JPH0651085B2 - Concentration and purification method of alcohol - Google Patents
Concentration and purification method of alcoholInfo
- Publication number
- JPH0651085B2 JPH0651085B2 JP2322329A JP32232990A JPH0651085B2 JP H0651085 B2 JPH0651085 B2 JP H0651085B2 JP 2322329 A JP2322329 A JP 2322329A JP 32232990 A JP32232990 A JP 32232990A JP H0651085 B2 JPH0651085 B2 JP H0651085B2
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- alcohol
- column
- phase
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、化学合成アルコール又は発酵アルコール製造
プロセスから生じる水／エタノール／不純物の混合物か
ら不純物を分離する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for separating impurities from a water / ethanol / impurity mixture resulting from a chemically synthesized or fermentative alcohol production process.
化学合成アルコールは通常エチレンの水和反応によって
製造され、合成反応後の組成は約20wt% のエタノールと
約８０wt% の水を主成分とするが、これ以外にエチルエ
ーテル、アセトアルデヒド、メチルエチルケトン、２−
ブタノール、アセトン等の微量の不純物を含んでおり、
アルコールの濃縮と独立に又は並行してこれらの不純物
を分離し、アルコール専売法又はＪＩＳ規格に適合する
ように精製する必要がある。Chemically synthesized alcohols are usually produced by the hydration reaction of ethylene, and the composition after the synthesis reaction is mainly composed of about 20 wt% ethanol and about 80 wt% water. Other than this, ethyl ether, acetaldehyde, methyl ethyl ketone, 2-
Contains trace amounts of impurities such as butanol and acetone,
It is necessary to separate these impurities independently or in parallel with the concentration of alcohol and purify them so as to comply with the alcohol proprietary method or JIS standard.
一方、発酵アルコールは約１０wt% のエタノールと約９
０wt% の水を主成分とするが、これ以外にアセトアルデ
ヒド、メタノール、酢酸エチル、ｎ−プロパノール、ｉ
−ブタノール、ｎ−ブタノール、ｉ−アミルアルコー
ル、ジアセチル、酢酸等の微量の不純物を含んでおり、
やはり規格に適用するように精製する必要がある。On the other hand, fermented alcohol is about 10 wt% ethanol and about 9
The main component is 0 wt% water, but other than this, acetaldehyde, methanol, ethyl acetate, n-propanol, i
-It contains trace amounts of impurities such as butanol, n-butanol, i-amyl alcohol, diacetyl, acetic acid,
After all, it is necessary to refine it so as to apply to the standard.
従来、これらの不純物の精製は蒸留又は溶剤抽出法によ
り行なわれている。蒸留法では、不純物のエタノールに
対する揮発度が不純物の種類及びエタノール濃度により
複雑に変化するために、プロセスが複雑となり多くのエ
ネルギーと多大の装置コストが必要である。溶剤抽出法
では液体又は超臨界状態のCO２を溶剤として用いる方法
が特願昭５９−１１６８１０（特開昭６０−４１６２７
号公報）にみられる。Conventionally, purification of these impurities has been carried out by distillation or solvent extraction. In the distillation method, the volatility of impurities with respect to ethanol varies in a complicated manner depending on the type of impurities and the concentration of ethanol, and therefore the process is complicated and requires a lot of energy and a large amount of equipment cost. In the solvent extraction method, a method of using CO 2 in a liquid or supercritical state as a solvent is disclosed in Japanese Patent Application No. 59-116810 (Japanese Patent Application Laid-Open No. 60-41627).
Issue).
本発明は、合成法又は発酵法により製造された水／エタ
ノール／不純物からなる混合物から、不純物を選択的に
分離する方法に関し、水／エタノールを無水化できる溶
剤として本発明者は先にプロパン、プロピレン、ブタン
を、該不純物の抽出溶剤として用いる方法を提案した
（特願平１−１６０６９６号＝特開平３−２７３３６号
公報参照）。The present invention relates to a method for selectively separating impurities from a mixture of water / ethanol / impurities produced by a synthetic method or a fermentation method. A method has been proposed in which propylene and butane are used as an extraction solvent for the impurities (see Japanese Patent Application No. 1-160696 and Japanese Patent Application Laid-Open No. 3-27336).
これらの溶剤を用いた方法ではそれなりに効果を奏する
が、多くの不純物のうち、メタノール、プロパノール、
アセトアルデヒド、酢酸、アセトンの分離が必ずしも満
足できるものとはいえず、より効率的な方法が望まれて
いる。The method using these solvents has some effect, but among many impurities, methanol, propanol,
Separation of acetaldehyde, acetic acid, and acetone is not always satisfactory, and a more efficient method is desired.
