに、炭素質吸着剤は、物理吸着によりガス状のギ酸を細孔に保持できるが、その単位体積あたりの吸着量は、ギ酸カルシウムとして固定できる水酸化カルシウムには及ばない。水酸化カルシウムと炭素質吸着剤を併用することで、まずは吸着速度の速い炭素質吸着剤がギ酸を吸着し、その後、炭素質吸着剤から徐々に放出されるギ酸を水酸化カルシウムが固定するため、大量のギ酸の吸着が可能となったと考えられる。
また、水酸化カルシウムは、ギ酸を化学吸着してギ酸カルシウムとして固定するため、使用後の処理剤を大気中においてもギ酸を放出せず、処理剤の交換作業中に使用後の処理剤からギ酸が漏出することがない。さらに、水酸化カルシウムは吸湿しても吸着能力が衰えないため、入口ガスに水分が含まれていても、環境中の水分を吸湿しても問題を生じない。
第二処理部15では、第一処理部13の出口ガスが多孔質吸着剤と接触し、出口ガス中のギ酸が多孔質吸着剤により除去されるようになっている。例えば、第二処理部15は、内部に多孔質吸着剤が充填された管状反応器などである。なお、第二処理部15内にガスの組成を均一にするような攪拌羽根や邪魔板が設けられていてもよい。
多孔質吸着剤は、ギ酸を物理吸着可能な、比表面積の高い多孔質材料であれば特に限定はされないが、炭素質吸着剤や、無機系吸着剤を用いることができ、具体的には、活性炭やゼオライト、シリカゲルを使用することができる。
多孔質吸着剤として使用できるゼオライト、シリカゲルとしては、そのBET比表面積が100m2/g以上であることが好ましく、200m2/g以上であることがより好ましく、300m2/g以上であることがさらに好ましい。例えば、ゼオライトとしては、A型、B型、X型、Y型などの各種の構造のゼオライトを用いることができる。なお、ゼオライトを使用する場合、ゼオライトにpH指示薬を添加してもよい。ギ酸の吸着に伴うpH指示薬の変色により、ゼオライトのpHを目視により確認でき、交換時期を確認することができる。
多孔質吸着剤として用いられる活性炭は、そのBET比表面積が500m2/g以上であることが好ましく、1000m2/g以上であることがより好ましく、1500m2/gであることがさらに好ましい。なお、活性炭としては、酸性ガスであるギ酸を吸着しやすいように、金属成分を添着させた活性炭、例えば、酸化銅及び酸化亜鉛を添着させた活性炭を用いることができる。金属添着活性炭は、活性炭表面に金属又はその化合物が付着しており、活性炭に対する金属の濃度は、金属換算で1〜10質量%程度である。
第二処理部15は、ギ酸の濃度が低濃度でも高速に吸着可能な物理吸着を利用してギ酸を処理するため、ギ酸を0.5体積ppm以下にまで低減することができる。また、第一処理部13の出口ガス中のギ酸濃度は、ppmレベルにまで低下しているため、第二処理部15でギ酸に由来した一酸化炭素が生成しても、非常に少ない量となり特に問題を生じない。また、第二処理部15の多孔質吸着剤は少量のギ酸を吸着すればよく、吸着能力を長期間にわたって維持することができる。
なお、第一処理部13で用いる第一処理剤と、第二処理部15で用いる多孔質吸着剤のいずれについても、その形状は特に限定されず、粉末状でも粒状でも造粒されたペレット状でもよい。
また、ギ酸処理装置11は、ギ酸の蒸気を含むガスを乾式で処理するため、燃焼除害や触媒加熱除害で必要な熱源が不要であり、省エネルギーであるとともに、装置を小型化することが可能である。また、使用している処理剤は、一般的に使用されている安価な材料であり、高価な貴金属系触媒等を使用する必要がなく、ギ酸処理装置11が安価であるし、ランニングコストも安価である。
