JPH0327336A - Dehydration of alcohol - Google Patents
Dehydration of alcoholInfo
- Publication number
- JPH0327336A JPH0327336A JP1160696A JP16069689A JPH0327336A JP H0327336 A JPH0327336 A JP H0327336A JP 1160696 A JP1160696 A JP 1160696A JP 16069689 A JP16069689 A JP 16069689A JP H0327336 A JPH0327336 A JP H0327336A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- alcohol
- column
- liquid 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.)
- Granted
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 230000018044 dehydration Effects 0.000 title claims description 9
- 238000006297 dehydration reaction Methods 0.000 title claims description 9
- 239000002904 solvent Substances 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 29
- 239000007791 liquid phase Substances 0.000 claims abstract description 28
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 15
- 239000001294 propane Substances 0.000 claims abstract description 11
- 230000005484 gravity Effects 0.000 claims abstract description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000638 solvent extraction Methods 0.000 claims abstract description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 208000005156 Dehydration Diseases 0.000 claims description 8
- 238000004807 desolvation Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000000895 extractive distillation Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- RYNHNIDEKCRWHJ-QFIPXVFZSA-N (2s)-2-[(2-methyl-3-oxo-5,7-dipropyl-1,2-benzoxazol-6-yl)oxy]-2-(4-propan-2-ylphenyl)acetic acid Chemical compound C1([C@@H](C(O)=O)OC2=C(CCC)C3=C(C(N(C)O3)=O)C=C2CCC)=CC=C(C(C)C)C=C1 RYNHNIDEKCRWHJ-QFIPXVFZSA-N 0.000 description 1
- 241000209134 Arundinaria Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- -1 cane Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 101150086272 cofG gene Proteins 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアルコールの精製濃縮方法に関し、合戊アルコ
ール、使用済アルコール水溶ηｋ及び発酵アルコール等
から高純度のアルコールを省エネルギー的に濃縮精製す
るのに適した方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for purifying and concentrating alcohol, and is a method for concentrating and purifying high-purity alcohol from synthetic alcohol, used alcohol aqueous solution ηk, fermented alcohol, etc. in an energy-saving manner. Regarding methods suitable for
甘しょ、さつまいも、とうもろこし等の炭水化物を原料
とする発酵アルコールは、飲利用及び工業用として重要
な出発原料であるが、発酵法で得られるアルコール水溶
液のアルコール濃度は１０〜２０ｗｔ％と低いため、約
９５〜１００ｗｔ％まで濃縮する必要がある。Fermented alcohol made from carbohydrates such as cane, sweet potato, and corn is an important starting material for drinking and industrial use, but the alcohol concentration of the alcohol aqueous solution obtained by the fermentation method is as low as 10 to 20 wt%. It is necessary to concentrate to about 95-100 wt%.
従来、この濃縮法として蒸留法が用いられてきたが、大
部分を占める水も８０〜１００℃まで昇温せねばならず
、経済的に不利であり、これに替わる省エネルギー型の
濃縮法の開発が望まれている。Conventionally, distillation has been used as a concentration method, but water, which makes up most of the water, must be heated to 80 to 100°C, which is economically disadvantageous, so there is a need to develop an energy-saving concentration method instead. is desired.
一方、省エネルギー型の濃縮法として超臨界状態又は擬
臨界状態の炭酸ガスを用いてアルコールを水より抽出・
分離して濃縮する方法が提案されている。（特開昭５６
−５６２０１及び同５９−１４１５２８号公報）
しかしながら、炭酸ガスを溶剤として用いた場合アルコ
ールの選択的抽出には限界があり、最大濃縮度は約９１
ｗｔ％が限界であり、これ以上に濃縮することは不可能
であることが最近報告されている。又、炭酸ガス中への
アルコールの溶解度は十分に大きくないことより、大量
の炭酸ガス（１０％アルコール水溶液１重量部に対して
１５重量部以上）を必要とするという問題点があり、そ
の改善が望まれている。On the other hand, as an energy-saving concentration method, alcohol can be extracted from water using carbon dioxide gas in a supercritical or quasi-critical state.
