JPH0529481B2 - - Google Patents
Info
- Publication number
- JPH0529481B2 JPH0529481B2 JP1003770A JP377089A JPH0529481B2 JP H0529481 B2 JPH0529481 B2 JP H0529481B2 JP 1003770 A JP1003770 A JP 1003770A JP 377089 A JP377089 A JP 377089A JP H0529481 B2 JPH0529481 B2 JP H0529481B2
- Authority
- JP
- Japan
- Prior art keywords
- butane
- alcohol
- solvent
- line
- butane solvent
- 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
Links
- 239000001273 butane Substances 0.000 claims description 90
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 90
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 81
- 239000002904 solvent Substances 0.000 claims description 72
- 238000004821 distillation Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 9
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 208000029650 alcohol withdrawal Diseases 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 description 15
- 239000012071 phase Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- -1 amashiyo Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 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
- 238000001816 cooling Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Extraction Or Liquid Replacement (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Description
〔産業上の利用分野〕
本発明はアルコールの精製濃縮方法及びその装
置に関し、合成アルコール、食品工業における使
用済アルコール水溶液及び特に発酵アルコール等
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及び装置に関する。
〔従来の技術〕
甘しよ、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、飲料用及び工
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。
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。
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91wt％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。
このため、現在、アルコール濃縮度を向上さ
せ、かつ、アルコール溶解度を大きくできる方法
及び装置が望まれている。
〔発明が解決しようとする課題〕
本発明はアルコール濃縮度を91wt％以上に向
上でき、かつ、アルコール溶解度を大きくでき少
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及び装置を提供しようとす
るものである。
〔課題を解決するための手段〕
すなわち、本発明は
(1) 向流接触装置中部の原料供給口より、アルコ
ール水溶液を供給し、該向流接触装置の下部よ
りブタン溶剤を供給し、該原料供給口より下部
においてはブタン溶剤を超臨界状態又は擬臨界
状態に保持し、該原料供給口より上部において
はブタン溶剤を液体状態に保持することによ
り、該向流接触装置上部より実質的に水分が分
離された濃縮アルコールを含んだブタン溶剤相
を抜き出し、これをブタン溶剤加圧蒸留塔に導
入し、該塔底により実質的に水分を含まずアル
コールを含むブタン液体を回収し、一方塔頂よ
り実質的にアルコールを含まず水分を含むブタ
ン気体を回収し、該ブタン気体を加圧後その圧
縮熱を該ブタン溶剤加圧蒸留塔の熱源に用いる
とともに、その一部は該ブタン溶剤加圧蒸留塔
へ還流し、他の残部は前記向流接触装置の上部
流体と間接熱交換後、前記向流接触装置の下部
に再び導入することを特徴とするアルコールの
濃縮精製方法、及び
(2) 中部にアルコール水溶液の供給ライン、底部
に重液取出ライン、頂部に軽液取出ラインが設
けられ、かつ上部より下部の分散器に超臨界状
態又は擬臨界状態のブタン溶剤を導く熱交換器
の作用を有するブタン溶剤供給ラインを内蔵し
た向流接触装置、前記軽液取出ラインと減圧弁
を介して連結し、頂部にブタン溶剤取出ライ
ン、底部に濃縮アルコール取出ラインを設けた
ブタン溶剤加圧蒸留塔及び前記ブタン溶剤取出
ラインを昇圧機並びに前記ブタン溶剤加圧蒸留
塔の塔底を介して前記向流接触装置のブタン溶
剤供給ラインと接続するラインよりなることを
特徴とするアルコール濃縮精製装置
である。
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、本発明で云うブタンの超臨界状態とは、臨
界温度Tc＝152℃、臨界圧力Pc＝37atm以上の温
度及び圧力に維持した状態であり、ブタンの擬臨
界状態とはその臨界温度Tc以下ではあるが約90
℃以上の温度であり、圧力はその温度におけるブ
タンの飽和蒸気圧以上に保持した状態を云う。
又、本発明に云うブタンの液体状態とは、70℃
以下の温度で、圧力はその温度における飽和蒸気
圧以上に保持した状態を云う。
以下、本発明の一実施態様を第１図に従つて詳
述する。
第１図において、１は向流接触装置（このもの
は、充填塔、棚段塔又は多段抽出塔であることが
好ましい。）、２は原料であるアルコールを含む水
溶液の供給ライン、３はブタン溶剤の供給ライ
ン、４は向流接触装置１の下部の重液（水が主成
分）の取出しライン、５は向流接触装置１の上部
の軽液（ブタン溶剤と濃縮アルコール分）の取出
しライン、６は原料供給ライン２より上部でアル
コール濃縮部、７は原料供給ライン２より下部で
アルコール回収部、８はブタン溶剤供給ラインで
熱交換器でもあり、９はブタン溶剤出口の分散
器、１０は減圧弁、１１はブタン溶剤加圧蒸留
