JPH0796508B2 - Fractionation method of aliphatic alcohol ethoxylates - Google Patents
Fractionation method of aliphatic alcohol ethoxylatesInfo
- Publication number
- JPH0796508B2 JPH0796508B2 JP63312924A JP31292488A JPH0796508B2 JP H0796508 B2 JPH0796508 B2 JP H0796508B2 JP 63312924 A JP63312924 A JP 63312924A JP 31292488 A JP31292488 A JP 31292488A JP H0796508 B2 JPH0796508 B2 JP H0796508B2
- Authority
- JP
- Japan
- Prior art keywords
- ethoxylate
- solvent
- aliphatic alcohol
- ethylene oxide
- extraction
- 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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 15
- 238000005194 fractionation Methods 0.000 title 1
- 239000002904 solvent Substances 0.000 claims description 58
- 238000000605 extraction Methods 0.000 claims description 44
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 21
- 238000011084 recovery Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、脂肪族アルコールに酸化エチレンを付加させ
て得られる酸化エチレン付加モル分布を有する脂肪族ア
ルコールエトキシレート（以下、エトキシレートと略
称）から、より狭い付加モル分布を有するエトキシレー
トを製造する方法に関するものである。The present invention relates to an aliphatic alcohol ethoxylate having an ethylene oxide addition molar distribution obtained by adding ethylene oxide to an aliphatic alcohol (hereinafter, abbreviated as ethoxylate). To an ethoxylate having a narrower added molar distribution.
更に詳しくは、超臨界又は擬臨界状態の流体を抽剤とし
て、酸化エチレンの付加モル分布を有するエトキシレー
ト（以下、広分布エトキシレートと略称）から、特定の
付加モル体を中心とする比較的狭い付加モル分布を有す
るエトキシレート（以下、狭分布エトキシレートと略
称）を抽出分離して取得する方法に関するものである。More specifically, by using a fluid in a supercritical or pseudocritical state as an extractant, an ethoxylate having an addition mole distribution of ethylene oxide (hereinafter, abbreviated as a wide distribution ethoxylate) is relatively concentrated around a specific addition mole. The present invention relates to a method for extracting and obtaining an ethoxylate having a narrow addition mole distribution (hereinafter, abbreviated as narrow distribution ethoxylate).
エトキシレートは脂肪族アルコールの炭素数、酸化エチ
レンの付加モル数等に応じて界面活性剤、溶剤及び種々
の化学品中間体などとして広く用いられており、工業的
にきわめて有用な化合物である。特に炭素数８−20のア
ルコールと酸化エチレンとの反応で得られるエトキシレ
ートの場合、種々の工業用クリーニング剤、洗浄剤、乳
化剤、繊維油剤に、或は又家庭用の衣料洗浄剤、台所用
洗浄剤、シヤンプー等の界面活性剤及びその原料として
用いられている。Ethoxylate is widely used as a surfactant, a solvent, various chemical intermediates, etc. depending on the number of carbon atoms of the aliphatic alcohol, the number of moles of ethylene oxide added, etc., and is an industrially extremely useful compound. In particular, in the case of ethoxylate obtained by the reaction of an alcohol having 8 to 20 carbon atoms with ethylene oxide, it can be used as various industrial cleaning agents, detergents, emulsifiers, fiber oil agents, or household laundry detergents, kitchen detergents. It is used as a detergent and a surfactant such as shampoo, and as a raw material thereof.
アルコールと酸化エチレンとを反応させて、エトキシレ
ートを製造する一般的な方法はよく知られており、工業
的に広く実施されている。A general method for producing an ethoxylate by reacting an alcohol with ethylene oxide is well known and widely practiced industrially.
工業的に最も広く用いられている塩基性触媒の場合、広
分布エトキシレートとなつてしまい、該エトキシレート
中には所望エトキシレート以外の未反応の遊離アルコー
ルや低モル付加体と同時に高モル付加体をも含有するこ
とになる。In the case of the basic catalyst most widely used industrially, it becomes a widely distributed ethoxylate, and in this ethoxylate, unreacted free alcohol other than the desired ethoxylate or a low molar adduct and a high molar addition are simultaneously formed. It will also contain the body.
一方、酸化エチレン付加モル数に応じてエトキシレート
の性質、性能は異なつてくるため、用途に応じて特定の
付加モル体を中心とする狭分布エトキシレートを製造す
る方法が望まれていた。On the other hand, since the properties and performances of ethoxylates differ depending on the number of moles of ethylene oxide added, there has been a demand for a method for producing a narrow distribution ethoxylate centered on a particular addition mole product depending on the application.