A method of separating and concentrating has been proposed. (Unexamined Japanese Patent Publication No. 56
-56201 and No. 59-141528) However, when carbon dioxide gas is used as a solvent, there is a limit to the selective extraction of alcohol, and the maximum concentration is approximately 91%.
It has recently been reported that wt% is the limit and it is impossible to concentrate beyond this limit. Furthermore, since the solubility of alcohol in carbon dioxide gas is not sufficiently high, there is a problem in that a large amount of carbon dioxide gas (15 parts by weight or more per 1 part by weight of a 10% alcohol aqueous solution) is required. is desired.
このため、現在、アルコールＩｌ１度を向上させかつア
ルコール溶解度を大きくできる方法が望まれている。For this reason, there is currently a need for a method that can improve the alcohol I1 degree and increase the alcohol solubility.
本発明は、アルコール濃縮度を９１ｗｔ％以上に向上で
き、かつアルコール溶解度が大きくでき少量の溶剤量で
アルコールを濃縮回収できる経済的なアルコール濃縮方
法を提供しようとするものである。The present invention aims to provide an economical method for concentrating alcohol that can improve alcohol concentration to 91 wt% or more, increase alcohol solubility, and concentrate and recover alcohol with a small amount of solvent.
すなわち、本発明は向流抽出格の上部よりアルコール及
び水を主戒分とする原判を下部よりプロパン、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′ａ＄１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′ａ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部臨界圧
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、及び該塔底混
合液体を蒸留操作により溶剤とアルコールに分離する脱
溶剤工程から紅ることを特徴とするアルコールの脱水方
法である。That is, in the present invention, a solvent containing alcohol and water as main components is supplied from the upper part of the countercurrent extractor, and one solvent from the group consisting of propane, propylene, n-butane, and i-butane is supplied from the lower part, Primary dehydration in which the solvent is kept in a supercritical or quasi-critical state in the countercurrent extraction column so that they are brought into contact with each other in countercurrent flow, and the solvent phase containing alcohol is extracted from the upper part of the countercurrent extraction column. Step, the solvent phase is cooled and separated by gravity sedimentation into a water-rich heavy liquid phase and a light liquid phase containing condensed alcohol, and the heavy liquid phase is refluxed to the upper part of the countercurrent extraction column for secondary dehydration. After reducing the pressure of the light liquid phase to below the upper critical pressure of the solvent, the light liquid phase is introduced into a solvent extraction distillation column, and the bottom mixed liquid of alcohol and solvent, which does not contain substantially water, is transferred from the bottom of the column to the top of the column. The alcohol is characterized by a tertiary dehydration step in which a mixed vapor of water and solvent that does not substantially contain alcohol is extracted, and a desolvation step in which the mixed liquid at the bottom of the column is separated into solvent and alcohol by a distillation operation. This is a dehydration method.
本発明は全てのアルコール水溶液のｓ ｉ！精ｓに適用
しつるものであるが、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、合或アルコールではアルコール濃度は
約２０ｗｔ％前後で残りは水である。The present invention is suitable for all alcohol aqueous solutions. As an example of fermented alcohol, the alcohol concentration is approximately 10 wt%, with the remainder being water. Further, in the case of combined alcohol, the alcohol concentration is around 20 wt%, with the remainder being 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 referred to in the present invention refers to the following.
プロピレン Ｃｓｌｌａ ９２ ４
５，６プロパン Ｃ，１１。 ！）６，８
４１．９ｎ−ブタン ｎ−Ｃｎｌｌ＋。 ｌ
５２．２ ３７．５ｉ １タンｉ−Ｃ＊ＩＬｏ
１３５．１ ：ｌ６， ０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及び臨界圧カＰ
ｃ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。Propylene Cslla 92 4
5,6 Propane C, 11. ! )6,8
41.9n-Butane n-Cnll+. l
52.2 37.5i 1tani-C*ILo
135.1: l6, 0 Also, the supercritical state of the solvent referred to in the present invention means that the critical temperature Tc and critical pressure P of the solvent are
A quasi-critical state is a state where the temperature and pressure are maintained at a temperature and pressure of 80°C or higher, and the quasi-critical state is a state where the temperature is below the critical temperature Tc but 80°C or higher, and the pressure is maintained at a level higher than the saturated vapor pressure of the solvent at that temperature. means.