塔、１２はブタン溶剤取出ライン、１３は濃縮ア
ルコール取出ライン、１４は昇圧機、１５はブタ
ン溶剤加圧蒸留塔加熱器、１６はバイパスライ
ン、１７はブタン溶剤の還流ライン、１８はブタ
ン溶剤供給ライン３と接続するブタン溶剤ライン
である。
原料のアルコール水溶液１重量部を原料供給ラ
イン２より、又ブタン溶剤３〜６重量部を供給ラ
イン３より向流接触装置１に供給し、該ブタン溶
剤は超臨界状態又は擬臨界状態で回収部７にてア
ルコール水溶液と向流接触させることにより、密
度の低いブタン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、軽液取
出レライン５により軽液として取り出される。
本発明者は回収部７においてはブタン溶剤を超
臨界状態又は擬臨界状態に保持することにより、
アルコールのブタンへの溶解度が大巾に向上し、
重液抜出しライン４からのアルコールの損失を防
止するに必要なブタン溶剤の使用量を大巾に低減
できることを見出した。
この回収部７においては、温度は約90℃〜200
℃が好ましく、最も好ましい温度は100〜170℃で
ある。圧力は50atm以上が好ましいが、最も好ま
しくは60〜200atmである。これ以上の圧力では
装置コストの増大となり好ましくない。
次に、本発明者はブタン溶剤相をアルコール濃
縮部６において、冷却用熱交換器８にて冷却する
ことにより水分が選択的にブタン溶剤相より相分
離し、濃縮部６を重液となつて下降し、ブタン溶
剤相中のアルコール濃度が95〜97wt％（ブタン
のない状態）まで濃縮されることを見出した。
濃縮部６では、ブタン溶剤を液体状態とする温
度、圧力が必要である。温度は10〜70℃が好まし
いが、最も好ましくは10〜60℃であり、温度が低
い程好ましい。圧力は回収部７と同等の条件が好
ましい。
一方、軽液抜出しライン５の軽液は、ブタン溶
剤及び濃縮アルコールからなつており、減圧弁１
０で減圧後ブタン溶剤加圧蒸留塔１１に導入さ
れ、ブタン溶剤と濃縮アルコールに分離され、濃
縮アルコールはライン１３より取り出され、実質
的にアルコールが含まれないブタン溶剤１２は昇
圧機１４で再加圧される。
該ブタン溶剤加圧蒸留塔１１の圧力は５〜
35atm、温度は10〜150℃の範囲が好ましい。又
化学工学の分野で公知のように、該蒸留塔１１は
棚段又は／及び充填物層とし、ライン１７よりブ
タン溶剤相の一部を該蒸留塔１１の上部に還流さ
せることにより、濃縮アルコールとブタンの分離
性能を向上させることが好ましい。
昇圧機１４で加圧されたブタンは断熱圧縮のた
めに温度レベルが上昇するので熱交換器１５によ
りブタン溶剤加圧蒸留塔１１の熱源として有効に
利用することができる。
１部のブタンは温度調整のためバイパスライン
１６を通り、ライン１８で連結される。
ライン１８の温度は10〜80℃であり、前記向流
接触装置１のブタン溶剤供給ライン３に連結し、
該向流接触装置１内の軽液相と向流で間接熱交換
するように熱交換器８を設け、その出口９を該向
流接触装置１の底部に設けることにより、濃縮部
６を冷却しアルコール濃縮効果が十分に行なえる
ようにする。
該熱交換器８は向流接触装置１の詳細図である
第２図に示すように蛇管の形状が好ましく、濃縮
部６で密に、回収部７で疎にするとより好ましい
温度条件にすることができる。即ち、濃縮部６で
は10〜70℃、回収部７で90〜170℃の温度にする
ことができる。なお、第２図中、１９は向流接触
装置１内の充填物のサポート、２０は原料アルコ
ール水溶液の分散器である。
以下、本発明の実施例をあげて本発明を詳細に
説明する。
実施例 １
アルコール10wt％、水90wt％からなる原料１
重量部を、内径50mm、長さ７ｍの充填塔形式の向
流接触装置の上部より３ｍの部分に供給し、又ブ
タン溶剤を該装置の底部より２〜10重量の範囲で
供給し、回収部７の温度を種々変化させた試験を
行ない、該装置の塔頂及び塔底のアルコール濃度
を分析し、表１の結果を得た。なお濃縮部６の温
度は40℃とした。
アルコール回収率は、既存の蒸留法の99wt％
を基準とし、99wt％以上を合格（○印）、95wt％
以下を不合格（×）、96wt％以上であるが99wt％
以下をやや合格（△印）とした。
本結果より、次のことが見出された。
ブタン溶剤を用いることにより、回収部７の温
度を90〜200℃、好ましくは100〜170℃とするこ
とによりブタン溶剤量が大巾に低減できた。（10
％アルコール水溶液１重量部に対し３重量部で十
分であつた。）
圧力は50〜300atmの範囲で十分であつた。
[Industrial Application Field] The present invention relates to a method and apparatus for purifying and concentrating alcohol, and is suitable for concentrating and refining high-purity alcohol from synthetic alcohol, aqueous solutions of used alcohol in the food industry, and especially fermented alcohol in an energy-saving manner. The present invention relates to a method and apparatus. [Prior art] Fermented alcohol made from carbohydrates such as amashiyo, sweet potato, and corn is an important starting material for beverages and industrial use, but the alcohol concentration of the alcohol aqueous solution obtained by the fermentation method is 10 to 10.
Since it is low at 20wt%, it is necessary to concentrate it to about 95-100wt%. 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.Therefore, an alternative energy-saving concentration method has been developed. is desired. On the other hand, as an energy-saving concentration method, a method has been proposed in which alcohol is extracted and separated from water using carbon dioxide gas in a supercritical or quasi-critical state and then concentrated. (JP-A-56-56201 and JP-A 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 limited to 91wt%. It has recently been reported that it is not possible to concentrate. Also, since the solubility of alcohol in carbon dioxide gas is not large enough, a large amount of carbon dioxide gas (10%