上記エトキシレートの製造を可能にすべく、これまでい
くつかの方法が提案されているが、いずれも満足すべき
ものではない。例えば、特公昭61−43333号、特公昭60
−29370号公報等にみられる如く、狭分布エトキシレー
トの製造に酸性触媒が有効であることが知られている。
しかしながら該触媒系では必ずしも所望する特定付加モ
ル体を中心とする狭分布エトキシレートを得ることがで
きない上、ポリエチレングリコール等の副生物を多量生
成するため、これらを除去しなければならず、きわめて
煩雑な工程を必要とする。Several methods have been proposed so far so as to enable the production of the above-mentioned ethoxylates, but none of them is satisfactory. For example, Japanese Patent Publication Nos. 61-43333 and 60
It is known that acidic catalysts are effective for producing narrow distribution ethoxylates, as seen in Japanese Patent Publication No. 29370.
However, the catalyst system cannot always obtain a desired narrowly-distributed ethoxylate centered on a specific addition mole, and also produces a large amount of by-products such as polyethylene glycol, which must be removed, which is extremely complicated. It requires various steps.
広分布エトキシレートから狭分布エトキシレートを所望
する方法として蒸留分離による方法がある。この方法で
は広分布エトキシレートから未反応の遊離アルコールや
低モル付加体を除去することはできるが、高モル付加体
の分離は困難であり、又、蒸留過程で加熱による着色や
変質劣化のおそれがある等、決して満足できる方法では
ない。As a method for obtaining a narrow distribution ethoxylate from a wide distribution ethoxylate, there is a method by distillation separation. Although unreacted free alcohol and low molar adducts can be removed from widely distributed ethoxylates by this method, it is difficult to separate high molar adducts, and there is a risk of coloring and deterioration due to heating during the distillation process. There is no such thing as a satisfactory method.
本発明者らは、産業上有用な価値を有する狭分布エトキ
シレートを有効に取得する方法について鋭意検討した結
果、超臨界、又は擬臨界状態のCO2を抽剤とする抽出分
離を上記エトキシレートに適用することにより従来技術
では困難であつた特定の付加モル体を中心とする狭分布
エトキシレートが分離できることを見出し、本発明に到
達したものである。As a result of diligent studies on a method for effectively obtaining a narrow distribution ethoxylate having industrially useful value, the present inventors have conducted extraction separation using CO 2 in a supercritical or pseudocritical state as an extractant to obtain the above ethoxylate. It was found that the narrowly distributed ethoxylate centered on a specific addition mole compound, which was difficult in the prior art, can be separated by applying the above method to the present invention, and thus the present invention has been accomplished.
すなわち、本発明は第１抽出塔の上部より酸化エチレン
の付加モル分布を有する脂肪族アルコールエトキシレー
トを、又、その下部より超臨界又は擬臨界状態のCO2溶
剤を供給して両者を向流接触させ、第１抽出塔の下方よ
り酸化エチレンの高モル付加体脂肪族アルコールエトキ
シレートを分離回収し、その上方から取出されるCO2相
を減圧又は昇温後、第２抽出塔の中部に供給し、その下
部から供給する超臨界又は擬臨界状態のCO2溶剤と向流
接触させ、第２抽出塔の下方より狭い酸化エチレンの付
加モル分布を有する中モル付加体脂肪族アルコールエト
キシレートを分離回収し、その上方から取出されるCO2
相を更に減圧又は昇温後、溶剤回収塔に供給し、実質的
に脂肪族アルコールエトキシレートを含まないCO2と酸
化エチレンの低モル付加体脂肪族アルコールエキシレー
トに分離し、分離したCO2を再圧縮して系内のCO2溶剤と
して循環使用することを特徴とする脂肪族アルコールエ
トキシレートの分画方法である。That is, in the present invention, an aliphatic alcohol ethoxylate having an added molar distribution of ethylene oxide is supplied from the upper part of the first extraction column, and a CO 2 solvent in a supercritical or pseudocritical state is supplied from the lower part of the first extraction column to countercurrently flow both. After contact, the high molar adduct of ethylene oxide, aliphatic alcohol ethoxylate, is separated and recovered from the lower part of the first extraction column, and the CO 2 phase taken out from the upper part is decompressed or heated up, and then is put in the middle part of the second extraction column. It is fed and brought into countercurrent contact with the CO 2 solvent in a supercritical or pseudocritical state fed from the lower part thereof to obtain a medium molar adduct fatty alcohol ethoxylate having a narrower addition molar distribution of ethylene oxide from the lower part of the second extraction column. CO 2 that is separated and collected and taken out from above
Further vacuum or After heating phase, is supplied to a solvent recovery column, substantially separated into the low-mol adduct aliphatic alcohol solution was rate CO 2 and ethylene oxide containing no aliphatic alcohol ethoxylates, separate CO 2 Is a method of fractionating an aliphatic alcohol ethoxylate, which is characterized in that it is recompressed and reused as a CO 2 solvent in the system.