以下、本発明の一実施例を第１図に従って詳述する。Hereinafter, one embodiment of the present invention will be described in detail with reference to FIG.
第１図において、ｌは向流抽出塔（充填塔、棚役塔又は
多投抽出堪などが好ましい。）、２は原料であるアルコ
ールを含む水溶液の原利供給ライン、３は抽出残液〈水
が主戒分）の取出しライン、４は溶剤相（溶剤と１次濃
縮γ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（水が主或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は溶剤紬出塔原利仇
給ライン、１３は溶剤抽出塔、ｌ４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１！Ｉ 整弁、ｌ６は塔頂蒸気（溶剤と水からな
る〉取出しライン、ｌ７は圧縮機、１８はりボイラー（
熱交換器） １９は水分離槽、２０は水抜出しライ
ン、２ｌ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は溶剤供給ラインである
。In Fig. 1, 1 is a countercurrent extraction column (preferably a packed column, tray column, or multi-throw extraction tank), 2 is a raw material supply line for an aqueous solution containing alcohol as a raw material, and 3 is an extraction residual liquid. 4 is a solvent phase (solvent and primary concentrated γ alcohol mixed phase) extraction line, 5 is a cooler, 6 is a gravity settling tank, 7 is a heavy liquid phase (water is a main component) 8 is the light liquid phase (containing a small amount of alcohol and solvent), and 8 is the light liquid phase (containing a small amount of alcohol and solvent).
9 is a liquid level adjustment valve for the heavy liquid in the gravity settling tank 6, 10 is a pressure adjustment valve for the gravity settling tank 6, 11 is a heavy liquid reflux line, 12 is a solvent supply line line, 13 is a solvent extraction column, 14 is a line for taking out the mixed liquid at the bottom of the column (consisting of anhydrous alcohol and solvent), and 15 is a column bottom liquid level of 1! I valve control, l6 is the top steam (consisting of solvent and water) extraction line, l7 is the compressor, 18 beam boiler (
Heat exchanger) 19 is a water separation tank, 20 is a water extraction line, 2l is a solvent extraction line, 22.23 is a solvent reflux line, 24 is a solvent heater, and 25 is a solvent supply line.
原料のアルコール水溶液１重量部を原利仇給ライン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。1 part by weight of an aqueous alcohol solution as a raw material is supplied to the countercurrent extraction column 1 from the raw material supply line 2 and 3 to 6 parts by weight of the solvent is supplied from the solvent supply line 25 to the countercurrent extraction column 1, and the solvent is converted into alcohol in a supercritical or pseudocritical state. By bringing it into countercurrent contact with the aqueous solution, the low-density solvent phase rises and selectively extracts alcohol from the alcohol aqueous solution, and is taken out as a light liquid through the solvent phase take-out line 4.
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ｌの好ましい摸作条件の範囲
を設定すべきである。At this time, as the temperature increases, the solubility of alcohol in the solvent increases, but conversely the selectivity of alcohol decreases, so the method of the present invention takes this point into consideration and adjusts the solubility according to the type of solvent used. A range of preferred operating conditions for the stream extraction column 1 should be established.
該向流抽出塔１では、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１次濃
縮すればよく、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 column 1, alcohol is almost completely extracted, and the extracted alcohol concentration only needs to be primarily concentrated to about 50 to 90 wt%.
The pressure should be above the saturated vapor pressure or above the critical pressure of the solvent used.
