JP4030439B2 - Method and apparatus for concentrating substances having higher boiling point than water in exhaust gas - Google Patents

Method and apparatus for concentrating substances having higher boiling point than water in exhaust gas Download PDF

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JP4030439B2
JP4030439B2 JP2003020725A JP2003020725A JP4030439B2 JP 4030439 B2 JP4030439 B2 JP 4030439B2 JP 2003020725 A JP2003020725 A JP 2003020725A JP 2003020725 A JP2003020725 A JP 2003020725A JP 4030439 B2 JP4030439 B2 JP 4030439B2
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water
tower
boiling point
exhaust gas
hydrophilic
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JP2004230265A (en
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泰人 川瀬
基良 李
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Nippon Refine Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon

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Description

【０００１】
【発明の属する技術分野】
本発明は、排ガス中に含有されている水より高沸点で、水と共沸しない親水性、揮発性化学物質を水との沸点の差を利用して濃縮、回収すると共に排ガスを浄化する方法および装置に関する。
【０００２】
【従来の技術】
従来、水より沸点の高い水溶性溶剤を含有する排ガスを浄化処理するには、吸収塔の下部から水溶性溶剤を含有する排ガスを吹きこみ、吸収塔の上部から多量の水を流して前記排ガスを洗浄していた。このような洗浄方法では、洗浄に多量の水を必要とするうえ、排水中に含まれる溶剤の濃度が極めて低いので、溶剤回収にコストがかかるため、実質的に溶剤回収は不可能であり、しかも廃水処理が必要になるという問題点があった。
【０００３】
もう１つの従来技術としては、ゼオライトなどの吸着剤を充填した横向き配置のドラムを回転させながら、室温程度に冷却された前記排ガスを通し、通過ガスの一部はそのまま大気中に放出し、他の一部は加熱（吸着剤に吸着した成分を追い出すため）した後再び前記ゼオライトなどの吸着剤を充填した横向き配置のドラムに通し、吸着剤に吸着している溶剤を脱着し、脱着した溶剤を高濃度で含む処理ガスは再び冷却して溶剤を回収していた。この方法も排ガスを一度冷却し、吸着処理後加熱し、溶剤回収のため再び冷却するという操作を必要とするため、エネルギー効率が極めて悪い。
【０００４】
例えば、リチウム電極の乾燥工程から排出される排ガス中に含まれるＮ−メチル−２−ピロリドン（ＮＭＰ）を除去するためには、従来吸着法が用いられていたが、水分が存在するとＮ−メチル−２−ピロリドンの吸着効率が著しく低下するという事情から、前記乾燥工程から排出される高温の排ガスを冷却する工程が必要であり、吸着剤にＮ−メチル−２−ピロリドンを吸着させた後には、吸着剤からＮ−メチル−２−ピロリドンをパージするため、今度は反対に加熱するという操作が必要であった。このような従来工程は図３に示す。
このように従来法によれば、冷却工程、吸着工程、脱着工程という三工程が必要であり、かつかなりの温度を持つ排ガスを冷却した後、再び加熱するため大きなエネルギー損失を伴うという問題を抱えていた。
【０００５】
【発明が解決しようとする課題】
本発明の第１の目的は、排ガス中に含まれている水より高沸点で、水と共沸しない親水性、揮発性化学物質、例えば水溶性溶剤を水蒸気と置換することにより効率良く回収するとともに、排ガスを清浄化する方法および装置を提供する点にある。
本発明の第２の目的は、通常、リチウムイオン電池電極製造工程等より１００℃〜１２０℃で排出される高温の排ガスの熱量を利用して、外部より導入される補給水を蒸発させることにより、排ガス中に含まれる水より沸点が高く水溶性の揮発性化学物質を凝縮させる、即ち、排ガス中の成分を水と置換する、ことにより効率よく回収するとともに、低温の補給水による吸収効果を付加することにより排ガスを清浄化する方法および装置を提供する点にある。
【０００６】
本発明の第１は、トレイ上に存在する水の中を通らなければガスが上部に抜けられない構造のトレイを多段に設けてなる段塔または親水性充填物を充填した充填塔の下部から、水より高沸点の物質を含む排ガスを導入し、一方、塔上部からは水を供給し、塔下部では排ガスと水との気液平衡関係により前記水より高沸点の物質を濃縮するとともに、塔上部では残存する排ガス中の前記物質をさらに水中に移行させることを特徴とする排ガス中の「水より高沸点で、水と共沸しない親水性、揮発性化学物質」を濃縮する方法であって、塔上部から供給する水の量は、塔下部の濃度情報に基づき制御し、塔下部から回収する水より高沸点で、水と共沸しない親水性、揮発性化学物質の濃度は２０〜１００重量％になるように制御するものである排ガス中の水より高沸点で、水と共沸しない親水性、揮発性化学物質を濃縮する方法に関する。