There is a problem that 15 parts by weight or more is required for 1 part by weight of the alcohol aqueous solution, and an improvement is desired. For this reason, there is currently a need for a method and apparatus that can improve alcohol concentration and increase alcohol solubility. [Problems to be Solved by the Invention] The present invention provides an economical method and apparatus for concentrating alcohol that can increase alcohol concentration to 91 wt% or more, increase alcohol solubility, and concentrate and recover alcohol with a small amount of solvent. This is what I am trying to do. [Means for Solving the Problems] That is, the present invention provides (1) supplying an alcohol aqueous solution from the raw material supply port in the middle of the countercurrent contactor, supplying a butane solvent from the lower part of the countercurrent contactor, and supplying the raw material By keeping the butane solvent in a supercritical or quasi-critical state below the supply port and in a liquid state above the raw material supply port, water is substantially removed from the top of the countercurrent contactor. The separated butane solvent phase containing concentrated alcohol is extracted and introduced into a butane solvent pressurized distillation column, and a substantially water-free and alcohol-containing butane liquid is recovered at the bottom of the column, while a butane liquid containing alcohol is recovered at the top of the column. Butane gas that does not substantially contain alcohol and contains water is recovered, and after pressurizing the butane gas, the heat of compression is used as a heat source for the butane solvent pressurizing distillation column, and a part of it is used as a heat source for the butane solvent pressurizing distillation column. (2) A method for concentrating and purifying alcohol, which is characterized in that the alcohol is refluxed to a distillation column, and the remainder is reintroduced into the lower part of the countercurrent contactor after indirect heat exchange with the upper fluid of the countercurrent contactor; and (2) The action of a heat exchanger that is equipped with an alcohol aqueous solution supply line in the middle, a heavy liquid take-out line at the bottom, and a light liquid take-out line at the top, and which guides butane solvent in a supercritical or quasi-critical state from the top to the lower disperser. a countercurrent contactor with a built-in butane solvent supply line, a butane solvent pressurized distillation column connected to the light liquid withdrawal line via a pressure reducing valve, and provided with a butane solvent withdrawal line at the top and a concentrated alcohol withdrawal line at the bottom. and a line connecting the butane solvent take-off line to the butane solvent supply line of the countercurrent contactor via a pressure booster and the bottom of the butane solvent pressurized distillation column. . The present invention can be applied to the concentration and purification of all aqueous alcohol solutions, but as an example, in the case of fermented alcohol, the alcohol concentration is approximately