本発明の対象となる脂肪族アルコールエトキシレート
は、主として炭素数８から20の脂肪族アルコールに酸性
もしくは塩基性触媒の存在下、酸化エチレンを付加して
得られるもので、一般的に次式で示される混合物であつ
て未反応の遊離アルコールを含む。The aliphatic alcohol ethoxylate which is the object of the present invention is obtained mainly by adding ethylene oxide to an aliphatic alcohol having 8 to 20 carbon atoms in the presence of an acidic or basic catalyst. The mixture shown contains unreacted free alcohol.
ROCH2CH2OnH （上式において、Ｒは炭素数８〜20の直鎖又は分岐鎖の
アルキル基を表わし、ｎは酸化エチレン平均付加モル数
で、０から約20の間の値である。） 本発明でいうCO2の超臨界状態とは、CO2の臨界温度Tc
（31℃）、臨界圧力Pc（73atm）以上の温度及び圧力にC
O2を保持した状態をいい、CO2の擬臨界状態とは約20℃
以上の温度で、圧力はその温度におけるCO2の飽和蒸気
圧以上に保持されたCO2の超臨界状態以外の状態をい
う。ROCH 2 CH 2 O n H (In the above formula, R represents a linear or branched alkyl group having 8 to 20 carbon atoms, n is the average number of moles of ethylene oxide added, and is a value between 0 and about 20. The supercritical state of CO 2 in the present invention means the critical temperature Tc of CO 2.
(31 ℃), C at a temperature and pressure above the critical pressure Pc (73atm)
A state in which O 2 is retained. The CO 2 pseudo-critical state is approximately 20 ° C.
At the above temperature, the pressure means a state other than the supercritical state of CO 2 which is maintained at the saturated vapor pressure of CO 2 or higher at that temperature.
以下、本発明の一実施態様を第１図に従つて詳述する。Hereinafter, one embodiment of the present invention will be described in detail with reference to FIG.
第１図において、１は充填塔、多孔板塔又は多段抽出塔
などのような第１抽出塔、２は広分布エトキシレートの
供給ライン、３はCO2溶剤の供給ライン、４は第１抽出
塔１上方のCO2相（CO2溶剤と低モル及び中モル付加体エ
トキシレートの混合物）の取出しライン、５は第１抽出
塔１下方のラフイネート（高モル付加体エトキシレート
とCO2溶剤の混合物）の取出しライン、６は減圧弁、７
は加熱器（CO2溶剤供給ライン３との熱交換器）、８は
第２抽出塔、９は第２抽出塔８への原料（取出しライン
４のCO2相）供給ライン、10は第２抽出塔８へのCO2溶剤
供給ライン、11は第２抽出塔８の上方のCO2相（CO2溶剤
と低モル付加体エトキシレートの混合物）の取出しライ
ン、12は第２抽出塔８の下方のラフイネート｛中モル付
加体エトキシレート（狭分布エトキシレート）とCO2溶
剤の混合物｝の取出しライン、13は減圧弁、14は加熱器
（CO2溶剤供給ライン10との熱交換器）、15は溶剤回収
塔、16は溶剤回収塔15への原料（取出しライン11のCO2
相）供給ライン、17は溶剤回収塔15下方のラフイネート
（低モル付加体エトキシレートとCO2溶剤の混合物）の
取出しライン、18は溶剤回収塔15上方のCO2相（実質的
にエトキシレートを含まないCO2溶剤）の取出しライ
ン、19はCO2溶剤再圧縮循環用コンプレツサ、20はCO2溶
剤循環バイパスライン及び21は溶剤回収塔15のボトム加
熱用熱交換器である。In FIG. 1, 1 is a first extraction column such as a packed column, a perforated plate column or a multi-stage extraction column, 2 is a widely distributed ethoxylate supply line, 3 is a CO 2 solvent supply line, and 4 is a first extraction. The CO 2 phase (a mixture of CO 2 solvent and low- and medium-molar adduct ethoxylates) at the top of column 1 is a take-out line, 5 is a raffinate at the bottom of the first extraction column 1 (of high-molar adduct ethoxylate and CO 2 solvent). (Mixture) take-out line, 6 is a pressure reducing valve, 7