本発明の第２は、前記水より高沸点で、水と共沸しない親水性、揮発性化学物質が、ＮＭＰ（Ｎ−メチルピロリドン）、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）、ＤＭＡＣ（Ｎ，Ｎ−ジメチルアセトアミド）、ＤＭＳＯ（ジメチルスルホキシド）、ＥＧ（エチレングリコール）、ＤＥＧ（ジエチレングリコール）、ＴＥＧ（トリエチレングリコール）、ＰＧＭＥ（プロピレングリコールモノエチルエーテル）、ＰＧ（プロピレングリコール）、１，４−ＢＤ（１，４−ブタンジオール）、ＭＥＡ（モノエタノールアミン）およびＤＧＭＥ（ジエチレングリコールモノメチルエーテル）よりなる群から選ばれた溶剤類である請求項１記載の排ガス中の水より高沸点で、水と共沸しない親水性、揮発性化学物質を濃縮する方法に関する。
本発明の第３は、
（１） トレイ上に存在する水の中を通らなければガスが上部に抜けられない構造の
トレイを多段に設けてなる段塔または親水性充填物を充填した充填塔、
（２） 前記多段トレイの上方であって前記段塔内に設けられた給水手段または充填層
の上方であって前記充填塔内に設けられた給水手段、
（３） 段塔の上部または充填層の上部に設けられた処理ガス放出口、
（４） 段塔の下部または充填層の下部に設けられた液状物排出口、
（５） 液状物排出口からパイプを通して連結された水より高沸点で、水と共沸しない
親水性、揮発性化学物質を含む液状物溜り、
（６） 段塔内または充填塔内に設けられた水より高沸点で、水と共沸しない親水性、
揮発性化学物質の系中濃度を検知するための測定手段、
（７） 前記測定手段からの情報により前記給水手段からの給水量を前記揮発性化学物
質の濃度が２０〜１００重量％になるように制御する手段、
よりなることを特徴とする排ガス中の「水より高沸点で、水と共沸しない親水性、揮発性化学物質」に対する濃縮装置に関する。
【０００７】
本発明は、通常相当高い温度（例えば８０〜１２０℃）を有していることが多い排ガスの熱量を有効利用し、段塔内または充填塔内に排ガスを通過させるという一工程で、排ガス中に含まれる水より沸点が高い物質の回収と排ガスの処理を同時に達成するという極めて効率的な方法と装置である。
本発明は、とくに、トレイ上に存在する水の中を通らなければガスが上部に抜けられない構造のトレイを多段に設けてなる段塔または親水性充填物を充填した充填塔の下部から、リチウムイオン電池電極製造工程より排出されるＮ−メチルピロリドンを含有する１００〜１２０℃の高温排ガスを導入し、一方、塔上部からは水を供給し、塔下部では排ガスの熱量を利用して供給された水を蒸発させ、反対に排ガス中に含まれる水より沸点が高く、水溶性のＮ−メチルピロリドンを凝縮させて塔下部に落し、塔上部では残存する排ガス中の前記Ｎ−メチルピロリドンをさらに水中に移行させることにより、リチウムイオン電池電極製造工場の排ガスを浄化するとともに、Ｎ−メチルピロリドンを回収する方法や装置として極めて好適である。
【０００８】
前記補給される水の量は、排ガス処理後に段塔上部から放出される処理済ガスに含まれて系から出てゆく水の量（Ｂ）と水より沸点の高い揮発性化学物質の凝縮物と共に塔下部より出てゆく水の量（Ｃ）とを補う量（Ａ）でよい。いいかえれば
Ａ≒Ｂ＋Ｃ
でよいから、従来技術における水洗による排ガス処理法に較べると水の使用量は桁違いに少なく、この点だけをみても、省資源を達成していると共に廃水処理を必要とする排水が実質的に発生しないという点も大きなメリットである。
【０００９】
塔頂部の温度は、外気温度より高いものとする。飽和含水量は温度が高い方が大きくなるから、段塔内のガス中の水分は簡単にいつも飽和点を下回っていることにより、補給水を加えても、Ｘａｃ≦Ｘｓを満たす条件をつくりだすことができる。なお、Ｘａｃは計算含水率であり、Ｘｓはガス飽和含水率である。補給水の温度は、吸収効率上は低い方がよいが、低すぎると塔内の流下水量が不足するだけでなく、冷却のためのエネルギーが必要となる。尚、外気は通常飽和ではなくて、湿度で表される飽和に達しない含水率で存在するので補給水の量は飽和の状態より多くなる。
【００１０】
本発明の水より高沸点の物質としては、揮発性化学物質を挙げることができる。
【００１１】
水より高沸点の揮発性化学物質としては、とくに水より沸点の高い水溶性溶剤が代表的なものである。
【００１２】
このような溶剤類としては、ＮＭＰ（Ｎ−メチルピロリドン、ＢＰ：１９７℃）、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド、ＢＰ：１５３℃）、ＤＭＡＣ（Ｎ，Ｎ−ジメチルアセトアミド、ＢＰ：１６５℃）、ＤＭＳＯ（ジメチルスルホキシド、ＢＰ：１８９℃）、ＥＧ（エチレングリコール、ＢＰ：１９７℃）、ＤＥＧ（ジエチレングリコール、ＢＰ：２４５℃）、ＴＥＧ（トリエチレングリコール、ＢＰ：２７８℃）、ＰＧＭＥ（プロピレングリコールモノエチルエーテル）、ＰＧ（プロピレングリコール、ＢＰ：１８８℃）、１，４−ＢＤ（１，４−ブタンジオール、ＢＰ：２３５℃）、ＭＥＡ（モノエタノールアミン、ＢＰ：１７０．５℃）およびＤＧＭＥ（ジエチレングリコールモノメチルエーテル）など水と共沸しない性質のものが好適である。
【００１３】
前記トレイ内に存在する水の中を通らなければガスが上部に抜けられない構造のトレイとしては、最も古くから用いられているバルブキャップトレイ（泡鐘板）があり、これ以外にはその後開発されたシーブトレイ（多孔板）などを挙げることができる。安定性の面からはバルブキャップトレイの方がよいが、コスト面からはシーブトレイの方がよい。
【００１４】
前記親水性充填物を充填した充填塔における親水性充填物は、規則充填物の形であっても不規則充填物の形であってもよいが、圧力損失のことを考えると規則充填物の方が好ましい。これらの充填物は親水性であり表面積の大きいもの、たとえば親水性の材質で作られた多孔質物、具体的には多孔質セラミックス、多孔質カーボンなどを挙げることができる。