本発明は上記技術水準に鑑み、より合目的なアルコール
の濃縮精製方法を提供しようとするものである。In view of the above-mentioned state of the art, the present invention aims to provide a more purposeful method for concentrating and purifying alcohol.
本発明は発酵法又は化学合成法により製造された水／エ
タノール／不純物からなる混合物を向流抽出塔の上部よ
り、下部よりプロパン、プロピレン、ｎ−ブタン及びｉ
−ブタンよりなる群のうちの一つの溶剤を供給し、向流
抽出塔内を該溶剤の超臨界状態又は擬臨界状態に維持す
るようにして両者を向流で接触させ、向流抽出塔上部よ
り濃縮アルコールを含んだ溶剤相を抜き出す一次脱水工
程、該溶剤相を冷却し、水分に富んだ重液相と濃縮アル
コールを含んだ軽液相に重力沈降分離し、該重液相は前
記向流抽出塔上部へ還流する二次脱水工程、該軽液相の
圧力を該溶剤の上記圧力以下に減圧後、溶剤抽出蒸留塔
に導入し、塔底より実質的に水分を含まないアルコール
と溶剤の塔底混合液体を、塔頂より実質的にアルコール
を含まない水分と溶剤の混合蒸気を各々抜き出す三次脱
水工程、該塔底混合液体を脱溶剤塔により溶剤とアルコ
ールに分離する脱溶剤工程及び該脱溶剤塔の塔頂混合蒸
気と該溶剤抽出蒸留塔の塔頂蒸気を冷却後、水を加えて
実質的に不純物を含まない溶剤相と不純物が濃縮された
水相に相分離させ、該溶剤相を該溶剤抽出蒸留塔の塔頂
及び該向流抽出塔の塔底へ循環することを特徴とするア
ルコールの濃縮精製方法である。The present invention relates to a mixture of water / ethanol / impurities produced by a fermentation method or a chemical synthesis method from the upper part of a countercurrent extraction column and from the lower part of propane, propylene, n-butane and i.
Supplying one solvent of the group consisting of butane, contacting them in countercurrent so as to maintain the supercritical state or pseudocritical state of the solvent in the countercurrent extraction column, and the countercurrent extraction column upper part A primary dehydration step of extracting the solvent phase containing more concentrated alcohol, cooling the solvent phase, and performing gravity settling separation into a heavy liquid phase rich in water and a light liquid phase containing concentrated alcohol. Secondary dehydration step of refluxing to the flow extraction column upper part, after reducing the pressure of the light liquid phase below the pressure of the solvent, introduced into the solvent extraction distillation column, alcohol and solvent substantially free of water from the bottom of the column The column bottom mixed liquid, a tertiary dehydration step of extracting the mixed vapor of water and solvent substantially free of alcohol from the top of the column, a desolvation step of separating the column bottom mixed liquid into a solvent and alcohol by a desolvation tower, and The mixed vapor at the top of the desolvation tower and the solvent extraction steam After cooling the top vapor of the column, water is added to cause phase separation into a solvent phase containing substantially no impurities and a water phase enriched with impurities, and the solvent phase is separated from the top of the solvent extraction distillation column and It is a method for concentrating and purifying alcohol which is characterized in that it is circulated to the bottom of a flow extraction column.
本発明は全てのアルコール水溶液の濃縮精製に適用しう
るものであるが、その一例として発酵アルコールについ
て云えばアルコール濃度は約１０wt% 前後で残りは水で
ある。又、合成アルコールではアルコール濃度は約２０
wt% 前後で残りは水である。The present invention can be applied to the concentration and purification of all alcohol aqueous solutions. As an example of the fermentation alcohol, the alcohol concentration is about 10 wt% and the rest is water. Also, with synthetic alcohol, the alcohol concentration is about 20.
Around wt%, the rest is water.
一方、本発明で云う溶剤とは下記のものを云う。On the other hand, the solvent used in the present invention means the following.
又、本発明で云う溶剤の超臨界状態とは溶剤の臨界温度
Ｔｃ及び臨界圧力Ｐｃ以上の温度及び圧力に維持した状
態であり、擬臨界状態とはその臨界温度Ｔｃ以下である
が、８０℃以上の温度であり、圧力はその温度における
溶剤の飽和蒸気圧以上に保持した状態をいう。 The supercritical state of the solvent referred to in the present invention is a state in which the temperature and the pressure are higher than the critical temperature Tc and the critical pressure Pc of the solvent, and the pseudocritical state is the critical temperature Tc or lower. It is the above temperature, and the pressure means a state in which the saturated vapor pressure of the solvent or more at that temperature is maintained.