なお、第一処理部13と第二処理部15は、図1では装置内に一つしか設けられていないが、それぞれ複数を設けてもよい。複数ある場合、複数に同時にガスを流通してもよく、一方を交換する場合にも他方にガスを流通させることで、処理を中断しないで済む。
ギ酸使用装置17は、ギ酸を何らかの処理で使用し、排気中にギ酸を含む装置であれば特に限定されないが、半田表面の酸化物を還元するためのガスとしてギ酸を用いる真空リフロー半田付け装置であることが好ましい。真空リフロー半田付け装置で使用するガスとしては、窒素ガスやアルゴンガス、ネオンガス、ヘリウムガスなどの不活性ガスや、水素ガスや一酸化炭素ガスなどの還元性ガスで希釈されたギ酸を使用することができる。さらに、ガス中にはギ酸以外に、酢酸、プロピオン酸、酪酸などのカルボン酸、メタノール、エタノールなどのアルコールを含んでもよい。
ギ酸処理装置11は、ギ酸使用装置17の排ガス以外にも、副生物などとして目的外に生成したギ酸が混入してしまったガスからギ酸を除去することや、何らかの目的に使用するガスにギ酸が混入してしまった場合にそのガスからギ酸を除去することにも使用できる。
以下、参考例と実施例により本発明をさらに詳細に説明するが、本発明は以下の実施例によってその範囲を限定されるものではない。
本発明者らは、まず一般的な処理剤のギ酸吸着能を調べるため、参考例1〜11を行った。
[参考例1〜6]
外径1インチのステンレス鋼管に、充填高200mmで、処理剤を充填した。そこに、窒素ガスで希釈したギ酸濃度5体積%の処理ガスを1L/minの速度で流通させた。出口ガスのギ酸濃度を監視し、5体積ppmを超えた時点で処理を終了し、処理開始から処理終了までの処理時間を測定し、ギ酸の処理量を計算した。その結果を表1に示す。
ゼオライトA:X型、カチオン=Ca、形状=1.5mmΦ、ペレット状
吸湿ゼオライトA:水分を25質量%添加したゼオライトA
ソーダライム:水酸化カルシウム79質量%、水酸化カリウム2質量%、水酸化ナトリウム質量1%、その他水分)
乾燥ソーダライム:前述のソーダライムを乾燥し、水分量を1質量%以下にしたもの
活性炭A:粒状活性炭、破砕状、粒径=8〜24メッシュ(2.36mm〜0.7mm)
活性炭入りソーダライム:粉末活性炭を20質量%含むソーダライム、ペレット状
処理剤にゼオライトを用いた参考例1では、ある程度のギ酸の処理能力を発揮した。また、出口ガスの一酸化炭素は、暴露許容濃度の25体積ppm未満であった。しかし、真空リフロー半田付け装置の排ガスに水分が含まれる場合や、大気中の水分を吸湿することを想定し、吸湿ゼオライトAを用いた参考例2では、ほとんどギ酸を処理できなかった。以上のことから、ゼオライト単独をギ酸処理剤として用いる場合は、水分に弱く、真空リフロー半田付け装置の排気ガスを処理するという用途には向いていないと考えられる。
ソーダライムを用いた参考例3では、期待したほどのギ酸の処理能力が得られなかった。処理後の処理剤を分析したところ、ギ酸カルシウムが生成していたが、水酸化カルシウムも残存していた。一方で、ソーダライムを乾燥して用いた参考例4では、ほとんどギ酸を処理できず、ソーダライムは乾燥に弱いことが分かった。ガスを流通させる場合に、ソーダライム中の水分が蒸発してソーダライムが乾燥してしまう場合も考えられるため、ソーダライム単独を用いる場合は、乾燥により処理ができなくなってしまう場合も考えられる。