It is around 10wt% and the rest is water. Furthermore, the supercritical state of butane referred to in the present invention is a state maintained at a temperature and pressure of critical temperature Tc = 152°C and critical pressure Pc = 37 atm or higher, and the quasi-critical state of butane is a state maintained at a temperature and pressure equal to or higher than its critical temperature Tc. But about 90
℃ or above, and the pressure is maintained above the saturated vapor pressure of butane at that temperature. In addition, the liquid state of butane referred to in the present invention is 70°C.
At the following temperatures, the pressure is maintained above the saturated vapor pressure at that temperature. Hereinafter, one embodiment of the present invention will be described in detail with reference to FIG. In FIG. 1, 1 is a countercurrent contactor (preferably a packed column, plate column, or multistage extraction column), 2 is a supply line for an aqueous solution containing alcohol as a raw material, and 3 is a butane reactor. Solvent supply line, 4 is a heavy liquid (main component water) take-out line at the bottom of the counter-current contact device 1, 5 is a light liquid (butane solvent and concentrated alcohol) take-out line at the top of the counter-current contact device 1 , 6 is an alcohol concentration section above the raw material supply line 2, 7 is an alcohol recovery section below the raw material supply line 2, 8 is a butane solvent supply line which is also a heat exchanger, 9 is a disperser at the butane solvent outlet, 10 1 is a pressure reducing valve, 11 is a butane solvent pressure distillation column, 12 is a butane solvent extraction line, 13 is a concentrated alcohol extraction line, 14 is a pressure booster, 15 is a butane solvent pressure distillation column heater, 16 is a bypass line, and 17 is a A butane solvent reflux line 18 is a butane solvent line connected to the butane solvent supply line 3. 1 part by weight of an aqueous alcohol solution as a raw material is supplied from a raw material supply line 2, and 3 to 6 parts by weight of a butane solvent is supplied from a supply line 3 to a countercurrent contactor 1, and the butane solvent is supplied to the recovery section in a supercritical or pseudocritical state. By bringing it into countercurrent contact with the alcohol aqueous solution at step 7, the low-density butane solvent phase rises while selectively extracting alcohol from the alcohol aqueous solution, and is taken out as a light liquid through the light liquid extraction line 5. The present inventor maintains the butane solvent in a supercritical state or a quasi-critical state in the recovery section 7.
The solubility of alcohol in butane is greatly improved,
It has been found that the amount of butane solvent required to prevent loss of alcohol from the heavy liquid extraction line 4 can be significantly reduced. In this recovery section 7, the temperature is approximately 90°C to 200°C.