以下、本発明の一実施例を第１図に従って詳述する。An embodiment of the present invention will be described below in detail with reference to FIG.
第１図において、１は向流抽出塔（充填塔、棚段塔又は
多段抽出塔などが好ましい。）、２は原料であるアルコ
ールを含む水溶液の原料供給ライン、３は抽出残液（水
が主成分）の取出しライン、４は溶剤相（溶剤と１次濃
縮アルコール混合相）取出しライン、５は冷却器、６は
重力沈降槽、７は重液相（水が主成分で少量のアルコー
ル、溶剤を含む）取出しライン、８は軽液相（溶剤と２
次濃縮アルコール混合物）取出しライン、９は重力沈降
槽６内重液の液位調整弁、１０は重力沈降槽６の圧力調
整弁、１１は重液還流ライン、１２は溶剤抽出蒸留塔原
料供給ライン、１３は溶剤抽出蒸留塔、１４は塔底混合
液体（無水アルコールと溶剤からなる）取出しライン、
１５は塔底液位調整弁、１６は塔頂蒸気（溶剤と水から
なる）取出しライン、１７は圧縮機、１８はリボイラ
（熱交換器）、１９は水分離槽、２０は水抜出しライ
ン、２１は溶剤抜出しライン、２２，２３は溶剤還流ラ
イン、２４は溶剤加熱器、２５は溶剤供給ライン、２６
は水供給ライン、２７は脱溶剤塔、２８は溶剤抽出塔の
塔底液体の脱溶剤塔への供給ライン、２９は脱溶剤塔塔
底液（実質的には溶剤が含まれていない液体アルコール
からなる）抜出しライン、３０は脱溶剤塔塔頂蒸気（実
質的にはアルコールが含まれていない溶剤蒸気からな
る）抜出しライン、３２は脱溶剤塔底液加熱用熱交換器
である。In FIG. 1, 1 is a countercurrent extraction column (preferably a packed column, a plate column or a multi-stage extraction column, etc.), 2 is a raw material supply line for an aqueous solution containing alcohol as a raw material, and 3 is an extraction residual liquid (water is Taking out line of the main component 4 is taken out line of the solvent phase (mixed phase of solvent and primary concentrated alcohol), 5 is a cooler, 6 is a gravity settling tank, 7 is a heavy liquid phase (water is the main component and a small amount of alcohol, Extraction line including solvent, 8 is light liquid phase (solvent and 2
Next concentrated alcohol mixture) take-out line, 9 is a liquid level adjusting valve of heavy liquid in the gravity settling tank 6, 10 is a pressure adjusting valve of the gravity settling tank 6, 11 is a heavy liquid reflux line, 12 is a solvent extraction distillation column raw material supply line , 13 is a solvent extraction distillation column, 14 is a column bottom mixed liquid (comprising anhydrous alcohol and solvent) take-out line,
15 is a bottom liquid level adjusting valve, 16 is a top vapor (comprising solvent and water) take-out line, 17 is a compressor, 18 is a reboiler (heat exchanger), 19 is a water separation tank, 20 is a water take-out line, 21 is a solvent extraction line, 22 and 23 are solvent reflux lines, 24 is a solvent heater, 25 is a solvent supply line, and 26 is a solvent supply line.
Is a water supply line, 27 is a desolvation tower, 28 is a supply line of the bottom liquid of the solvent extraction tower to the desolvation tower, 29 is a desolvation tower bottom liquid (substantially solvent-free liquid alcohol Is a removal line, 30 is a desolvation tower overhead vapor (comprising substantially solvent-free solvent vapor) withdrawal line, and 32 is a heat exchanger for heating the desolvation column bottom liquid.
原料の水／エタノール／不純物からなるアルコール水溶
液１重量部を原料供給ライン２より、又溶剤３〜６重量
部を溶剤供給ライン２５より向流抽出塔１に供給し、該
溶剤を超臨界状態又は擬臨界状態でアルコール水溶液と
向流接触させることにより、密度の低い溶剤相は上昇し
ながらアルコール水溶液よりアルコール及び一部の不純
物を選択的に抽出し、溶剤相取出しライン４より軽液と
して取り出される。不純物の内、メタノール及び酢酸の
一部は抽出残渣取出しライン３より水とともに抜き出さ
れる。1 part by weight of an aqueous alcohol solution consisting of water / ethanol / impurity as a raw material is supplied from a raw material supply line 2 and 3 to 6 parts by weight of a solvent to a countercurrent extraction column 1 from a solvent supply line 25, and the solvent is in a supercritical state or By making countercurrent contact with the aqueous alcohol solution in the pseudocritical state, the solvent phase having a low density rises and selectively extracts alcohol and some impurities from the aqueous alcohol solution and is taken out from the solvent phase extraction line 4 as a light liquid. . Of the impurities, part of methanol and acetic acid is extracted together with water from the extraction residue extraction line 3.