【００１５】
本発明は、とくにリチウムイオン電池の製造工場において、Ｎ−メチル−２−ピロリドン（ＮＭＰ）溶剤を除去するための乾燥工程から排出される排ガスの処理に好適に利用できる。図１に示すように、Ｎ−メチル−２−ピロリドン（ＮＭＰ）溶剤を除去するためには、工場外から通常空気を取り込み、これを濾過した後、加熱した空気を送風機により乾燥工程に送風する。
通常の工場外からの取り込み空気は
外気温度 ｔ
流量 Ｖ Ｎｍ３／ｍｉｎ
含水率 Ｘａ ｋｇ／ｍ３
水分量 Ｖ・〔（２７３＋ｔ）／２７３〕・Ｘａ ｋｇ／ｍｉｎ
である。リチウムイオン電池製造工場におけるＮ−メチル−２−ピロリドン（ＮＭＰ）溶剤を除去するための乾燥工程から排出される排ガスは
排ガス温度 ｔ１＝１００〜１２０℃
ＮＭＰ含有量 Ｃｎ＝０．０００５〜０．０１ ｋｇ／Ｎｍ３
（１１３〜２２６０ｐｐｍ，ｖｏｌ．／ｖｏｌ．）
ＮＭＰ流量 ＶＣｎ ｋｇ／ｍｉｎ
排ガスの流量 Ｖ Ｎｍ３／ｍｉｎ
水分量 Ｖ・〔（２７３＋ｔ）／２７３〕・Ｘａ ｋｇ／ｍｉｎ
の条件で段塔（水置換塔）の下部から吹き込まれる。水置換塔内に多段に設けられたバルブキャップトレイやシーブトレイなどの最上段から、通常常温たとえばｔ３℃の補給水をＭ ｋｇ／ｍｉｎの流量で供給する。水置換塔上部から放出される処理済ガス（ガス温度ｔ２）は、ＲをＮＭＰなどの揮発性化学物質の回収率（重量分率）として、
放出量 Ｖ Ｎｍ３／ｍｉｎ
計算含水量 Ｖ・〔（２７３＋１５）／２７３〕・Ｘａ＋
〔Ｍ−ＶＣｎＲ（１／Ｘｎ−１）〕 ｋｇ／ｍｉｎ
計算含水率 Ｘａｃ＝｛〔（２７３＋１５）／２７３〕・Ｘａ＋
〔Ｍ−ＶＣｎＲ（１／Ｘｎ−１）〕／Ｖ｝・
〔２７３／（２７３＋ｔ ２ ）〕 ｋｇ／ｍ３
ガス温度ｔ２の時、ガス飽和含水率：Ｘｓ
制御条件としては、Ｘａｃ≦Ｘｓの時
本装置は正常に運転可能である。
一方、水置換塔下部からは水を含有するＮ−メチル−２−ピロリドン（液温ｔ４）が回収される。
【００１６】
【実施例】
以下に実施例を挙げて本発明を説明するが、本発明はこれにより何等限定されるものではない。実施例中の％は指示がないかぎり重量％である。
【００１７】
実施例１
図１に示すリチウムイオン電池のＮ−メチル−２−ピロリドン（ＮＭＰ）溶剤を除去するための乾燥工程における取り込み空気は、
外気温度 ｔ＝１５℃
流量 Ｖ＝４ Ｎｍ３／ｍｉｎ
含水率 Ｘａ＝０．０１２８ ｋｇ／ｍ３（飽和状態と仮定する）
水分量 Ｖ・〔（２７３＋１５）／２７３〕・Ｘａ＝０．０５４ ｋｇ／ｍｉｎであった。リチウムイオン電池製造工場におけるＮ−メチル−２−ピロリドン（ＮＭＰ）溶剤を除去するための乾燥工程から排出される排ガスは
排ガス温度 ｔ１＝１２０℃
ＮＭＰ含有量 Ｃｎ＝０．００３１ ｋｇ／Ｎｍ３
（７００ｐｐｍ，ｖｏｌ．／ｖｏｌ．）
ＮＭＰ流量 ＶＣｎ＝０．０１２４ ｋｇ／ｍｉｎ
排ガスの流量 Ｖ＝４ Ｎｍ３／ｍｉｎ
水分量 Ｖ・〔（２７３＋１５）／２７３〕・Ｘａ＝０．０５４ｋｇ／ｍｉｎの条件で段塔（水置換塔）の下部から吹き込まれる。水置換塔内に多段に設けられたバルブキャップトレイの最上段から水温ｔ３＝２０℃の補給水をＭ＝０．１７８６ ｋｇ／ｍｉｎの流量で供給する。水置換塔上部から放出される処理済ガス（ガス温度ｔ２＝４２℃）は
放出量 Ｖ＝４ Ｎｍ３／ｍｉｎ
計算含水量 Ｖ〔（２７３＋１５）／２７３〕・Ｘａ＋
〔Ｍ−ＶＣｎＲ（１／Ｘｎ−１）〕＝０．２２０８ ｋｇ／ｍｉｎ
計算含水率 Ｘａｃ＝｛〔（２７３＋１５）／２７３〕・Ｘａ＋
〔Ｍ−ＶＣｎＲ（１／Ｘｎ−１）〕／Ｖ｝・
〔２７３／（２７３＋ｔ ２ ）〕＝０．０４７８ ｋｇ／ｍ３
ガス温度ｔ２＝４２℃の時、ガス飽和含水率：Ｘｓ＝０．０５６５ ｋｇ／ｍ３
従って、
Ｘａｃ＝０．０４７８ ｋｇ／ｍ３≦Ｘｓ＝０．０５６５ ｋｇ／ｍ３
ＮＭＰ含有量 Ｃｎ（１−Ｒ）＝０．０００１５ ｋｇ／Ｎｍ３
本装置は正常に運転可能である。
一方、水置換塔下部からは下記条件で水を含有するＮ−メチル−２−ピロリドン（液温ｔ４＝８０℃）が回収できた。
ｔ４＝８０℃
収集液中の水 ＶＣｎＲ（１／Ｘｎ−１）＝０．０１１８ ｋｇ／ｍｉｎ
収集液中のＮＭＰ ＶＣｎＲ＝０．０１１８ ｋｇ／ｍｉｎ
ＮＭＰの回収率 Ｒ＝０．９５（重量分率）
ＮＭＰ濃度 Ｘｎ＝０．５０（重量分率）
なお、水置換塔物質収支は図２に示すとおりであった。
【００１８】
【発明の効果】
（１）本発明により、著しい工程の簡略化と省エネルギー化が達成できた。
（２）従来法においては、回収すべき溶剤成分などを上部から水を供給して、その水に溶剤を溶解させて下に流し落とすという手段が採用されている。この場合、系の温度が高いと水に溶けた溶剤が再び揮発してしまうから、洗浄塔に供給される水はあらかじめ室温程度まで冷却しておく必要がある。したがって冷却のためのエネルギーが必要である。一方、本発明では排ガスの熱を有効利用するものであるから、濃縮装置に供給される排ガスは加熱や冷却をすることなく、そのまま供給できるので、熱効率が極めて高い。
（３）本発明によれば、回収に使用する水は、ほんのわずかの補給水ですむが、従来技術ではいわゆる洗浄水を用いることになるので、本発明においては従来法に較べて水の使用量は約千分の１程度に少なくすることができる。
【図面の簡単な説明】
【図１】実施例１に用いた本発明の回収方法を示すフローシートである。
【図２】実施例１の熱収支分析図および物質収支を示すフローシートである。
【図３】従来の吸着剤を用いた回収方法を示すフローシートである。[0001]
BACKGROUND OF THE INVENTION