℃ is preferred, and the most preferred temperature is 100-170℃. The pressure is preferably 50 atm or higher, most preferably 60 to 200 atm. A pressure higher than this is undesirable because it increases the cost of the device. Next, the present inventor cooled the butane solvent phase in the alcohol concentrating section 6 with a cooling heat exchanger 8, whereby water was selectively separated from the butane solvent phase, and the concentrating section 6 became a heavy liquid. It was found that the alcohol concentration in the butane solvent phase was concentrated to 95-97 wt% (without butane). In the concentration section 6, a temperature and pressure are required to turn the butane solvent into a liquid state. The temperature is preferably 10 to 70°C, most preferably 10 to 60°C, and the lower the temperature is, the more preferable it is. It is preferable that the pressure be the same as in the recovery section 7. On the other hand, the light liquid in the light liquid extraction line 5 consists of butane solvent and concentrated alcohol, and the light liquid in the light liquid extraction line 5 is composed of a butane solvent and concentrated alcohol.
After the pressure is reduced at 0, the butane solvent is introduced into the pressurized distillation column 11 and separated into butane solvent and concentrated alcohol.The concentrated alcohol is taken out from the line 13, and the butane solvent 12, which does not substantially contain alcohol, is recycled in the booster 14. Pressurized. The pressure of the butane solvent pressurized distillation column 11 is 5~
35 atm and a temperature range of 10 to 150°C are preferred. Also, as is known in the field of chemical engineering, the distillation column 11 is configured with trays and/or packed beds, and a portion of the butane solvent phase is refluxed through line 17 to the top of the distillation column 11 to produce concentrated alcohol. It is preferable to improve the separation performance of and butane. Since the temperature level of the butane pressurized by the pressure booster 14 increases due to adiabatic compression, it can be effectively used as a heat source for the butane solvent pressurized distillation column 11 by the heat exchanger 15. A portion of the butane passes through a bypass line 16 for temperature regulation and is connected by line 18. The temperature of the line 18 is 10-80°C, and it is connected to the butane solvent supply line 3 of the countercurrent contactor 1;
A heat exchanger 8 is provided to perform indirect heat exchange in countercurrent with the light liquid phase in the countercurrent contactor 1, and an outlet 9 of the heat exchanger 8 is provided at the bottom of the countercurrent contactor 1 to cool the concentration section 6. to ensure that the alcohol concentration effect is sufficient. As shown in FIG. 2, which is a detailed view of the countercurrent contacting device 1, the heat exchanger 8 preferably has a spiral tube shape, and it is preferable to make the heat exchanger 8 dense in the concentration section 6 and sparse in the recovery section 7 to achieve more preferable temperature conditions. I can do it. That is, the concentration section 6 can have a temperature of 10 to 70°C, and the recovery section 7 can have a temperature of 90 to 170°C. In FIG. 2, reference numeral 19 indicates a support for the packing in the countercurrent contact device 1, and reference numeral 20 indicates a disperser for the raw alcohol aqueous solution. Hereinafter, the present invention will be explained in detail by giving examples of the present invention. Example 1 Raw material 1 consisting of 10wt% alcohol and 90wt% water
The weight part is supplied to a part 3 m from the top of a packed column-type countercurrent contacting device with an inner diameter of 50 mm and a length of 7 m, and a butane solvent is supplied in a range of 2 to 10 parts by weight from the bottom of the device. Tests were carried out by varying the temperature of Example 7, and the alcohol concentrations at the top and bottom of the apparatus were analyzed, and the results shown in Table 1 were obtained. Note that the temperature of the concentration section 6 was 40°C. Alcohol recovery rate is 99wt% compared to existing distillation method
is the standard, passing 99wt% or higher (○ mark), 95wt%
Fail the following (×), 96wt% or more but 99wt%
The following were considered somewhat acceptable (marked △). From this result, the following was discovered. By using a butane solvent, the amount of butane solvent could be significantly reduced by setting the temperature of the recovery section 7 to 90 to 200°C, preferably 100 to 170°C. (Ten
3 parts by weight per 1 part by weight of the % alcohol aqueous solution was sufficient. ) A pressure range of 50 to 300 atm was sufficient.
【表】
実施例 ２
実施例１に説明した向流接触装置を用い、同じ
アルコール原料１重量部に対し、ブタン溶剤を３
重量部供給し、回収部７の圧力は濃縮部６の圧力
と同じにし、温度を120℃とし、濃縮部の温度を
種々変化させた試験を行ない、表２の結果を得
た。
塔頂の溶剤相中のアルコール濃度が含水アルコ
ール製品の基準である約95wt％以上の場合を合
格（○印）と判定した。
この結果、濃縮部の温度は10〜70℃とすること
により、95wt％以上の含水アルコールに濃縮で
きることが見出された。[Table] Example 2 Using the countercurrent contactor described in Example 1, 3 parts of butane solvent was added to 1 part by weight of the same alcohol raw material.