この際、温度の増加とともに該溶剤へのアルコールの溶
解度は増加するが、逆にアルコールの選択性は減少する
ので、本発明方法ではこの点を考慮し、使用する溶剤の
種類に応じて該向流抽出塔１の好ましい操作条件の範囲
を設定すべきである。At this time, the solubility of alcohol in the solvent increases with an increase in temperature, but on the contrary, the selectivity of alcohol decreases. Therefore, in the method of the present invention, this point is taken into consideration, and the solubility of alcohol depends on the type of solvent used. A range of preferred operating conditions for the flow extraction column 1 should be set.
該向流抽出塔１ではアルコール抽出に着目しており、ア
ルコールはほぼ完全に抽出され、抽出アルコール濃度は
５０〜９０wt% 程度に一次濃縮（一次脱水工程）すれば
よく、そのためには温度は８０℃以上とし、圧力は使用
溶剤の飽和蒸気圧以上又は臨界圧力以上にすべきであ
る。In the countercurrent extraction tower 1, attention is paid to alcohol extraction. Alcohol is almost completely extracted, and the concentration of the extracted alcohol may be primarily concentrated (primary dehydration step) to about 50 to 90 wt%, for which the temperature is 80%. The temperature should be above ℃, and the pressure should be above the saturated vapor pressure of the solvent used or above the critical pressure.
次に、溶剤相取出しライン４から取出された溶剤相を冷
却器５で冷却することにより、重力沈降槽６で重液相取
出しライン７からの重液相と軽液相取出しライン８から
の軽液相に相分離し、水が主成分で不純物及び僅かなア
ルコールと溶剤を含有する重液相と、溶剤が主成分で二
次濃縮（二次脱水工程）されたアルコール及び不純物を
含有している軽液相に相分離する。冷却温度は低ければ
低い程、軽液相中のアルコール濃度は高くなるが、アル
コール濃度の最大値は約９５wt% であり、これ以上は濃
縮できなかった。Next, the solvent phase taken out from the solvent phase taking-out line 4 is cooled by the cooler 5, so that the heavy liquid phase from the heavy liquid phase taking-out line 7 and the light liquid phase from the light liquid phase taking-out line 8 in the gravity settling tank 6 are cooled. Phase separation into a liquid phase, water is the main component and impurities and a small amount of alcohol and solvent are contained in the heavy liquid phase, and the solvent is the main component and contains secondary concentrated (secondary dehydration step) alcohol and impurities. Phase separation into a light liquid phase. The lower the cooling temperature, the higher the alcohol concentration in the light liquid phase, but the maximum alcohol concentration was about 95 wt%, and it was not possible to concentrate further.
該重力沈降槽６の好ましい圧力は、前記向流抽出塔１と
同一で、好ましい温度は一次脱水工程より低くしなけれ
ばならぬが、その温度は溶剤の種類により異なり、軽液
相中のアルコール濃度が約９５wt% になるように設定す
べきであるが、最終的には全体の熱エネルギーバランス
から最適化するのが好ましい。また、前記重液相は少量
のアルコールと溶剤を回収するために液位調整弁９、重
液還流ライン１１を介し該向流抽出塔１の上部付近へ還
流するのが好ましい。The preferred pressure in the gravity settling tank 6 is the same as that in the countercurrent extraction column 1, and the preferred temperature must be lower than that in the primary dehydration step, but the temperature varies depending on the type of solvent, and the alcohol in the light liquid phase is different. The concentration should be set to about 95 wt%, but it is preferable to optimize the final heat energy balance. Further, the heavy liquid phase is preferably refluxed near the upper part of the countercurrent extraction column 1 through a liquid level adjusting valve 9 and a heavy liquid reflux line 11 in order to recover a small amount of alcohol and a solvent.
