JP2017500197A - ポリオール複合溶液でガス中のSOxを除去する方法 - Google Patents
ポリオール複合溶液でガス中のSOxを除去する方法 Download PDFInfo
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- JP2017500197A JP2017500197A JP2016539118A JP2016539118A JP2017500197A JP 2017500197 A JP2017500197 A JP 2017500197A JP 2016539118 A JP2016539118 A JP 2016539118A JP 2016539118 A JP2016539118 A JP 2016539118A JP 2017500197 A JP2017500197 A JP 2017500197A
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- Prior art keywords
- gas
- acid
- organic
- polyol
- sox
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- -1 organic acid salt Chemical class 0.000 claims abstract description 39
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- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
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- 230000008569 process Effects 0.000 claims description 47
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
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- URKBBEIOEBOBIY-UHFFFAOYSA-N pentane-1,1,1,2-tetrol Chemical compound CCCC(O)C(O)(O)O URKBBEIOEBOBIY-UHFFFAOYSA-N 0.000 claims description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
Description
本発明は、煙道ガス、硫黄含有廃ガス及び/又は工業用原料ガスの浄化方法に関し、具体的に、煙道ガス、SOx含有廃ガス及び/又は工業用原料ガス中のSOx(x=2および/または3)を除去する方法に関する。
工業の迅速な発展によって、煙道ガス、硫黄含有工業用原料ガスおよびその他の廃ガスの消耗や排出量が日々増え続けている。硫黄含有廃ガスの排出は、深刻な環境汚染、例えば、酸性雨の形成、建築物の酸腐食、呼吸道疾患および皮膚病などを引き起こし、人々の健康に直接害を及ぼしている。数年来、世界中の科学者は、煙道ガス、硫黄含有工業用原料ガスおよびその他の廃ガスの脱硫技術に対して多くの研究を行い、たくさんの研究資料を蓄積してきた。環境意識の高まりにつれて、煙道ガス、硫黄含有工業用原料ガスおよびその他の廃ガスの脱硫問題が重視されつつある。しかしながら、今まで、煙道ガス、硫黄含有工業用原料ガスおよびその他の廃ガスの脱硫技術は、まだ飛躍的な進歩を遂げていない。煙道ガス、硫黄含有工業用原料ガスおよびその他の廃ガスの脱硫問題は、今でもチャレンジングな課題である。
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発明内容
本発明者のこの前の特許「ポリエチレングリコールでガス中のSOxを除去する方法(中国特許番号ZL200910009058.1)」及び「エチレングリコールで煙道ガス中のSOxを除去する方法(中国特許番号ZL200710110446.X」における上記不足を解決し、溶液の沸点を向上させ、溶剤の損失を減少させると共に溶液の脱硫能力を向上させ、スルフィン酸エステルおよびスルホン酸エステル系物質の生成を避ける又は大幅に減少させるために、本発明は、ポリオールと有機酸及び/または有機酸塩からなる溶液を採用してガス中のSOXを吸収している。その中、前記ポリオールとは、エチレングリコールとポリエチレングリコール以外の、同一の有機分子において同時に2個または2個以上のヒドロキシ基を有する有機化合物、例えば、プロパンジオール、プロパントリオール、ブタンジオール、ブタントリオール、イソブタンジオール、イソブタントリオール、ペンタンジオール、ペンタントリオール、ペンタンテトラオール、イソペンタンジオール、イソペンタントリオール、イソペンタンテトラオール、ポリプロパノール、ポリブタノール等を指す。前記ポリオールは、その沸点が高いが、例えば、プロパントリオールその自身の沸点が290℃と高く、さらに、ポリオールは有機酸及び/または有機酸塩と安定した水素結合会合物を形成すると共に、安定したポリオールエステール系物質を形成して、ポリオール複合溶液の安定性を顕著に増加でき、ポリオール複合溶液の耐アルカリ破壊能力、耐酸破壊能力を顕著に向上させるだけではなく、さらに、ポリオール複合溶液の沸点を顕著に向上できる。