次に、溶剤鞘取出しライン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、重力分離槽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２次濃縮され
たアルコールを含有してい゛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むかった。Next, by cooling the solvent phase taken out from the solvent sheath take-out line 4 in the cooler 5, the heavy liquid phase from the heavy liquid phase take-out line 7 and the light liquid phase from the light liquid phase take-out line 8 are separated in the gravity separation tank 6. The liquid phase separates into a heavy liquid phase containing water as the main component and a small amount of alcohol and solvent, and a light liquid phase containing solvent as the main component and secondary concentrated alcohol. 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 difficult to concentrate beyond this.
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１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むり、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奸ましい。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ｌ１を介し核向流抽出塔ｌの上部付近へ
還流するのが奸ましい。The preferred pressure of the gravity settling tank 6 is the same as that of the countercurrent extraction column 1, and the preferred temperature must be lower than that of the primary dehydration step, but the temperature varies depending on the type of solvent. The alcohol concentration should be set to about 95 wt%, but ultimately it is advisable to optimize it from the overall thermal energy balance. The heavy liquid phase also includes a liquid level adjustment valve 9 to recover a small amount of alcohol and solvent;
It is preferable to reflux the heavy liquid to the vicinity of the upper part of the nuclear countercurrent extraction column 1 via the heavy liquid reflux line 11.
次に、前記軽液相は圧力ｍ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ｌ３に｛』（給される。Next, the light liquid phase is reduced in pressure to below the critical pressure of the solvent by a pressure regulating valve 10, and is fed to a solvent extractive distillation column 13.
溶剤抽出蒸留塔１３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より水分を実質的
に含まない飢水アルコールと溶剤の混合液体を塔頂蒸気
取出しラインｌ６よりアルコールを実質的に含まない水
分と溶剤の混合ガスを取出す。By supplying the solvent sent from the process described below from the solvent reflux line 22 at the upper part of the solvent extractive distillation column 13 to the solvent extractive distilling column 13 as an alcohol extraction material and performing extractive distillation, the "column bottom mixed liquid take-off line 14 A mixed liquid of alcohol and solvent that does not substantially contain water is taken out from the top steam extraction line 16 as a mixed gas of water and solvent that does not substantially contain alcohol.
該塔底混合液体取出しライン１４からの混合液体は、沸
点が大幅に異八る２戒分系（アルコールと溶剤）であり
通常の蒸留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
得られる。The mixed liquid from the bottom mixed liquid extraction line 14 is a two-component system (alcohol and solvent) with greatly different boiling points, and can be easily separated into anhydrous alcohol and solvent by ordinary distillation, and is substantially water-free. and solvent-free absolute alcohol are obtained.
溶剤抽出塔ｌ３においては、溶剤を、溶剤の蒸気と液が
共存する状態に保持し、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む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。In the solvent extraction column 13, the solvent is maintained in a state where the solvent vapor and liquid coexist, and when it is brought into contact with an alcohol aqueous solution under the conditions where the solvent vapor and liquid coexist, the alcohol is selectively extracted due to the difference in affinity. Under conditions where water is extracted with a solvent and a large amount of solvent is present in the liquid phase relative to the alcohol, water is hardly dissolved in the liquid phase and the water concentration in the solvent vapor phase falls below the saturation concentration of water. If you set conditions such that
Moisture can be selectively transferred to the solvent vapor phase.
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 this way, alcohol and water can be separated using a solvent, and anhydrous alcohol can be obtained.
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或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 coexist with the liquid in the extractive distillation column 13, the temperature must be below the critical temperature Tc of the solvent, and the pressure must be equal to the liquid phase composition at this temperature or the corresponding equilibrium vapor pressure (the maximum value is The critical pressure of the solvent should be Pc).
なお、溶剤還流ライン２２からの溶剤の量は溶剤抽出塔
原料供給ラインｌ２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？
，Ｃ量に決定されるべきである。Note that the amount of solvent from the solvent reflux line 22 should be changed depending on the alcohol concentration in the raw material from the solvent extraction column raw material supply line 12 and the product alcohol concentration, Is it economical due to the chemical engineering method like general distillation due to the number of stages?