次に、前記軽液相は圧力調整弁１０で溶剤の臨界圧力以
下に減圧され、溶剤抽出蒸留塔原料供給ライン１２を経
て溶剤抽出蒸留塔１３に供給される。溶剤抽出蒸留塔１
３上部の溶剤還流ライン２２より後記の工程から送られ
てくる溶剤をアルコールの抽出材として溶剤抽出蒸留塔
１３に供給し抽出蒸留を行うことにより、塔底混合液体
取出しライン１４より水分及び不純物を実質的に含まな
い無水アルコールと溶剤の混合液体を、又塔頂蒸気取出
しライン１６よりアルコールを実質的に含まない水分及
び不純物と溶剤の混合ガスを取出す（三次脱水工程）。Next, the light liquid phase is depressurized to a pressure not higher than the critical pressure of the solvent by the pressure control valve 10 and supplied to the solvent extraction distillation column 13 through the solvent extraction distillation column raw material supply line 12. Solvent extraction distillation column 1
3 The solvent sent from the process described below through the solvent reflux line 22 at the upper part is supplied to the solvent extraction distillation column 13 as an alcohol extractant to carry out extractive distillation, thereby removing water and impurities from the column bottom mixed liquid take-out line 14. A mixed liquid of anhydrous alcohol and a solvent which does not substantially contain alcohol and a mixed gas of water and impurities and a solvent which does not substantially contain alcohol are extracted from the overhead vapor extraction line 16 (third dehydration step).
該塔底混合液体取出しライン１４からの混合液体は、沸
点が大幅に異なる２成分系（アルコールと溶剤）であ
り、通常の脱溶剤塔２７により容易に無水アルコールと
溶剤に分離でき、実質的に水分及び溶剤を含まない無水
アルコールが該塔の塔底液抜出しライン２９より得られ
る。The mixed liquid from the column bottom mixed liquid take-out line 14 is a two-component system (alcohol and solvent) having significantly different boiling points, and can be easily separated into anhydrous alcohol and solvent by the ordinary desolvation column 27, Anhydrous alcohol free of water and solvent is obtained from the bottom liquid withdrawing line 29 of the tower.
すなわち、溶剤抽出塔１３の塔底混合液体取出しライン
１４中の液体中にはアルコール中に溶剤がほゞ同量溶解
しており、脱溶剤塔２７に供給ライン２８より供給し、
溶剤とアルコールの揮発度の差を利用した蒸留分離操作
を行ない、液体溶剤還流ライン３１からは脱溶剤塔塔頂
蒸気抜出しライン３０へのアルコール損失を防止するた
めに液体溶剤を還流することによって、塔底液抜出しラ
イン２９からは実質的に溶剤の分離されたアルコール
を、又塔頂蒸気抜出しライン３０からは実質的にアルコ
ールを含まない溶剤を分離できるのである（脱溶剤工
程）。That is, almost the same amount of solvent is dissolved in alcohol in the liquid in the bottom mixed liquid extraction line 14 of the solvent extraction tower 13, and the solvent is supplied to the desolvation tower 27 from the supply line 28.
By performing a distillation separation operation utilizing the difference in volatility of the solvent and alcohol, by refluxing the liquid solvent from the liquid solvent reflux line 31 to prevent alcohol loss to the desolventizer overhead vapor extraction line 30, The alcohol from which the solvent is substantially separated can be separated from the column bottom liquid withdrawing line 29, and the solvent containing substantially no alcohol can be separated from the column top vapor drawing line 30 (desolvation step).
該ライン３０の溶剤蒸気は溶剤抽出蒸留塔１３の塔頂蒸
気抜出しライン１６中の蒸気と共に圧縮機１７によって
再圧縮し、その圧縮熱を溶剤抽出蒸留塔１３のリボイラ
１８で利用するようにするのが好ましい。The solvent vapor in the line 30 is recompressed by the compressor 17 together with the vapor in the overhead vapor extraction line 16 of the solvent extraction distillation column 13, and the heat of compression is used in the reboiler 18 of the solvent extraction distillation column 13. Is preferred.
溶剤抽出蒸留塔１３においては、溶剤を溶剤の蒸気と液
が共存す状態に保持し、溶剤の蒸気と液が共存する条件
下でアルコール水溶液と接触させると、アルコールは親
和力の差異により選択的に溶剤に抽出され、更にアルコ
ールに対して溶剤が多量に液相中に存在する条件下で
は、水分は液相に殆んど溶解せず、溶剤蒸気相中の水分
濃度が水の飽和濃度以下になるような条件を設定する
と、水分を溶剤蒸気相へ選択的に移行させることができ
る。かくして溶剤を媒体にアルコールと水の分離がで
き、無水アルコールが得られる。In the solvent extraction distillation column 13, when the solvent is kept in a state in which the solvent vapor and the liquid coexist and is brought into contact with the alcohol aqueous solution under the condition in which the solvent vapor and the liquid coexist, the alcohol is selectively selected due to the difference in affinity. Under the condition that the solvent is extracted and a large amount of the solvent is present in the liquid phase with respect to alcohol, the water is hardly dissolved in the liquid phase, and the water concentration in the solvent vapor phase becomes equal to or lower than the saturation concentration of water. By setting such conditions, it is possible to selectively transfer water to the solvent vapor phase. In this way, alcohol and water can be separated using a solvent as a medium to obtain anhydrous alcohol.