Is a heater (heat exchanger with the CO 2 solvent supply line 3), 8 is a second extraction tower, 9 is a raw material (CO 2 phase of the take-out line 4) supply line to the second extraction tower 8, and 10 is a second CO 2 solvent supply line to the extraction column 8, 11 is an upper CO 2 phase (mixture of CO 2 solvent and low molar adduct ethoxylate) extraction line of the second extraction column 8, and 12 is of the second extraction column 8. Lower take-out line of raffinate (mixture of medium-molar adduct ethoxylate (narrow-distribution ethoxylate) and CO 2 solvent), 13 pressure reducing valve, 14 heater (heat exchanger with CO 2 solvent supply line 10), 15 is a solvent recovery tower, 16 is a raw material for the solvent recovery tower 15 (CO 2 in the take- out line 11)
Phase) supply line, 17 is a raffinate (low-molar adduct ethoxylate and CO 2 solvent mixture) take-out line below the solvent recovery column 15, and 18 is a CO 2 phase (substantially ethoxylate above the solvent recovery column 15). CO 2 solvent (not included) take-out line, 19 is a compressor for CO 2 solvent recompression circulation, 20 is a CO 2 solvent circulation bypass line, and 21 is a heat exchanger for bottom heating of the solvent recovery tower 15.
原料の広分布エトキシレートを供給ライン２より、超臨
界又は擬臨界状態のCO2溶剤を供給ライン３より第１抽
出塔１に供給し、両者を向流接触させると、CO2溶剤相
はエトキシレートより密度が小さいため、上昇しながら
エトキシレート中の未反応アルコール、低モル付加及び
中モル付加体エトキシレートを選択的に抽出し取出しラ
イン４より取出される。すなわち、エトキシレート中の
付加モル数の小ないものから選択的に高密度状態のCO2
に溶解するものである。これはCO2とエトキシレートの
親和力が適度なものであるためと考えられる。通常、溶
剤として用いられるｎ−ヘキサンではエトキシレートと
の親和力が強すぎて均一に溶解させてしまい、付加モル
数の異なるエトキシレートを選択的に抽出することは不
可能である。When the widely distributed ethoxylate of the raw material is supplied from the supply line 2 to the CO 2 solvent in the supercritical or pseudocritical state to the first extraction column 1 from the supply line 3 and both are brought into countercurrent contact, the CO 2 solvent phase becomes ethoxy. Since the density is lower than the rate, unreacted alcohol, low-molar addition and medium-molar adduct ethoxylates in the ethoxylate are selectively extracted and taken out through the take-out line 4 while increasing. That is, CO 2 in a high-density state is selectively selected from those having a small number of added moles in ethoxylate.
It dissolves in. It is considered that this is because the affinity between CO 2 and ethoxylate is appropriate. Usually, n-hexane used as a solvent has a too strong affinity with ethoxylate and is uniformly dissolved, and it is impossible to selectively extract ethoxylates having different addition mole numbers.
第１抽出塔１の操作条件は、CO2の超臨界又は擬臨界状
態に維持できるような条件にすべきである。CO2の超臨
界又は擬臨界状態では、液体溶剤に較べて、 CO2の拡散係数が大きく、低モル付加体エトキシレ
ートを早い速度で選択的に抽出できる。The operating conditions of the first extraction column 1 should be such that CO 2 can be maintained in a supercritical or pseudocritical state. The supercritical or pseudocritical state of CO 2, compared to the liquid solvent, larger diffusion coefficient of CO 2 can selectively extracting low mole adduct ethoxylates at a high speed.
CO2の粘度が小さく、高モル付加体エトキシレート
及び灰分（無機質）を容易に重力沈降により分離でき
る。The viscosity of CO 2 is low, and high molar adduct ethoxylate and ash (inorganic) can be easily separated by gravity settling.