The present invention is a method for concentrating and recovering hydrophilic and volatile chemical substances having a boiling point higher than that of water contained in exhaust gas and not azeotropically with water using the difference in boiling point with water and purifying the exhaust gas. And device .
[0002]
[Prior art]
Conventionally, in order to purify exhaust gas containing a water-soluble solvent having a boiling point higher than that of water, the exhaust gas containing a water-soluble solvent is blown from the lower part of the absorption tower, and a large amount of water is allowed to flow from the upper part of the absorption tower. Was washing. In such a cleaning method, a large amount of water is required for cleaning, and since the concentration of the solvent contained in the waste water is extremely low, the solvent recovery is costly, so that the solvent recovery is practically impossible. Moreover, there is a problem that wastewater treatment is required.
[0003]
As another prior art, while rotating the horizontally arranged drum filled with an adsorbent such as zeolite, the exhaust gas cooled to about room temperature is passed through, and a part of the passing gas is released into the atmosphere as it is. Part of the sample is heated (to expel the component adsorbed on the adsorbent) and then passed again through a horizontally arranged drum filled with adsorbent such as zeolite, and the solvent adsorbed on the adsorbent is desorbed. The process gas containing a high concentration of was cooled again to recover the solvent. This method is also very inefficient in energy efficiency because it requires an operation of cooling the exhaust gas once, heating it after the adsorption treatment, and cooling it again for solvent recovery.
[0004]
For example, a conventional adsorption method has been used to remove N-methyl-2-pyrrolidone (NMP) contained in exhaust gas discharged from the drying process of the lithium electrode. In view of the fact that the adsorption efficiency of -2-pyrrolidone is significantly reduced, a step of cooling the high-temperature exhaust gas discharged from the drying step is necessary, and after adsorbing N-methyl-2-pyrrolidone on the adsorbent In order to purge N-methyl-2-pyrrolidone from the adsorbent, this time, an operation of heating in the opposite direction was necessary. Such prior art processes are shown in Figure 3.
According to the conventional method, the cooling step, the adsorption step, it must be a three steps of the desorption step, and after cooling the exhaust gas with a considerable temperature, the problem of involving a large energy loss for heating again had It was.