A test was conducted in which parts by weight were supplied, the pressure in the recovery part 7 was the same as the pressure in the concentrating part 6, and the temperature was 120° C., and the temperature in the concentrating part was varied variously, and the results shown in Table 2 were obtained. When the alcohol concentration in the solvent phase at the top of the column was approximately 95 wt% or higher, which is the standard for hydroalcoholic products, it was judged as passing (marked with an ○). As a result, it was found that by setting the temperature of the concentrating section to 10 to 70°C, it was possible to concentrate to 95 wt% or more of hydrous alcohol.
【表】
実施例 ３
以下、第１図に示したフローに従つた具体的な
実例をあげる。
アルコール10wt％、水90wt％からなる原料１
重量部を、内径50mm、長さ７ｍで３mmのデイクソ
ンパツキンを充填した充填塔形式の向流接触装置
１の上部より３ｍの部分にライン２より供給し、
又ブタン溶剤を該装置１の上部のライン３より２
〜10重量部の範囲で蛇管８を経由して、該装置１
の底部の分散器９より供給し、該装置１の塔頂か
ら圧力制御弁１０で圧力を100Kg／cm2Ｇに調節し
ながらブタン溶剤相をブタン溶剤加圧蒸留塔１１
に導入した。
ブタン溶剤加圧蒸留塔１１は内径100mm、長さ
５ｍで３mmのデイクソンパツキンを充填したもの
で、下部より２ｍの位置に前記向流接触装置塔頂
からのブタン溶剤相を導入し、温度は塔頂75℃、
塔底80℃、圧力は26atmで加圧蒸留し、塔頂から
ライン１２によつて取出されるブタンガスは圧縮
機１４で105Kg／cm2Ｇに圧縮後、一部はライン１
５を通してブタン溶剤加圧蒸留塔１１の底部を経
由させ、残部はバイパスライン１６を経由してラ
イン１８に合流させ、そのうちの一部は還流比
0.4でブタン溶剤加圧蒸留塔１１に還流させ、他
は前記向流接触装置１にライン３より循環供給
し、全体が定常になるまで運転した。
表３には、原料及びブタン溶剤の温度を種々変
化させた場合の、アルコール回収率、アルコール
濃度を示した。[Table] Example 3 Hereinafter, a specific example following the flow shown in FIG. 1 will be given. Raw material 1 consisting of 10wt% alcohol and 90wt% water
The weight part is supplied from line 2 to a portion 3 m from the top of a countercurrent contact device 1 in the form of a packed column, which has an inner diameter of 50 mm, a length of 7 m, and is filled with a 3 mm Dickson packing,
In addition, butane solvent is supplied from line 3 at the top of the device 1 to 2.
~10 parts by weight of the device 1 via the flexible tube 8.
The butane solvent phase is supplied from the butane solvent pressurized distillation column 11 while adjusting the pressure to 100 kg/cm 2 G from the top of the column of the apparatus 1 with the pressure control valve 10.
It was introduced in The butane solvent pressure distillation column 11 has an inner diameter of 100 mm, a length of 5 m, and is packed with a 3 mm Dixon packing.The butane solvent phase from the top of the countercurrent contactor is introduced at a position 2 m from the bottom, and the temperature is Tower top 75℃,
Pressure distillation is carried out at the bottom of the column at 80°C and the pressure is 26 atm, and the butane gas taken out from the top of the column through line 12 is compressed to 105 kg/cm 2 G by compressor 14, and a portion is transferred to line 1.
5 is passed through the bottom of the butane solvent pressurized distillation column 11, and the remainder is passed through the bypass line 16 to join the line 18, a part of which is at the reflux ratio.