等の利点も見出された。The advantages such as the above were also found.
一方、第１抽出塔１の下方の取出しライン５からは、低
モル付加体及び中モル付加体エトキシレートが分離され
た高モル付加体エトキシレートが取出される。このよう
に、第１抽出塔１の温度、圧力は所望のモル付加体エト
キシレートが得られるように制御することができる。On the other hand, the high-mole adduct ethoxylate from which the low-mole adduct and the medium-mole adduct ethoxylate are separated is taken out from the take-out line 5 below the first extraction column 1. In this way, the temperature and pressure of the first extraction column 1 can be controlled so that the desired molar adduct ethoxylate can be obtained.
次に、取出しライン４から取出されたCO2溶剤相は減圧
弁６又は加熱器７を経て減圧又は加熱されてCO2溶剤相
の密度を下げ、ライン９を経て第２抽出塔８の中段に供
給される。このようにCO2溶剤相の密度を下げてエトキ
シレートの溶解度を制御することにより、低モル付加体
エトキシレートをCO2溶剤に溶解した状態に維持し、中
モル付加体エトキシレートをCO2溶剤に溶解させないで
分離させることができるようになる。更に、中モル付加
体エトキシレート中への低モル付加体エトキシレートの
混入を防止するには、第２抽出塔８の下部より新たにCO
2溶剤を供給し、第２抽出塔８下部から中段で新たなCO2
溶剤と向流接触させ残留低モル付加体エトキシレートを
抽出することが極めて有効である。そのためには、第２
抽出塔８の温度、圧力はCO2が超臨界又は擬臨界状態と
なり、所望の中モル付加体エトキシレートが得られるよ
うに制御すべきで、一般的にはこの新たなCO2溶剤の密
度が第１抽出塔１の較べて低くなるような条件に設定さ
れる。Next, the CO 2 solvent phase taken out from the take-out line 4 is decompressed or heated through the pressure reducing valve 6 or the heater 7 to reduce the density of the CO 2 solvent phase, and then passed through the line 9 to the middle stage of the second extraction column 8. Supplied. In this way, by lowering the density of the CO 2 solvent phase and controlling the solubility of the ethoxylate, the low molar adduct ethoxylate is maintained in the state of being dissolved in the CO 2 solvent, and the medium molar adduct ethoxylate is reduced to the CO 2 solvent. It becomes possible to separate without dissolving in. Further, in order to prevent the low molar adduct ethoxylate from being mixed in the medium molar adduct ethoxylate, CO 2 is newly added from the lower part of the second extraction column 8.
2 Solvent is supplied, and new CO 2
It is extremely effective to extract the residual low molar adduct ethoxylate by contacting with a solvent countercurrently. For that, the second
The temperature and pressure of the extraction column 8 should be controlled so that CO 2 is in a supercritical or pseudocritical state and the desired intermediate molar adduct ethoxylate is obtained. Generally, the density of this new CO 2 solvent is The conditions are set so as to be lower than those of the first extraction tower 1.
上述のように第２抽出塔８の条件を設定することによ
り、第２抽出塔８の上方の取出しライン11からはCO2溶
剤と低モル付加体エトキシレートの混合物が取出され、
このものは減圧弁13又は加熱器14により更に減圧又は加
熱されて密度が低められ、ライン16を経て溶剤回収塔15
に供給される。このようにCO2溶剤の密度を更に下げる
ことにより、エトキシレートを実質的に含まないCO2溶
剤は溶剤回収塔15の上方の取出しライン18より取出さ
れ、一方、低モル付加体エトキシレートは該塔15の下方
の取出しライ17より取出される。By setting the conditions of the second extraction column 8 as described above, a mixture of the CO 2 solvent and the low molar adduct ethoxylate is taken out from the take-out line 11 above the second extraction column 8,
This is further reduced in pressure or heated by the pressure reducing valve 13 or the heater 14 to reduce the density, and the solvent recovery tower 15 is passed through the line 16.
Is supplied to. By lowering in this manner further the density of the CO 2 solvent, CO 2 solvent that does not contain ethoxylate substantially are removed from above the extraction line 18 of the solvent recovery column 15, while low-mol adduct ethoxylates Said It is taken out from the take-out lie 17 below the tower 15.