[0005]
[Problems to be solved by the invention]
The first object of the present invention is to recover efficiently by substituting water vapor with a hydrophilic or volatile chemical substance that has a boiling point higher than that of water contained in the exhaust gas and does not azeotrope with water , for example, a water-soluble solvent. A further object is to provide a method and apparatus for purifying exhaust gas.
The second object of the present invention is to evaporate the makeup water introduced from the outside by using the calorific value of the high temperature exhaust gas discharged from 100 ° C. to 120 ° C. from the lithium ion battery electrode manufacturing process or the like. The water-soluble volatile chemicals that have a higher boiling point than the water contained in the exhaust gas are condensed, that is, the components in the exhaust gas are replaced with water for efficient recovery, and the absorption effect of the low-temperature makeup water is improved. It is the point which provides the method and apparatus which cleans waste gas by adding.
[0006]
In the first aspect of the present invention, a tray having a structure in which gas cannot escape to the upper part unless passing through water existing on the tray is provided in a multistage manner, or from a lower portion of a packed tower packed with a hydrophilic packing. In addition, an exhaust gas containing a substance having a boiling point higher than that of water is introduced, while water is supplied from the upper part of the tower, and a substance having a higher boiling point than that of water is concentrated in the lower part of the tower due to a gas-liquid equilibrium relationship between the exhaust gas and water, "in a boiling point higher than that of water, forming an azeotropic mixture with water and not hydrophilic, volatile chemicals" in the exhaust gas in the upper portion of the column, characterized in that shifting to more water the substances in the exhaust gas remaining method for concentrating met Thus, the amount of water supplied from the top of the tower is controlled based on the concentration information at the bottom of the tower, and the concentration of hydrophilic and volatile chemical substances having a boiling point higher than that of water recovered from the bottom of the tower and not azeotropic with water is 20 to Exhaust that is controlled to 100% by weight In a boiling point higher than that of water in the scan, forming an azeotropic mixture with water and not hydrophilic, to a method of concentrating the volatile chemicals.
In the second aspect of the present invention, hydrophilic and volatile chemical substances having a boiling point higher than that of water and not azeotropic with water are NMP (N-methylpyrrolidone), DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide), DMSO (dimethyl sulfoxide), EG (ethylene glycol), DEG (diethylene glycol), TEG (triethylene glycol), PGME (propylene glycol monoethyl ether), PG (propylene glycol), 1,4-BD (1,4-butanediol), MEA (monoethanolamine) and DGME at a boiling point higher than that of water in the exhaust gas according to claim 1, wherein the (diethylene glycol monomethyl ether) solvents, selected from the group consisting of water and co The present invention relates to a method for concentrating non-boiling hydrophilic and volatile chemical substances.
The third aspect of the present invention is
(1) A multi-stage tray tower or a packed tower packed with a hydrophilic packing, in which the gas cannot escape upward unless it passes through the water present on the tray,
(2) A water supply means provided in the stage tower above the multi-stage tray or above the packed bed or a water supply means provided in the packed tower above
(3) A processing gas discharge port provided at the top of the plate tower or the top of the packed bed,
(4) Liquid discharge port provided at the lower part of the column tower or the lower part of the packed bed,
(5) A liquid reservoir containing hydrophilic and volatile chemicals that has a higher boiling point than water connected through a pipe from the liquid discharge outlet and does not azeotrope with water.
(6) Hydrophilicity that has a higher boiling point than water provided in the stage column or packed column and does not azeotrope with water.
Measuring means for detecting the concentration of volatile chemicals in the system,
(7) The amount of water supplied from the water supply means is determined by the information from the measurement means as the volatile chemical.
Means for controlling the quality concentration to be 20-100% by weight ;
The present invention relates to a concentrating device for “hydrophilic and volatile chemical substances having a boiling point higher than water and not azeotropic with water” in exhaust gas.
[0007]
In the present invention, the amount of heat of exhaust gas, which usually has a considerably high temperature (for example, 80 to 120 ° C.), is effectively used , and the exhaust gas is passed through the stage column or packed column in one step. Is an extremely efficient method and apparatus for simultaneously recovering substances having a boiling point higher than that of water and treating exhaust gas.
The present invention, in particular, from the lower part of a stage column or a packed column packed with a hydrophilic packing, in which a tray having a structure in which the gas cannot escape to the upper part unless passing through the water present on the tray, High temperature exhaust gas at 100 to 120 ° C. containing N-methylpyrrolidone discharged from the lithium ion battery electrode manufacturing process is introduced, while water is supplied from the upper part of the tower and supplied using the calorific value of the exhaust gas at the lower part of the tower. On the other hand, water having a boiling point higher than that of water contained in the exhaust gas and water-soluble N-methylpyrrolidone is condensed and dropped to the lower part of the tower. Furthermore, it is very suitable as a method and apparatus for purifying exhaust gas from a lithium ion battery electrode manufacturing factory and recovering N-methylpyrrolidone by transferring it to water.
[0008]
The amount of water to be replenished is the amount of water (B) that is contained in the treated gas released from the upper part of the column tower after exhaust gas treatment and the condensate of volatile chemicals having a boiling point higher than that of water. At the same time, it may be an amount (A) that compensates for the amount of water (C) coming out from the bottom of the tower. In other words A ≒ B + C
Therefore, the amount of water used is much less than that of the conventional exhaust gas treatment method by water washing, and even if only this point is seen, it has achieved resource saving and substantially discharged wastewater that requires wastewater treatment. It is also a great merit that it does not occur.