, C amount should be determined.
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、圧縮機１７で再圧縮された後、その断熱圧縮熱
を、該抽出蒸留塔１３のリボイラー１８の熱源として利
用後、水分ｆｉ槽１９で水抜出しライン２０、溶剤抜出
しライン２１により水と溶剤に分離後、溶剤還流ライン
２２及び２３により溶剤を循環使用する。The overhead vapor (consisting of solvent and water and substantially free of alcohol) from the overhead vapor take-off line 16 of the extractive distillation column 13 is recompressed in the compressor 17, and then its heat of adiabatic compression is transferred to the After being used as a heat source for the reboiler 18 of the extractive distillation column 13, water and solvent are separated in the water fi tank 19 through a water withdrawal line 20 and a solvent withdrawal line 21, and then the solvent is circulated and used through solvent reflux lines 22 and 23.
抽出蒸留塔１３の塔頂と塔底の温度差は４〜１０℃と小
さく圧１１機ｌ７の少ない圧縮比によりリボイラー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。The temperature difference between the top and bottom of the extractive distillation column 13 is 4 to 10°C, and the reboiler 18
This allows for heat exchange, resulting in significant energy savings compared to existing distillation methods.
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、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 solvent in the solvent reflux line 23 is given heat by the cooler 5, and after its temperature is adjusted by the heater 24, it 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 explained in detail by giving examples of the present invention.
（実施例ｌ）
第２図に示すように、アルコールｌＯｗｔ％、水９０ｗ
ｔ％からなる原利を原利供給ライン２より１ ｋｇ ／
ｈの流量で向流抽出塔〈内径５０＋ｎｍ、高さ４ｍ）
１の上部より、又、プロパン溶剤を５ ｋｇ ／ ｈの
流量で下部の溶剤イ』（給ライン２５より供給し、向流
抽出操作を温度１３０℃、圧力１ ０ ０ ｋｇ／ｃｄ
Ｇで行った。(Example 1) As shown in Figure 2, alcohol 10wt%, water 90w
1 kg/1 kg of raw material consisting of t% from raw material supply line 2
Countercurrent extraction column with a flow rate of h (inner diameter 50+nm, height 4m)
Propane solvent was supplied from the upper part of No. 1 at a flow rate of 5 kg/h to the lower solvent No. 1 (supply line 25), and the countercurrent extraction operation was carried out at a temperature of 130°C and a pressure of 100 kg/cd.
I went with 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、重液は向流抽出塔上
部へ重液還流ラインｌ１より全量還流させた。軽液は圧
力調整弁ＩＯにより圧力１ ０ ０ ｋｇ／ｃｏｆＧか
ら圧力１９ｋｇ ／ ａ＋ｆ Ｇ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 take-off line 4 at the top of the countercurrent extraction tower 1 is cooled to 60°C in a heat exchanger 5, separated into a light liquid and a heavy liquid in a gravity settling tank 6, and then separated into a heavy liquid and a heavy liquid. The entire amount of the liquid was refluxed to the upper part of the countercurrent extraction tower through the heavy liquid reflux line 11. After reducing the pressure of the light liquid from 100 kg/cofG to 19 kg/a+fG by the pressure regulating valve IO, it is introduced into the middle of the extractive distillation column 13, and 2.5 kg/cof of propane solvent is introduced from the solvent line 22 at the top of the column. Extractive distillation with propane was carried out.
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９ ９． ９ ｗｔ
％にまで濃縮され、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ｌ４より得られた。As a result, the material balance is as shown in Figure 2, and the raw material 1
0wt% alcohol is 80wt% in the first concentration, 95wt% in the second concentration, and 9% in the final tertiary concentration.9. 9wt
%, and a mixture of absolute alcohol and propane was obtained from the bottom mixed liquid take-off line 14.
無水アルコールとブロバンは共沸点がなく、又沸点差が
大きく通常の蒸留操作により完全に分離できた。Anhydrous alcohol and broban have no azeotropic point and have a large difference in boiling point, so they can be completely separated by normal distillation.