取出しライン18より取出されたCO2溶剤はコンプレッサ1
9で昇圧され、そのCO2溶剤の一部は溶剤回収塔15の熱交
換器21を経由し、他部はバイパスライン20を経由して、
第１抽出塔１のCO2溶剤供給ライン及び第２抽出塔８のC
O2溶剤供給ライン10に導かれる。The CO 2 solvent extracted from the extraction line 18 is the compressor 1
The pressure is increased by 9, a part of the CO 2 solvent passes through the heat exchanger 21 of the solvent recovery tower 15, and the other part passes through the bypass line 20.
CO 2 solvent supply line of the first extraction tower 1 and C of the second extraction tower 8
Guided to the O 2 solvent supply line 10.
溶剤回収塔15の温度、圧力はエトキシレートがCO2溶剤
に実質的に溶解しない条件にすべきである。この条件と
しては、温度をCO2の臨界温度Tc＝31℃以上で、圧力をC
O2臨界圧力Pc＝73atm以下にするのがよく、最も好まし
い条件は温度40〜80℃、圧力30〜60kg/cm2Gである。す
なわち、CO2の臨界温度Tc以上では溶剤回収塔15のCO2の
圧力を第２抽出塔15の圧力よりも減圧してもCO2の相変
化はなく、CO2の蒸発潜熱は不要となり、省エネルギ的
に容易にCO2を回収できる利点があるからである。The temperature and pressure of the solvent recovery column 15 should be set so that the ethoxylate is not substantially dissolved in the CO 2 solvent. The conditions are as follows: the temperature is the critical temperature of CO 2 , Tc = 31 ℃ or higher, and the pressure is C.
The O 2 critical pressure Pc is preferably 73 atm or less, and the most preferable conditions are a temperature of 40 to 80 ° C. and a pressure of 30 to 60 kg / cm 2 G. That is, the phase change of CO 2 be depressurized than the pressure of the pressure second extraction column 15 for CO 2 solvent recovery column 15 at the critical temperature Tc or more CO 2 is not, the latent heat of vaporization of CO 2 is not required, This is because there is an advantage that CO 2 can be easily recovered in an energy saving manner.
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〕 炭素数12及び13の直鎖率76％脂肪族アルコール混合物
（三菱油化株式会社製“ドバノール23"）に酸化エチレ
ンを平均3.0モル付加させて得たエトキシレート100g/h
を、内径3cm、高さ2mの第１抽出塔（充填物:3φデイク
ソン）の上部より、又CO25kg/hを第１抽出塔の下部より
連続的に供給し、温度40℃、圧力100kg/cm2Gの条件下で
向流抽出操作を行ない、下方より高モル付加体エトキシ
レートを、又上方よりCO2溶剤相を連続的に取出した。[Example 1] 100 g / h of ethoxylate obtained by adding 3.0 mol of ethylene oxide on average to a mixture of aliphatic alcohols having a linearity of 76% and having 12 and 13 carbon atoms ("Dovanol 23" manufactured by Mitsubishi Petrochemical Co., Ltd.)
Is continuously supplied from the upper part of the first extraction column (packing: 3φ Dickson) with an inner diameter of 3 cm and a height of 2 m, and CO 2 5 kg / h from the lower part of the first extraction column, at a temperature of 40 ° C and a pressure of 100 kg. The counter-current extraction operation was carried out under the condition of / cm 2 G to continuously take out the high molar adduct ethoxylate from the lower part and the CO 2 solvent phase from the upper part.
次に、このCO2溶剤層を50℃に昇温して、内径3cm、高さ
2mの第２抽出塔の中部に供給し、下部からは2kg/hのCO2
溶剤を連続的に供給し、温度50℃、圧力98kg/cm2Gの条
件下で向流抽出操作を行ない、下方より中モル付加体エ
トキシレートを回収し、上方からはCO2溶剤相を連続的
に取出し、該CO2溶剤を圧力50kg/cm2G、温度50℃の条件
下で内容積１の容器に導入し、CO2と低付加モル体エ
トキシレートに分離した。Next, the temperature of this CO 2 solvent layer is raised to 50 ° C, and the inner diameter is 3 cm and the height is 3 cm.
It is supplied to the middle part of the 2m 2nd extraction tower and 2kg / h of CO 2 from the bottom.
The solvent is continuously supplied, and the countercurrent extraction operation is performed under the conditions of temperature of 50 ° C and pressure of 98 kg / cm 2 G to recover the intermediate molar adduct ethoxylate from the bottom, and the CO 2 solvent phase continuously from the top. The CO 2 solvent was introduced into a container having an internal volume of 1 under the conditions of a pressure of 50 kg / cm 2 G and a temperature of 50 ° C. to separate CO 2 and low addition mole ethoxylate.