[0009]
The temperature at the top of the column is higher than the outside air temperature. Since the higher the temperature, the higher the saturated moisture content, the moisture in the gas in the column tower is always below the saturation point, so even if make-up water is added, the conditions to satisfy Xac ≦ Xs can be created. Can do. Xac is the calculated moisture content, and Xs is the gas saturated moisture content. The temperature of the make-up water is preferably low in terms of absorption efficiency, but if it is too low, not only the amount of water flowing down in the tower will be insufficient, but also energy for cooling will be required. Since the outside air is not normally saturated and exists at a moisture content that does not reach saturation represented by humidity, the amount of makeup water is larger than that in the saturated state.
[0010]
Examples of the substance having a boiling point higher than that of the water of the present invention include volatile chemical substances.
[0011]
And a high boiling point of the volatile chemical substances from the water, and more particularly to a high water-soluble solvent having a boiling point than water representative.
[0012]
Examples of such solvents include NMP (N-methylpyrrolidone, BP: 197 ° C), DMF (N, N-dimethylformamide, BP: 153 ° C), DMAC (N, N-dimethylacetamide, BP: 165 ° C). , DMSO (dimethyl sulfoxide, BP: 189 ° C.), EG (ethylene glycol, BP: 197 ° C.), DEG (diethylene glycol, BP: 245 ° C.), TEG (triethylene glycol, BP: 278 ° C.), PGME (propylene glycol mono Ethyl ether), PG (propylene glycol, BP: 188 ° C), 1,4-BD (1,4-butanediol, BP: 235 ° C), MEA (monoethanolamine, BP: 170.5 ° C) and DGME ( Diethylene glycol monomethyl ether) and other non-azeotropic properties It is preferred.
[0013]
There is a valve cap tray (bubble bell plate) that has been used since the oldest as a tray with a structure that allows gas to escape to the top if it does not pass through the water present in the tray. And a sieve tray (perforated plate). The valve cap tray is better from the viewpoint of stability, but the sheave tray is better from the viewpoint of cost.
[0014]
The hydrophilic packing in the packed tower packed with the hydrophilic packing may be in the form of regular packing or irregular packing, but considering the pressure loss, Is preferred. These fillers are hydrophilic and have a large surface area, such as porous materials made of a hydrophilic material, specifically porous ceramics and porous carbon.
[0015]
The present invention can be suitably used for treating exhaust gas discharged from a drying process for removing N-methyl-2-pyrrolidone (NMP) solvent, particularly in a lithium ion battery manufacturing plant. As shown in FIG. 1, in order to remove the N-methyl-2-pyrrolidone (NMP) solvent, normal air is taken from outside the factory, filtered, and then heated air is blown to the drying process by a blower. .
Normal intake air from outside the factory is outside temperature t
Flow rate V Nm 3 / min
Moisture content Xa kg / m 3
Water content V · [(273 + t) / 273] · Xa kg / min
It is. The exhaust gas discharged from the drying process for removing the N-methyl-2-pyrrolidone (NMP) solvent in the lithium ion battery manufacturing factory is exhaust gas temperature t 1 = 100 to 120 ° C.
NMP content Cn = 0.005-0.01 kg / N m 3
(113-2260 ppm, vol./vol.)
NMP flow rate VCn kg / min
Flow rate of exhaust gas V Nm 3 / min
Water content V · [(273 + t) / 273] · Xa kg / min
It is blown from the lower part of the stage tower (water displacement tower) under the conditions of From the uppermost stage such as valve cap trays and sheave trays provided in multiple stages in the water displacement tower, make-up water at normal temperature, for example, t 3 ° C is supplied at a flow rate of M kg / min. The treated gas (gas temperature t 2 ) released from the upper part of the water displacement tower is obtained by using R as the recovery rate (weight fraction) of volatile chemical substances such as NMP.
Release amount V Nm 3 / min
Calculated water content V · [(273 + 15) / 273] · Xa +
[M-VCnR (1 / Xn-1)] kg / min
Calculated moisture content Xac = {[(273 + 15) / 273] · Xa +
[M-VCnR (1 / Xn-1)] / V}.
[273 / (273 + t 2 )] kg / m 3
When the gas temperature t 2, gas saturated water content: Xs
As a control condition, when Xac ≦ Xs, the apparatus can be operated normally.
On the other hand, N-methyl-2-pyrrolidone (liquid temperature t 4 ) containing water is recovered from the lower part of the water displacement column.
[0016]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the examples, percentages are by weight unless otherwise indicated.
[0017]
Example 1
The intake air in the drying process for removing the N-methyl-2-pyrrolidone (NMP) solvent of the lithium ion battery shown in FIG.
Outside air temperature t = 15 ℃
Flow rate V = 4 Nm 3 / min
Moisture content Xa = 0.0128 kg / m 3 (assuming saturation)
The water content was V · [(273 + 15) / 273] · Xa = 0.054 kg / min. The exhaust gas discharged from the drying process for removing the N-methyl-2-pyrrolidone (NMP) solvent in the lithium ion battery manufacturing plant is exhaust gas temperature t 1 = 120 ° C.