The butane solvent was refluxed to the pressurized distillation column 11 at 0.4, and the rest was circulated and supplied to the countercurrent contactor 1 from the line 3, and the operation was continued until the whole became steady. Table 3 shows the alcohol recovery rate and alcohol concentration when the temperature of the raw material and the butane solvent was varied.
【表】
比較例 １
実施例１と同じ向流接触装置、アルコール水溶
液を用い、ブタン溶剤を３重量部供給し、回収部
及び濃縮部の温度40℃とし、圧力を100Kg／cm2Ｇ
とした。
この場合塔頂からは96wt％のアルコールが得
られたが、塔底からアルコールの損失がみられ、
アルコール回収率は75wt％で低かつた。
比較例 ２
比較例１において、回収部及び濃縮部の温度を
110℃とした。この場合、アルコールの回収率は
99.7wt％で合格であつたが、塔頂のアルコール濃
度87wt％で低かつた。
比較例 ３
実施例１と同じ向流接触装置、原料アルコール
水溶液を用い、ブタンの代りにCO2を用いた試験
を行ない、表４の結果を得た。
なお、この場合、濃縮部の温度を20〜100℃の
範囲と変化させたが、塔頂のアルコール濃度は最
大91wt％であつた。[Table] Comparative Example 1 Using the same countercurrent contact device and alcohol aqueous solution as in Example 1, 3 parts by weight of butane solvent was supplied, the temperature of the recovery section and concentration section was 40℃, and the pressure was 100Kg/cm 2 G.
And so. In this case, 96wt% alcohol was obtained from the top of the tower, but alcohol was lost from the bottom of the tower.
The alcohol recovery rate was low at 75wt%. Comparative Example 2 In Comparative Example 1, the temperature of the recovery section and concentration section was
The temperature was 110℃. In this case, the alcohol recovery rate is
It passed the test at 99.7wt%, but the alcohol concentration at the top of the tower was low at 87wt%. Comparative Example 3 A test was conducted using the same countercurrent contact apparatus and raw alcohol aqueous solution as in Example 1, and using CO 2 instead of butane, and the results shown in Table 4 were obtained. In this case, although the temperature of the concentration section was varied within the range of 20 to 100°C, the alcohol concentration at the top of the column was 91 wt% at maximum.
本発明は、以上詳記したようにアルコール水溶
液からブタン溶剤を用いてアルコールを濃縮回収
するに際し、超臨界状態又は擬臨界状態のブタン
を用いることにより少量のブタンでアルコールを
99wt％以上抽出回収し、更に液体状態のブタン
に冷却してアルコールの選択性を向上させアルコ
ール濃度を95wt％以上に濃縮できるものであり、
少量の溶剤使用のための装置のコンパクト化及び
エネルギー負荷が軽減されて経済的な効果を生ず
るとともに、製品価値の高い95wt％以上のアル
コールを得るという効果を奏する。
As detailed above, when concentrating and recovering alcohol from an aqueous alcohol solution using a butane solvent, the present invention uses butane in a supercritical or quasi-critical state to convert alcohol with a small amount of butane.
It is possible to extract and recover 99wt% or more and further cool it to liquid butane to improve alcohol selectivity and concentrate the alcohol concentration to 95wt% or more.
The device is made more compact due to the use of a small amount of solvent, and the energy load is reduced, resulting in economical effects, as well as the effect of obtaining alcohol with a high product value of 95 wt% or more.
第１図は、本発明を実施するためのフローを示
す図、第２図は第１図の向流接触装置の説明図で
ある。
FIG. 1 is a diagram showing a flow for carrying out the present invention, and FIG. 2 is an explanatory diagram of the countercurrent contact device of FIG. 1.