溶剤抽出蒸留塔１３内で溶剤の蒸気は液が共存する条件
とするためには、温度は溶剤の臨界温度Ｔｃ以下で、圧
力はこの温度における液相組成に対応した平衡蒸気圧
（最大値は溶剤の臨界圧力Ｐｃ）にすべきである。In order to make the solvent vapor in the solvent extraction distillation column 13 coexist with the liquid, the temperature is equal to or lower than the critical temperature Tc of the solvent, and the pressure is the equilibrium vapor pressure corresponding to the liquid phase composition (the maximum value is It should be the critical pressure of the solvent Pc).
なお、溶剤還流ライン２２からの溶剤の量は溶剤抽出蒸
留塔原料供給ライン１２からの原料中のアルコール濃
度、製品アルコール濃度により変えるべきであり、溶剤
還流ライン２２からの溶剤の量は溶剤抽出蒸留塔１３の
段数により一般の蒸留と同じように化学工学的手法によ
り経済的な量に決定されるべきである。The amount of the solvent from the solvent reflux line 22 should be changed depending on the alcohol concentration in the raw material and the product alcohol concentration from the solvent extraction distillation column raw material supply line 12, and the amount of the solvent from the solvent reflux line 22 is the solvent extractive distillation. Depending on the number of plates in the column 13, it should be determined in an economical amount by chemical engineering techniques as in general distillation.
溶剤抽出蒸留塔１３の塔頂蒸気取出しライン１６からの
塔頂蒸気（溶剤と水からなり、実質的にアルコールを含
まない）は、前記脱溶剤塔２７の塔頂蒸気と混合後圧縮
機１７で再圧縮された後、その断熱圧縮熱を該溶剤抽出
蒸留塔１３のリボイラ１８の熱源として利用後、水供給
ライン２６より水を加えることにより水分離槽１９で水
抜出しライン２０、溶剤抜出しライン２１により不純物
を含む水と実質的に不純物を含まない溶剤に分離後、溶
剤還流ライン２２及び２３により溶剤を溶剤抽出蒸留塔
１３の頂部及び向流抽出塔１の底部に送って循環使用す
る。The overhead vapor (consisting of solvent and water and substantially free of alcohol) from the overhead vapor extraction line 16 of the solvent extraction distillation column 13 is mixed with the overhead vapor of the desolvation column 27 in the compressor 17. After being recompressed, its adiabatic compression heat is used as a heat source for the reboiler 18 of the solvent extraction distillation column 13, and then water is added from the water supply line 26 to the water separation line 19 for extracting water and the solvent extraction line 21. After separating into water containing impurities and a solvent containing substantially no impurities, the solvent is sent to the top of the solvent extraction distillation column 13 and the bottom of the countercurrent extraction column 1 by solvent reflux lines 22 and 23 for circulation.
溶剤抽出蒸留塔１３の塔頂と塔底の温度差は４〜１０℃
と小さく圧縮機１７の少ない圧縮比によりリボイラ１８
で熱交換可能で既存の蒸留法に較べて大幅にエネルギー
の節約ができる。なお溶剤還流ライン２３の溶剤は冷却
器５で熱を与えられ、溶剤加熱器２４で温度を調整後溶
剤供給ライン２５より向流抽出塔１の下部から供給され
る。The temperature difference between the top and bottom of the solvent extraction distillation column 13 is 4 to 10 ° C.
With a small compression ratio of the compressor 17, the reboiler 18
The heat can be exchanged and the energy can be saved significantly compared to the existing distillation method. The solvent in the solvent reflux line 23 is heated by the cooler 5, the temperature is adjusted by the solvent heater 24, and then the solvent is supplied from the lower part of the countercurrent extraction column 1 through the solvent supply line 25.
以下、本発明の実施例をあげて本発明を詳細に説明す
る。Hereinafter, the present invention will be described in detail with reference to Examples of the present invention.