NMP content Cn = 0.0031 kg / N m 3
(700 ppm, vol./vol.)
NMP flow rate VCn = 0.124 kg / min
Flow rate of exhaust gas V = 4 Nm 3 / min
Moisture amount V · [(273 + 15) / 273] · Xa = 0.054 kg / min. Make-up water with a water temperature t 3 = 20 ° C. is supplied at a flow rate of M = 0.1786 kg / min from the uppermost stage of the valve cap tray provided in multiple stages in the water displacement tower. The treated gas released from the upper part of the water displacement tower (gas temperature t 2 = 42 ° C.) is released V = 4 Nm 3 / min
Calculated water content V [(273 + 15) / 273] · Xa +
[M-VCnR (1 / Xn-1)] = 0.2208 kg / min
Calculated moisture content Xac = {[(273 + 15) / 273] · Xa +
[M-VCnR (1 / Xn-1)] / V}.
[273 / (273 + t 2 )] = 0.0478 kg / m 3
When gas temperature t 2 = 42 ° C., gas saturated moisture content: Xs = 0.0565 kg / m 3
Therefore,
Xac = 0.0478 kg / m 3 ≦ Xs = 0.0565 kg / m 3
NMP content Cn (1-R) = 0.00015 kg / N m 3
This device can be operated normally.
On the other hand, N-methyl-2-pyrrolidone (liquid temperature t 4 = 80 ° C.) containing water was recovered from the lower part of the water displacement column under the following conditions.
t 4 = 80 ° C
Water in the collected liquid VCnR (1 / Xn-1) = 0.118 kg / min
NMP in the collected liquid VCnR = 0.118 kg / min
NMP recovery rate R = 0.95 (weight fraction)
NMP concentration Xn = 0.50 (weight fraction)
The water displacement column material balance was as shown in FIG.
[0018]
【The invention's effect】
(1) According to the present invention, remarkable simplification of the process and energy saving can be achieved.
(2) In the conventional method, a means is adopted in which water is supplied from the top of the solvent component to be recovered, etc., and the solvent is dissolved in the water and poured down. In this case, if the temperature of the system is high, the solvent dissolved in the water volatilizes again, so that the water supplied to the washing tower needs to be cooled to about room temperature in advance. Therefore, energy for cooling is required. On the other hand, in the present invention, the heat of the exhaust gas is used effectively, so that the exhaust gas supplied to the concentrating device can be supplied as it is without heating or cooling, so that the thermal efficiency is extremely high.
(3) According to the present invention, only a small amount of replenishing water is required for recovery, but so-called washing water is used in the prior art, so in the present invention, water is used compared to the conventional method. The amount can be reduced to about a thousandth.
[Brief description of the drawings]
1 is a flow sheet showing the recovery method of the present invention used in Example 1. FIG.
FIG. 2 is a flow sheet showing a heat balance analysis diagram and a material balance of Example 1.
FIG. 3 is a flow sheet showing a recovery method using a conventional adsorbent.

Claims (3)

トレイ上に存在する水の中を通らなければガスが上部に抜けられない構造のトレイを多段に設けてなる段塔または親水性充填物を充填した充填塔の下部から、水より高沸点の物質を含む排ガスを導入し、一方、塔上部からは水を供給し、塔下部では排ガスと水との気液平衡関係により前記水より高沸点の物質を濃縮するとともに、塔上部では残存する排ガス中の前記物質をさらに水中に移行させることを特徴とする排ガス中の「水より高沸点で、水と共沸しない親水性、揮発性化学物質」を濃縮する方法であって、塔上部から供給する水の量は、塔下部の濃度情報に基づき制御し、塔下部から回収する水より高沸点で、水と共沸しない親水性、揮発性化学物質の濃度は２０〜１００重量％になるように制御するものである排ガス中の水より高沸点で、水と共沸しない親水性、揮発性化学物質を濃縮する方法。Substances with a boiling point higher than water from the bottom of a packed column or a packed column filled with a hydrophilic packing, in which multiple trays with a structure in which gas cannot escape through the water present on the tray are not allowed to escape. On the other hand, water is supplied from the upper part of the tower, and substances having a higher boiling point than the water are concentrated in the lower part of the tower due to the vapor-liquid equilibrium relationship between the exhaust gas and water, and in the remaining exhaust gas at the upper part of the tower The above-mentioned substance is further transferred to water, which is a method for concentrating “hydrophilic and volatile chemical substances having a higher boiling point than water and not azeotropic with water” in exhaust gas , which is supplied from the upper part of the tower The amount of water is controlled based on the concentration information at the bottom of the tower so that the concentration of hydrophilic and volatile chemicals that have a higher boiling point than water recovered from the bottom of the tower and does not azeotrope with water is 20 to 100% by weight. Higher than the water in the exhaust gas being controlled In point, the method of concentrating water azeotroped not hydrophilic, volatile chemicals. 