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 entire 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、塔頂ガスの再圧縮熱を利用したヒー
トボンプシステムにとって非常に有利であり、圧縮機の
わすかむ圧縮比によりリボイラーの熱源を全量補入るこ
とが、プロセスシミュレーションによりＷｔ ＫＢされ
、全工程の所要エネルギーは約８ ０ ０ ｋｃａｌ／
ｋｇ ・エタノールとなり、既存蒸留法の約１７３
〜１／５の省エネルギーが達せられることがわかった。In addition, the top and bottom temperatures of the extractive distillation column 13 are as low as 57°C and 61°C, respectively, which is very advantageous for a heat pump system that utilizes the heat of recompression of the top gas, and the low compression ratio of the compressor. According to the process simulation, the total amount of heat source for the reboiler is supplemented by Wt KB, and the energy required for the entire process is approximately 800 kcal/
kg ・Ethanol, which is approximately 173 kg compared to the existing distillation method.
It was found that an energy saving of ~1/5 can be achieved.
（実施例２）
実施例１において、溶剤としてプロパンの他にプロピレ
ン、ｎ−ブタン及びｉ−ブタンを用い、向流抽出塔、重
力沈降槽、抽出蒸留塔の温度、圧力を変えた試験を行な
い、好ましい温度及び圧力の範囲を把題した。(Example 2) In Example 1, a test was conducted using propylene, n-butane, and i-butane in addition to propane as the solvent, and changing the temperature and pressure of the countercurrent extraction column, gravity settling tank, and extractive distillation column. , the preferred temperature and pressure ranges have been summarized.
（比較例）
実施例ｌにおいて、溶剤としてＣ０１、エタン、ｎ−へ
キサン、ベンゼンを用いた試験を行なったが、表２に示
すように無水アルコールは得られむかった。(Comparative Example) In Example 1, a test was conducted using C01, ethane, n-hexane, and benzene as solvents, but as shown in Table 2, it was difficult to obtain anhydrous alcohol.
本発明は以上詳記したようにアルコール演度１０〜２０
ｗｔ％の水溶液から水分を分離して無水アルコールを製
造するに際し、特定の溶剤（プロピレン、プロパン、ｎ
−ブタン、ｉ−ブタン）を用い、その溶剤としての特定
の特性を温度、圧力を変化させ巧みに利用すにことによ
り１次、２次、及び３次濃縮を行ない、容易に専売法及
びＪＩＳ規格を満Ｉこすアルコール濃度（９９．２ｗｔ
％以上の無水アルコールが得られ、かつ、既存の蒸留法
に較べて、溶剤の圧縮熱をリボイラー熱源に利用するヒ
ートボンブシステムにより大幅な省エネルギーができる
という効果を奏する。As detailed above, the present invention has an alcohol content of 10 to 20.
When producing anhydrous alcohol by separating water from a wt% aqueous solution, certain solvents (propylene, propane, n
-butane, i-butane), and by skillfully utilizing its specific properties as a solvent by changing temperature and pressure, it is possible to perform primary, secondary, and tertiary concentration, easily complying with the proprietary method and JIS. Alcohol concentration that meets the standard (99.2wt)
% or more of anhydrous alcohol can be obtained, and compared to existing distillation methods, the heat bomb system uses the compression heat of the solvent as a reboiler heat source, resulting in significant energy savings.
第１図は本発明を実施するためのプロセスフロー、第２
図は実施例１の結果を示すプロセスフロー及び物質収支
を示す図である。Figure 1 is a process flow for implementing the present invention;
The figure is a diagram showing the process flow and material balance showing the results of Example 1.