活性炭を用いた参考例5では、ゼオライトやソーダライムに比べても多量のギ酸を処理できたが、出口ガスに25体積ppm以上の一酸化炭素が検出された。これは、活性炭を構成するカーボンによるギ酸の還元や、活性炭中に微量に含まれる金属不純物の触媒効果によりギ酸の分解(例えば、HCOOH→CO+H2Oなど)により、一酸化炭素が生成したと考えられる。また、活性炭は物理吸着によりギ酸を吸着しているため、環境の変化によりギ酸を放出する恐れがあり、気温の変化や処理剤の交換時にギ酸を漏出してしまう恐れがあるという問題点がある。したがって、第一処理部として活性炭を使用すると、第二処理部にて一酸化炭素の処理も行う必要がある上に、活性炭が比較的早く破過してしまう為に頻繁に交換する必要が生じてしまう。
活性炭入りソーダライムを用いた参考例6では、同じ体積の参考例1〜5に比べて、大量のギ酸を処理できた。しかしながら、出口ガスに0.5〜4体積ppmのギ酸が残存し、ギ酸濃度0.5体積ppm未満の出口ガスを得ることが難しかった。更なるギ酸濃度の低減を目指すため、二段目の処理方法を模索することとした。
[参考例7〜11]
外径1/2インチのステンレス鋼管に、充填高40mmで、処理剤を入れた。そこに、窒素ガスで希釈したギ酸濃度0.2体積%の処理ガスを10L/minの速度で流通させた。出口ガスのギ酸濃度を監視し、5体積ppmを超えた時点で処理を終了し、処理開始から処理終了までの処理時間を測定し、ギ酸の処理量を計算した。その結果を表2に示す。
ゼオライトA:X型、カチオン=Ca、形状=1.5mmΦ、ペレット状
ゼオライトB:X型、カチオン=Na、形状=1.6mmΦ、ペレット状
ゼオライトC:ゼオライトBに対して、pH指示薬(ブロモクレゾールグリーン)を加えたもの。
活性炭A:粒状活性炭、破砕状、粒径=8〜24メッシュ(2.36mm〜0.7mm)
吸湿活性炭:上記活性炭Aに水分を20質量%添加したもの。
参考例7〜11においては、第一処理部の出口ガスを想定し、ギ酸濃度0.2体積%のガスを導入したため、各ゼオライト、各活性炭のいずれもある程度の吸着能力を発揮した。また、それぞれの出口ガスは、初期にはいずれも0.5体積ppm以下であった。また、参考例9においては、pH指示薬を添加したが、特に問題なくギ酸の処理が可能で、出口ガスのギ酸濃度が5体積ppmを超える際にはゼオライトが既に変色しており、pH変化を目視で確認可能であった。
[実施例1〜3、比較例1〜4]
第一処理部と第二処理部に表3に記載の処理剤を用いて、ギ酸の処理を行った。
第一処理部として、外径1インチのステンレス鋼管に、充填高200mmで、処理剤を入れた。また、第二処理部として、外径1/2インチのステンレス鋼管に、充填高40mmで、処理剤を入れた。第一処理部には、窒素ガスで希釈したギ酸濃度5体積%の処理ガスを1L/minの速度で流通させた。第一処理部の出口ガスを第二処理部に流通させ、第二処理部の出口ガスのギ酸濃度を監視し、0.5体積ppmを超えた時点の処理時間を測定し、さらに5体積ppmを超えた時点で処理を終了し、処理開始から処理終了までの処理時間からギ酸の処理量を計算した。その結果を表3に示す。
活性炭入ソーダライム:粉末活性炭を20質量%含むソーダライム、ペレット状
乾燥活性炭入ソーダライム:上記活性炭入ソーダライムを乾燥し、水分量を1質量%以下にしたもの
活性炭A:粒状活性炭、破砕状、粒径=8〜24メッシュ(2.36mm〜0.7mm)
ゼオライトA:X型、カチオン=Ca、形状=1.5mmΦ、ペレット状
ソーダライム:水酸化カルシウム79質量%、水酸化カリウム2質量%、水酸化ナトリウム1質量%、その他水分)
[実施例4]
処理ガスとして、水素ガスで希釈したギ酸濃度5体積%のガスを用いた以外は、実施例1と同様にして、ギ酸の処理を行った。