この操作により得れた高、中及び低モル付加体エトキシ
レートの分子量分布及び原料の分子量分布を第２図に示
す。FIG. 2 shows the molecular weight distributions of the high-, medium-, and low-mole adduct ethoxylates obtained by this operation and the molecular weight distribution of the raw materials.
この第２図から、広分布エトキシレートを分子量により
分画できることが実証された。From this FIG. 2, it was demonstrated that a wide distribution ethoxylate can be fractionated by the molecular weight.
なお、各エトキシレート中の灰分及びポリエチレングリ
コール濃度を測定したところ、それらは殆んど高付加モ
ル体エトキシレート中に残留濃縮されていることが判つ
た。When the ash content and polyethylene glycol concentration in each ethoxylate were measured, it was found that they were almost concentrated in the high-addition mole ethoxylate.
〔実施例２〕 実施例１において、第１及び第２抽出塔及び溶剤回収塔
（容器）の温度及び圧力を変えたテストを行ない、高、
中及び低モル付加体エトキシレートの平均モル付加数を
測定した。この結果を下表に示す。[Example 2] In Example 1, a test was conducted in which the temperatures and pressures of the first and second extraction towers and the solvent recovery tower (container) were changed.
The average molar addition numbers of the medium and low molar adduct ethoxylates were measured. The results are shown in the table below.
〔比較例〕 実施例１に用いた装置によつて、CO2溶剤の代りにプロ
パン及びｎ−ヘキサンを用いて、温度20〜100℃、圧力5
0〜200kg/cm2・Ｇの範囲の条件下で同じ広分布エトキシ
レートの抽出テストを行つが、低分子アルコールエトキ
シレートの酸化エチレン付加モル数の差により選択的抽
出はできなかつた。 Comparative Example With the apparatus used in Example 1, propane and n-hexane were used in place of the CO 2 solvent, the temperature was 20 to 100 ° C., and the pressure was 5
The same extraction test of broadly distributed ethoxylates was conducted under the condition of 0 to 200 kg / cm 2 · G, but selective extraction could not be performed due to the difference in the number of moles of ethylene oxide added of the low molecular alcohol ethoxylates.
これはプロパン及びｎ−ヘキサンとエトキシレートの親
和力が強すぎて全てのエトキシレートが溶解してしまつ
たためである。This is because the affinity of ethoxylates with propane and n-hexane was too strong, and all the ethoxylates were dissolved.
本発明は、以上詳記したようにアルコールエトキシレー
トを分画するに際し、アルコールエトキシレートと適度
な親和性を有する超臨界状態又は擬臨界状態のCO2を溶
剤として用いることにより、酸化エチレン付加モル数の
小さいアルコールエトキシレートと大きいものに省エネ
ルギー的に容易に分画でき、用途の多様化、付加価値の
向上という効果を奏する。The present invention, when fractionating alcohol ethoxylates as described above, by using CO 2 in a supercritical state or a pseudocritical state having a suitable affinity for alcohol ethoxylates as a solvent, ethylene oxide addition moles Energy-saving can be easily fractionated into a small number of alcohol ethoxylates and a large number of alcohol ethoxylates, and the effects of diversifying applications and improving added value are achieved.
又、本発明は狭分布エトキシレートを得ることのほか、
従来技術に較べ、いくつかのきわめてすぐれた利点を有
する。すなわち、蒸留法に比べると、高温に加熱するこ
とがないため、着色や変質劣化のおそれがないこと、又
酸性触媒法に比べると任意の狭分布エトキシレートを得
ることができるほか、ポリエチレングリコール等の不純
物の含有量が低レベルであり、更にエトキシレートに含
まれる灰分（無機質）含有量も低いという利点がある。Further, the present invention, in addition to obtaining a narrow distribution ethoxylate,
It has some outstanding advantages over the prior art. That is, compared to the distillation method, since it is not heated to a high temperature, there is no risk of coloring or deterioration, and it is possible to obtain any narrowly distributed ethoxylate compared to the acid catalyst method, polyethylene glycol, etc. Has the advantage that the content of impurities is low and the content of ash (inorganic) contained in ethoxylate is also low.