Claims (1)
とする原料を下部よりプロパン、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部臨界圧力以下に減圧後、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、及び該塔底混合液体を蒸留操作に
より溶剤とアルコールに分離する脱溶剤工程からなるこ
とを特徴とするアルコールの脱水方法。(1) A raw material mainly consisting of alcohol and water is supplied from the upper part of the counter-current extraction tower, and one solvent from the group consisting of propane, propylene, n-butane, and i-butane is supplied from the lower part of the counter-current extraction tower. A primary dehydration step in which the solvent phase is brought into contact with each other in a countercurrent state while maintaining the inside of the solvent in a supercritical state or a quasi-critical state, and a solvent phase containing concentrated alcohol is extracted from the upper part of the countercurrent extraction column, and the solvent phase is cooled. Then, a heavy liquid phase rich in moisture and a light liquid phase containing concentrated alcohol are separated by gravity sedimentation, and the heavy liquid phase is refluxed to the upper part of the countercurrent extraction column in a secondary dehydration step, in which the pressure of the light liquid phase is reduced. After reducing the pressure to below the upper critical pressure of the solvent, it is introduced into a solvent extraction distillation column, and the bottom mixed liquid of alcohol and solvent, which does not contain substantially water, is transferred from the bottom of the column, and water, which does not contain substantially alcohol, is transferred from the top of the column. 1. A method for dehydrating alcohol, comprising a tertiary dehydration step in which a mixed vapor of and a solvent is extracted, and a desolvation step in which the mixed liquid at the bottom of the column is separated into a solvent and alcohol by a distillation operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1160696A JPH0327336A (en) | 1989-06-26 | 1989-06-26 | Dehydration of alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1160696A JPH0327336A (en) | 1989-06-26 | 1989-06-26 | Dehydration of alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0327336A true JPH0327336A (en) | 1991-02-05 |
| JPH0536418B2 JPH0536418B2 (en) | 1993-05-31 |
Family
ID=15720494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1160696A Granted JPH0327336A (en) | 1989-06-26 | 1989-06-26 | Dehydration of alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0327336A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0728721A2 (en) * | 1995-02-24 | 1996-08-28 | Mitsui Toatsu Chemicals, Inc. | Process for producing isopropyl alcohol |
| SG50572A1 (en) * | 1995-02-24 | 2003-07-18 | Mitsui Chemicals Inc | Process for producing isopropyl alcohol |
| JP2008299224A (en) * | 2007-06-01 | 2008-12-11 | Kyoritsu Denki Kk | Vibration method for evaluating camera shake correcting function |
| CN102040471A (en) * | 2010-11-16 | 2011-05-04 | 广东中科天元新能源科技有限公司 | Distillation dehydration device and process for co-producing ethanol fuels and custom grade edible alcohols |
| WO2016080531A1 (en) * | 2014-11-20 | 2016-05-26 | 国立大学法人名古屋大学 | Method for concentrating and dehydrating butanol |
-
1989
- 1989-06-26 JP JP1160696A patent/JPH0327336A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0728721A2 (en) * | 1995-02-24 | 1996-08-28 | Mitsui Toatsu Chemicals, Inc. | Process for producing isopropyl alcohol |
| EP0728721A3 (en) * | 1995-02-24 | 1997-01-22 | Mitsui Toatsu Chemicals | Process for producing isopropyl alcohol |
| US5763693A (en) * | 1995-02-24 | 1998-06-09 | Mitsui Chemicals, Inc. | Process for producing isopropyl alcohol |
| SG50572A1 (en) * | 1995-02-24 | 2003-07-18 | Mitsui Chemicals Inc | Process for producing isopropyl alcohol |
| JP2008299224A (en) * | 2007-06-01 | 2008-12-11 | Kyoritsu Denki Kk | Vibration method for evaluating camera shake correcting function |
| CN102040471A (en) * | 2010-11-16 | 2011-05-04 | 广东中科天元新能源科技有限公司 | Distillation dehydration device and process for co-producing ethanol fuels and custom grade edible alcohols |
| WO2016080531A1 (en) * | 2014-11-20 | 2016-05-26 | 国立大学法人名古屋大学 | Method for concentrating and dehydrating butanol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0536418B2 (en) | 1993-05-31 |
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