表3に示すとおり、実施例1〜3では、活性炭入りソーダライムによる第一処理とゼオライト又は活性炭による第二処理を組み合わせることで、第一処理及び第二処理とも活性炭入りソーダライムのみを用いた比較例1に比べて、同体積でも5体積ppm以下処理可能時間を延ばすことができ、大量にギ酸を処理できるとともに、長期間にわたってギ酸濃度0.5体積ppm以下の清浄な出口ガスを得ることができた。
また、比較例2と4では、第一処理及び第二処理とも物理吸着を利用する活性炭やゼオライトで処理するため、0.5体積ppm以下にまで処理可能であったが、同じ体積の処理剤を用いたにもかかわらず、実施例1〜3に比べると、短期間で出口ガスのギ酸濃度が0.5体積ppmを超えたうえに、5体積ppm以下処理可能時間も短く、処理可能量が少なかった。また、比較例2では、高濃度のギ酸が活性炭と接触したことによる一酸化炭素の生成が確認された。
また、比較例1と比較例3では、第一処理及び第二処理とも化学吸着を利用する活性炭入ソーダライムとソーダライムをそれぞれ利用するため、0.5体積ppm以下の低濃度にまでギ酸を処理できなかったため、0.5体積ppm以下処理可能時間は0分となった。
そのため、活性炭による第一処理と活性炭入りソーダライムによる第二処理を組み合わせた比較例5では、実施例1〜3とは異なり、短期間で出口ガスのギ酸濃度が0.5体積ppmを超えたうえに、5体積ppm以下処理可能時間も短く、処理可能量が少なかった。また、高濃度のギ酸が活性炭と接触したことによる一酸化炭素の生成が確認された。
なお、実施例・比較例で使用した活性炭入りソーダライムは粉末活性炭を含むが、活性炭の割合が20質量%と少ないため、活性炭による物理吸着よりも、化学吸着が支配的であったため、比較例1では0.5体積ppm以下の低濃度にまでギ酸を処理できなかったと考えられる。
ギ酸の希釈ガスが水素である実施例4は、希釈ガスが窒素である実施例1と同等のギ酸処理を行うことができた。
11 ギ酸処理装置
13 第一処理部
15 第二処理部
17 ギ酸使用装置
Claims (8)
- ギ酸を含むガスから、ギ酸を除去する処理方法であって、
前記ガスに含まれるギ酸を、炭素質吸着剤と水酸化カルシウムを含む第一処理剤を用いて処理する第一処理工程と、
前記第一処理工程後のガスを、さらに多孔質吸着剤を用いて処理する第二処理工程と、
を有するギ酸の処理方法。 - 前記第一処理剤が、ソーダライムを含むことを特徴とする請求項1に記載のギ酸の処理方法。
- 前記第一処理剤に含まれる前記炭素質吸着剤が、活性炭又は金属添着活性炭であることを特徴とする請求項1に記載のギ酸の処理方法。
- 前記第一処理剤が、活性炭とソーダライムを含むことを特徴とする請求項1に記載のギ酸の処理方法。
- 前記第一処理剤に含まれる水酸化カルシウムと炭素質吸着剤の割合は、質量比で、水酸化カルシウム:炭素質吸着剤=1:0.1〜0.5であることを特徴とする請求項1〜4に記載のギ酸の処理方法。
- 前記第二処理工程で用いられる前記多孔質吸着剤が、活性炭、金属添着活性炭又はゼオライトであることを特徴とする請求項1〜5のいずれか1項に記載のギ酸の処理方法。
- 前記第二処理工程で用いられる前記多孔質吸着剤が、pH指示薬を含有するゼオライトであることを特徴とする請求項1〜5のいずれか1項に記載のギ酸の処理方法。
- ギ酸使用装置からギ酸を含む排気が供給され、炭素質吸着剤と水酸化カルシウムを含む第一処理剤を有する第一処理部と、
前記第一処理部の出口ガスが供給され、多孔質吸着剤を有する第二処理部と、
を有する排気中のギ酸の処理装置。
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