本発明のポリオール複合溶液脱硫法において、まず、ポリオール複合溶液を用いてガス中のSOx(x=2および/または3)を吸収し、そして、SOxを吸収したポリオール複合溶液を、加熱法、真空法、ストリッピング法、超音波法、マイクロ波法および放射法中の1種または複数種の方法で再生して、再生後のポリオール複合溶液を循環利用する。また、再生後のポリオール複合溶液中の水の含有量が多くて脱硫効果に影響を及ぼす場合、ポリオール複合溶液中の一部の水を除去する必要がある。水の除去方法として、加熱精留法、吸水剤吸収法があり、これらの方法を併用してもよく、そして一部の水除去後のポリオール複合溶液を循環利用する。
〔図1〕図1は、脱硫吸収プロセスの概略図である。
〔図2〕図2は、脱硫液の加熱再生方式の概略図である。
〔図3〕図3は、脱硫液の真空再生方式の概略図である。
〔図4〕図4は、脱硫液のストリッピング再生方式の概略図である。
〔図5〕図5は、脱硫液の超音波および/またはマイクロ波および/または放射再生方式の概略図である。
〔図6〕図6は、小型の脱硫吸収装置の構造概略図である。
〔図7〕図7は、小型の加熱ストリッピング(stripping)再生装置の構造概略図である。
以下、具体的な実施形態を併せて、本発明のポリオール複合溶液脱硫法を説明する。本実施形態は、本発明をよりよく説明するためのものであり、本発明の特許請求の範囲を制限するものと解してはならない。
Claims (10)
- ポリオールと、有機酸及び/または有機酸塩との混合液を含むポリオール複合溶液をSOx含有ガスと接触させることで、ガス中のSOx(ただし、x=2及び/又は3)を吸収させる、ガス中のSOxを除去する方法であって、
前記ポリオールは、エチレングリコール及びポリエチレングリコール以外の、同一の有機分子において同時に2個または2個以上のヒドロキシ基を含有する有機化合物である、ガス中のSOxを除去する方法。 - 前記ポリオールは、プロパンジオール、プロパントリオール、ブタンジオール、ブタントリオール、イソブタンジオール、イソブタントリオール、ペンタンジオール、ペンタントリオール、ペンタンテトラオール、イソペンタンジオール、イソペンタントリオール、イソペンタンテトラオール、ポリプロパノール及びポリブタノールからなる群より選択される一種または多種であることを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
- 前記ポリオール複合溶液中に、さらに、エチレングリコール、またはポリエチレングリコール、またはエチレングリコールとポリエチレングリコールとの混合物を、適量に含有し、該エチレングリコール、またはポリエチレングリコール、またはエチレングリコールとポリエチレングリコールとの混合物の、ポリオール複合溶液中の質量含量が30%未満であることを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
- 前記有機酸は、有機モノカルボン酸と、有機ポリカルボン酸とを含み、前記有機酸塩は、有機モノカルボン酸塩と有機ポリカルボン酸塩とを含むことを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
- 前記有機モノカルボン酸は、ぎ酸、酢酸、酪酸及び各種のアミノ酸からなる群より選択される一種または多種であり、前記有機ポリカルボン酸は、シュウ酸、マロン酸、コハク酸、アミノシュウ酸、ニトリロ三酢酸、EDTA、タンニン酸、ポリ没食子酸及びクエン酸からなる群より選択される一種または多種であり、前記有機モノカルボン酸塩は、前記有機モノカルボン酸のカルボキシル基がアンモニウムイオン、ナトリウムイオン、カリウムイオン、マグネシウムイオン、カルシウムイオン及び/または遷移金属イオンと結合してなるカルボン酸塩類からなる群より選択される一種または多種であり、前記有機ポリカルボン酸塩は、前記有機ポリカルボン酸の少なくとも一個のカルボキシル基がアンモニウムイオン、ナトリウムイオン、カリウムイオン、マグネシウムイオン、カルシウムイオン及び/または遷移金属イオンと結合してなるカルボン酸塩類からなる群より選択される一種または多種であることを特徴とする、請求項4に記載のガス中のSOxを除去する方法。
- 前記ポリオール複合溶液中の、ポリオールと有機酸及び/または有機酸塩との合計質量含量が50%以上であり、水の質量含量が50%未満であり、且つ、有機酸及び/または有機酸塩の、ポリオール複合溶液中の質量含量が30%未満であることを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
- 前記ポリオール複合溶液は、所定量の添加剤を含み、該添加剤が、有機アミン類、アルコールアミン類、アミド類、スルホン類、スルホキシド類及び金属有機化合物系物質からなる群より選択される一種または多種であり、前記添加剤の、前記ポリオール複合溶液中の質量含量が10%未満であることを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
- 前記ポリオール複合溶液が、常圧又は加圧の条件下でガス中のSOxを吸収し、吸収温度が−20〜80℃であることを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
- SOxを吸収したポリオール複合溶液を、加熱法、真空法、ストリッピング法、超音波法、マイクロ波法および放射法中の1種又は複数種の方法で再生し、再生温度が0〜300℃であり、再生過程で二酸化硫黄および/又は三酸化硫黄を放出し、再生後のポリオール複合溶液を循環利用することを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
- 前記ガスが、煙道ガス、SOx含有廃ガス及び/又は工業用原料ガスであることを特徴とする、請求項1に記載のガス中のSOxを除去する方法。
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