特定の用途分野ではこれら灰分をきらうため、煩雑な脱
触媒処理が必要であつたが、本発明によつて得られる狭
分布エトキシレートの場合、かかる操作がなくても灰分
量の少ないエトキシレートを得ることができる。In a specific field of application, it is necessary to perform a complicated decatalytic treatment in order to avoid these ash contents.However, in the case of the narrow distribution ethoxylate obtained by the present invention, an ethoxylate having a small ash content can be obtained without such an operation. Obtainable.
第１図は本発明を実施するためのプロセスフローの概略
図、第２図は、実施例１の結果を示す図表である。FIG. 1 is a schematic diagram of a process flow for carrying out the present invention, and FIG. 2 is a chart showing the results of Example 1.
Claims (2)
モル分布を有する脂肪族アルコールエトキシレートを、
又、その下部より超臨界又は擬臨界状態のCO2溶剤を供
給して両者を向流接触させ、第１抽出塔の下方より酸化
エチレンの高モル付加体脂肪族アルコールエトキシレー
トを分離回収し、その上方から取出されるCO2相を減圧
又は昇温後、第２抽出塔の中部に供給し、その下部から
供給する超臨界又は擬臨界状態のCO2溶剤と向流接触さ
せ、第２抽出塔の下方より狭い酸化エチレンの付加モル
分布を有する中モル付加体脂肪族アルコールエトキシレ
ートを分離回収し、その上方から取出されるCO2相を更
に減圧又は昇温後、溶剤回収塔に供給し、実質的に脂肪
族アルコールエトキシレートを含まないCO2と酸化エチ
レンの低モル付加体脂肪族アルコールエトキシレートに
分離し、分離したCO2を再圧縮して系内のCO2溶剤として
循環使用することを特徴とする脂肪族アルコールエトキ
シレートの分画方法。1. An aliphatic alcohol ethoxylate having an addition molar distribution of ethylene oxide from the upper part of the first extraction column,
Further, a CO 2 solvent in a supercritical or pseudocritical state is supplied from the lower part thereof to bring them into countercurrent contact, and a high molar adduct of ethylene oxide aliphatic alcohol ethoxylate is separated and recovered from the lower part of the first extraction column, After decompressing or raising the temperature of the CO 2 phase taken out from the upper part, it is supplied to the middle part of the second extraction column and brought into countercurrent contact with the supercritical or pseudocritical CO 2 solvent supplied from the lower part of the second extraction column to carry out the second extraction. The intermediate molar adduct aliphatic alcohol ethoxylate having a narrower addition mole distribution of ethylene oxide than the lower part of the column is separated and recovered, and the CO 2 phase taken out from the upper part is further depressurized or heated and then supplied to the solvent recovery column. , CO 2 substantially free of aliphatic alcohol ethoxylate and ethylene oxide low-molar adduct, separated into aliphatic alcohol ethoxylate, re-compressed the separated CO 2 and reused as CO 2 solvent in the system Characterized by Method for fractionating aliphatic alcohol ethoxylates.
族アルコールに酸性もしくは塩基性触媒の存在下、酸化
エチレンを付加して得られたものである特許請求の範囲
（１）記載の方法。2. The method according to claim 1, wherein the aliphatic alcohol ethoxylate is obtained by adding ethylene oxide to an aliphatic alcohol in the presence of an acidic or basic catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63312924A JPH0796508B2 (en) | 1988-12-13 | 1988-12-13 | Fractionation method of aliphatic alcohol ethoxylates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63312924A JPH0796508B2 (en) | 1988-12-13 | 1988-12-13 | Fractionation method of aliphatic alcohol ethoxylates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02160738A JPH02160738A (en) | 1990-06-20 |
| JPH0796508B2 true JPH0796508B2 (en) | 1995-10-18 |
Family
ID=18035109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63312924A Expired - Lifetime JPH0796508B2 (en) | 1988-12-13 | 1988-12-13 | Fractionation method of aliphatic alcohol ethoxylates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796508B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0697034T3 (en) * | 1993-04-29 | 1997-07-14 | Norsk Hydro As | Methods for chromatographic fractionation of fatty acids and their derivatives |
| EP1607382A1 (en) * | 2004-06-17 | 2005-12-21 | Linde Aktiengesellschaft | Method for producing narrow range alcoxylates |
-
1988
- 1988-12-13 JP JP63312924A patent/JPH0796508B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02160738A (en) | 1990-06-20 |
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