Claims (1)
ール水溶液を供給し、該向流接触装置の下部より
ブタン溶剤を供給し、該原料供給口より下部にお
いてはブタン溶剤を超臨界状態又は擬臨界状態に
保持し、該原料供給口より上部においてはブタン
溶剤を液体状態に保持することにより、該向流接
触装置上部より実質的に水分が分離された濃縮ア
ルコールを含んだブタン溶剤相を抜き出し、これ
をブタン溶剤加圧蒸留塔に導入し、該塔底より実
質的に水分を含まずアルコールを含むブタン液体
を回収し、一方塔頂より実質的にアルコールを含
まず水分を含むブタン気体を回収し、該ブタン気
体を加圧後その圧縮熱を該ブタン溶剤加圧蒸留塔
の熱源に用いるとともに、その一部は該ブタン溶
剤加圧蒸留塔へ還流し、他の残部は前記向流接触
装置の上部流体と間接熱交換後、前記向流接触装
置の下部に再び導入することを特徴とするアルコ
ールの濃縮精製方法。 ２ 中部にアルコール水溶液の供給ライン、底部
に重液取出ライン、頂部に軽液取出ラインが設け
られ、かつ上部より下部の分散器に超臨界状態又
は擬臨界状態のブタン溶剤を導く熱交換器の作用
を有するブタン溶剤供給ラインを内蔵した向流接
触装置、前記軽液取出ラインと減圧弁を介して連
結し、頂部にブタン溶剤取出ライン、底部に濃縮
アルコール取出ラインを設けたブタン溶剤加圧蒸
留塔及び前記ブタン溶剤取出ラインを昇圧機並び
に前記ブタン溶剤加圧蒸留塔の塔底を介して前記
向流接触装置のブタン溶剤供給ラインと接続する
ラインよりなることを特徴とするアルコール濃縮
精製装置。[Scope of Claims] 1. An alcohol aqueous solution is supplied from a raw material supply port in the middle of the countercurrent contactor, and a butane solvent is supplied from the lower part of the countercurrent contactor, and the amount of water exceeding the butane solvent is supplied below the raw material supply port. Butane containing concentrated alcohol from which water has been substantially separated from the upper part of the countercurrent contactor is maintained in a critical or quasi-critical state and the butane solvent is kept in a liquid state above the raw material supply port. The solvent phase is extracted and introduced into a butane solvent pressurized distillation column, and a butane liquid containing substantially no water and containing alcohol is recovered from the bottom of the column, while a liquid containing substantially no water and containing alcohol is recovered from the top of the column. The butane gas containing is recovered, and after pressurizing the butane gas, the heat of compression is used as a heat source for the butane solvent pressurized distillation column, and a part of it is refluxed to the butane solvent pressurized distillation column, and the rest is A method for concentrating and purifying alcohol, characterized in that after indirect heat exchange with the upper fluid of the countercurrent contactor, the alcohol is reintroduced into the lower part of the countercurrent contactor. 2 A heat exchanger equipped with an alcohol aqueous solution supply line in the middle, a heavy liquid extraction line at the bottom, and a light liquid extraction line at the top, and which leads butane solvent in a supercritical or quasi-critical state from the upper part to the lower disperser. A countercurrent contact device with a built-in functional butane solvent supply line, connected to the light liquid withdrawal line via a pressure reducing valve, and a butane solvent withdrawal line at the top and a concentrated alcohol withdrawal line at the bottom. Pressurized distillation of butane solvent. An alcohol concentration and purification device comprising a line connecting the column and the butane solvent take-off line to the butane solvent supply line of the countercurrent contactor via a booster and the bottom of the butane solvent pressurized distillation column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1003770A JPH02184388A (en) | 1989-01-12 | 1989-01-12 | Method and equipment for concentrating and purifying alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1003770A JPH02184388A (en) | 1989-01-12 | 1989-01-12 | Method and equipment for concentrating and purifying alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02184388A JPH02184388A (en) | 1990-07-18 |
| JPH0529481B2 true JPH0529481B2 (en) | 1993-04-30 |
Family
ID=11566409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1003770A Granted JPH02184388A (en) | 1989-01-12 | 1989-01-12 | Method and equipment for concentrating and purifying alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02184388A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3254472B2 (en) * | 1998-08-31 | 2002-02-04 | 独立行政法人産業技術総合研究所 | Treatment method and treatment device for wastewater containing chemical substances using supercritical fluid |
| BRPI0908412A2 (en) * | 2008-02-29 | 2017-10-17 | Ube Industries | method to purify fermentation alcohol |
-
1989
- 1989-01-12 JP JP1003770A patent/JPH02184388A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02184388A (en) | 1990-07-18 |
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