前記水より高沸点で、水と共沸しない親水性、揮発性化学物質が、ＮＭＰ（Ｎ−メチルピロリドン）、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）、ＤＭＡＣ（Ｎ，Ｎ−ジメチルアセトアミド）、ＤＭＳＯ（ジメチルスルホキシド）、ＥＧ（エチレングリコール）、ＤＥＧ（ジエチレングリコール）、ＴＥＧ（トリエチレングリコール）、ＰＧＭＥ（プロピレングリコールモノエチルエーテル）、ＰＧ（プロピレングリコール）、１，４−ＢＤ（１，４−ブタンジオール）、ＭＥＡ（モノエタノールアミン）およびＤＧＭＥ（ジエチレングリコールモノメチルエーテル）よりなる群から選ばれた溶剤類である請求項１記載の排ガス中の水より高沸点で、水と共沸しない親水性、揮発性化学物質を濃縮する方法。Hydrophilic and volatile chemical substances having a boiling point higher than that of water and not azeotropic with water are NMP (N-methylpyrrolidone), DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide), DMSO. (Dimethyl sulfoxide), EG (ethylene glycol), DEG (diethylene glycol), TEG (triethylene glycol), PGME (propylene glycol monoethyl ether), PG (propylene glycol), 1,4-BD (1,4-butanediol) ), MEA (monoethanolamine) and DGME (boiling point higher than that of water in the exhaust gas according to claim 1, wherein the solvents, selected from the group consisting of diethylene glycol monomethyl ether), water and azeotroped not hydrophilic, volatile A method of concentrating chemical substances. （１） トレイ上に存在する水の中を通らなければガスが上部に抜けられない構造の
トレイを多段に設けてなる段塔または親水性充填物を充填した充填塔、
（２） 前記多段トレイの上方であって前記段塔内に設けられた給水手段または充填層
の上方であって前記充填塔内に設けられた給水手段、
（３） 段塔の上部または充填層の上部に設けられた処理ガス放出口、
（４） 段塔の下部または充填層の下部に設けられた液状物排出口、
（５） 液状物排出口からパイプを通して連結された水より高沸点で、水と共沸しない
親水性、揮発性化学物質を含む液状物溜り、
（６） 段塔内または充填塔内に設けられた水より高沸点で、水と共沸しない親水性、
揮発性化学物質の系中濃度を検知するための測定手段、
（７） 前記測定手段からの情報により前記給水手段からの給水量を前記揮発性化学物
質の濃度が２０〜１００重量％になるように制御する手段、
よりなることを特徴とする排ガス中の「水より高沸点で、水と共沸しない親水性、揮発性化学物質」に対する濃縮装置。(1) A multi-stage tray tower or a packed tower packed with a hydrophilic packing, in which the gas cannot escape upward unless it passes through the water present on the tray,
(2) A water supply means provided in the stage tower above the multi-stage tray or above the packed bed or a water supply means provided in the packed tower above
(3) Process gas discharge port provided at the upper part of the column tower or the upper part of the packed bed,
(4) Liquid discharge port provided at the lower part of the column tower or the lower part of the packed bed,
(5) A liquid reservoir containing hydrophilic and volatile chemicals that has a higher boiling point than water connected through a pipe from the liquid discharge outlet and does not azeotrope with water.
(6) Hydrophilicity that has a higher boiling point than water provided in the stage column or packed column and does not azeotrope with water.
Measuring means for detecting the concentration of volatile chemicals in the system,
(7) The amount of water supplied from the water supply means is determined by the information from the measurement means as the volatile chemical.
Means for controlling the quality concentration to be 20-100% by weight ;
A concentrating device for "hydrophilic and volatile chemical substances having a boiling point higher than water and not azeotropic with water" in exhaust gas, characterized by comprising:
JP2003020725A 2003-01-29 2003-01-29 Method and apparatus for concentrating substances having higher boiling point than water in exhaust gas Expired - Lifetime JP4030439B2 (en)

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JP2003020725A JP4030439B2 (en) 2003-01-29 2003-01-29 Method and apparatus for concentrating substances having higher boiling point than water in exhaust gas
TW092114542A TWI255732B (en) 2003-01-29 2003-05-29 Method and device for condensing materials with a boiling point higher than that of water from an exhaust
CNB031483461A CN100563788C (en) 2003-01-29 2003-06-30 Concentrate the method and apparatus of material higher in the exhaust than water boiling point
KR1020030045180A KR100981073B1 (en) 2003-01-29 2003-07-04 Method and apparatus for concentrating a substance having a higher boiling point than water in an exhaust gas

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JP4593264B2 (en) * 2004-01-30 2010-12-08 三菱化学エンジニアリング株式会社 N-methyl-2-pyrrolidone recovery device and recovery method thereof
JP4778403B2 (en) * 2006-11-08 2011-09-21 日本リファイン株式会社 A method and apparatus for purifying exhaust gas by collecting and concentrating VOC from exhaust gas containing VOC.
CN101791509B (en) * 2010-03-31 2011-12-28 苏州巨联科技有限公司 Ternary cycle DMF waste gas recovery method and device
JP6180704B2 (en) 2011-12-12 2017-08-16 日本リファイン株式会社 Gas-liquid contact device
JP6665063B2 (en) 2015-11-24 2020-03-13 株式会社西部技研 Drying equipment
CN107715651A (en) * 2017-10-17 2018-02-23 华南理工大学 A kind of efficient low damage solvent for being used to absorb toluene and flow

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CN100563788C (en) 2009-12-02
TW200413077A (en) 2004-08-01
TWI255732B (en) 2006-06-01
KR20040069939A (en) 2004-08-06
KR100981073B1 (en) 2010-09-08
CN1517144A (en) 2004-08-04

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