〔実施例１〕 第２図に示すように模擬の不純物を含むアルコール水溶
液を原料供給ライン２より１kg／ｈの流量で向流抽出塔
（内径５０mm、高さ４ｍ）１の上部より、又、プロパン
溶剤を５kg／ｈの流量で下部の溶剤供給ライン２５より
供給し、向流抽出操作を温度１３０℃、圧力１００kg／
cm2Gで行った。[Example 1] As shown in FIG. 2, an aqueous alcohol solution containing simulated impurities was fed from a raw material supply line 2 at a flow rate of 1 kg / h from the upper part of a countercurrent extraction column (inner diameter 50 mm, height 4 m) 1, and Propane solvent is supplied from the lower solvent supply line 25 at a flow rate of 5 kg / h, and the countercurrent extraction operation is performed at a temperature of 130 ° C. and a pressure of 100 kg / h.
Performed in cm 2 G.
次に、向流抽出塔１の塔頂の溶剤相取出しライン４から
取出された溶剤相は熱交換器５で６０℃に冷却され、重
力沈降槽６で軽液と重液に分離し、重液は向流抽出塔１
上部へ重液還流ライン１１より全量還流させた。軽液は
圧力調整弁１０により圧力１００kg／cm2Gから圧力１９
kg／cm2Gに減圧後、抽出蒸留塔１３の中部へ導入され、
その塔頂の溶剤ライン２２よりプロパン溶剤を２．５kg
／ｈで供給し、プロパンによる抽出蒸留を行った。Next, the solvent phase taken out from the solvent phase taking-out line 4 at the top of the countercurrent extraction tower 1 is cooled to 60 ° C. in the heat exchanger 5, and is separated into the light liquid and the heavy liquid in the gravity settling tank 6, Liquid is countercurrent extraction tower 1
The entire amount was refluxed to the upper portion through the heavy liquid reflux line 11. The pressure of the light liquid is adjusted from 100kg / cm 2 G to 19 by the pressure control valve 10.
After reducing the pressure to kg / cm 2 G, it is introduced into the middle part of the extractive distillation column 13,
2.5 kg of propane solvent from the solvent line 22 at the top of the tower
/ H and subjected to extractive distillation with propane.
この結果、第２図に示すような物質収支となり、原料１
０wt% アルコールは、１次濃縮で８０wt% 、２次濃縮で
９５wt% 、最終の３次濃縮で９９．９wt%にまで濃縮さ
れ、不純物が殆ど分離された無水アルコールとプロパン
混合物が塔底混合液体取出しライン１４より得られた。As a result, the material balance shown in FIG.
0 wt% alcohol was concentrated to 80 wt% in the first concentration, 95 wt% in the second concentration, and 99.9 wt% in the final third concentration. Anhydrous alcohol and propane mixture in which impurities were almost separated were mixed in the bottom liquid mixture. Obtained from the take-out line 14.
次に、ライン１４より抜出された混合物を、圧力１７kg
／cm2Gの条件下で、第１図に示す脱溶剤塔２７で蒸留を
行なったところ、塔頂よりエタノール、水及びその他の
不純物が含まれないプロパンが、又塔底よりエタノール
１００に対しての組成比率が、水：０．１、メタノー
ル：０．０５、酢酸：０．０５、アセトアルデヒド：
０．０５、ｎ−プロパノール：０．０４、アセトン：
０．０のものが得られ、実質的にプロパン及び微量不純
物が分離されたエタノールを回収できた。Next, the mixture withdrawn from the line 14 has a pressure of 17 kg.
Distillation was carried out in the desolvation tower 27 shown in FIG. 1 under the condition of / cm 2 G. Ethanol, propane containing no water and other impurities from the top of the tower, and 100 parts of ethanol from the bottom of the tower. The composition ratios of all are water: 0.1, methanol: 0.05, acetic acid: 0.05, acetaldehyde:
0.05, n-propanol: 0.04, acetone:
0.0 was obtained, and ethanol in which propane and trace impurities were substantially separated could be recovered.
一方、アルコール損失は全工程を通じてみられなかっ
た。On the other hand, no alcohol loss was observed throughout the process.
又、抽出蒸留塔１３の塔頂及び塔底温度は各々５７℃及
び６１℃と小さく、塔頂ガスの再生縮熱を利用したヒー
トポンプシステムにとって非常に有利であり、圧縮機の
わずかな圧縮比によりリボイラ１８の熱源を全量捕える
ことが、プロセスシミュレーションにより確認され、全
工程の所要エネルギーは約８００kcal／kg・エタノール
となり、既存蒸留法の約 1/3〜1/5 の省エネルギーが達
せられることがわかった。Also, the top and bottom temperatures of the extractive distillation column 13 are as small as 57 ° C. and 61 ° C., respectively, which is very advantageous for a heat pump system utilizing the regenerative condensation heat of the overhead gas, and due to the slight compression ratio of the compressor, It was confirmed by a process simulation that all the heat sources of the reboiler 18 were captured, and it was found that the required energy for all the steps was about 800 kcal / kg · ethanol, and the energy saving of about 1/3 to 1/5 of the existing distillation method could be achieved. It was
本発明方法により、従来の方法では分離が困難であった
メタノール、酢酸、アセトアルデヒド、アセトン、プロ
パノールなどの不純物の分離が容易となる効果を奏す
る。The method of the present invention has the effect of facilitating the separation of impurities such as methanol, acetic acid, acetaldehyde, acetone and propanol, which were difficult to separate by conventional methods.
第１図は本発明の一実施態様の説明図、第２図は本発明
の一実施例の物質収支を示す説明図である。FIG. 1 is an explanatory diagram of an embodiment of the present invention, and FIG. 2 is an explanatory diagram showing a material balance of an embodiment of the present invention.
Claims (1)
／エタノール／不純物からなる混合物を向流抽出塔の上
部より、下部よりプロパン、プロピレン、ｎ−ブタン及
びｉ−ブタンよりなる群のうちの一つの溶剤を供給し、
向流抽出塔内を該溶剤の超臨界状態又は擬臨界状態に維
持するようにして両者を向流で接触させ、向流抽出塔上
部より濃縮アルコールを含んだ溶剤相を抜き出す一次脱
水工程、該溶剤相を冷却し、水分に富んだ重液相と濃縮
アルコールを含んだ軽液相に重力沈降分離し、該重液相
は前記向流抽出塔上部へ還流する二次脱水工程、該軽液
相の圧力を該溶剤の上記圧力以下に減圧後、溶剤抽出蒸
留塔に導入し、塔底より実質的に水分を含まないアルコ
ールと溶剤の塔底混合液体を、塔頂より実質的にアルコ
ールを含まない水分と溶剤の混合蒸気を各々抜き出す三
次脱水工程、該塔底混合液体を脱溶剤塔により溶剤とア
ルコールに分離する脱溶剤工程及び該脱溶剤塔の塔頂混
合蒸気と該溶剤抽出蒸留塔の塔頂蒸気を冷却後、水を加
えて実質的に不純物を含まない溶剤相と不純物が濃縮さ
れた水相に相分離させ、該溶剤相を該溶剤抽出蒸留塔の
塔頂及び該向流抽出塔の塔底へ循環することを特徴とす
るアルコールの濃縮精製方法。1. A mixture of water / ethanol / impurities produced by a fermentation method or a chemical synthesis method from the upper part of a countercurrent extraction column and from the lower part of a group consisting of propane, propylene, n-butane and i-butane. Supply one solvent of
A primary dehydration step of extracting the solvent phase containing concentrated alcohol from the upper part of the countercurrent extraction column by contacting them in countercurrent so as to maintain the supercritical state or pseudocritical state of the solvent in the countercurrent extraction column, A secondary dehydration step in which the solvent phase is cooled and gravity separated into a heavy liquid phase rich in water and a light liquid phase containing concentrated alcohol, and the heavy liquid phase is refluxed to the upper part of the countercurrent extraction column, the light liquid After reducing the pressure of the phase below the above-mentioned pressure of the solvent, it is introduced into a solvent extraction distillation column, a mixed liquid of a bottom of a solvent and an alcohol substantially free of water from the bottom, substantially alcohol from the top of the column. Tertiary dehydration step for extracting each of mixed vapor of water and solvent not containing, desolvation step for separating the column bottom mixed liquid into solvent and alcohol by a desolvation column, mixed vapor at the top of the desolvation column and the solvent extraction distillation column After cooling the top vapor of the Concentration of alcohol characterized by phase-separating into a solvent phase containing no and a water phase enriched with impurities, and circulating the solvent phase to the top of the solvent extraction distillation column and the bottom of the countercurrent extraction column. Purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322329A JPH0651085B2 (en) | 1990-11-28 | 1990-11-28 | Concentration and purification method of alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322329A JPH0651085B2 (en) | 1990-11-28 | 1990-11-28 | Concentration and purification method of alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04193304A JPH04193304A (en) | 1992-07-13 |
| JPH0651085B2 true JPH0651085B2 (en) | 1994-07-06 |
Family
ID=18142428
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2322329A Expired - Lifetime JPH0651085B2 (en) | 1990-11-28 | 1990-11-28 | Concentration and purification method of alcohol |
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| Country | Link |
|---|---|
| JP (1) | JPH0651085B2 (en) |
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- 1990-11-28 JP JP2322329A patent/JPH0651085B2/en not_active Expired - Lifetime
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