CN1292774A - 蒸馏含丁二醇的混合物的方法 - Google Patents
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Abstract
一种蒸馏分离混合物的方法,该混合物含有1,4-丁二醇和至少一种选自4-羟基丁醛、它与至少一种其他醇的化合物,该法包括在碱性化合物存在下进行蒸馏。待分离的混合物优选含有4-羟基丁醛与沸点低于丁二醇的其他醇的环状全缩醛,还含有游离形式的其他醇。该法特别适用于蒸馏分离在马来酸衍生物加氢中生成的混合物。
Description
本发明涉及一种蒸馏含有1,4-丁二醇和4-羟基丁醛或其环状缩醛的混合物的方法。
马来酸衍生物催化加氢生产1,4-丁二醇的反应产物通常除其他其次要组分外还含有4-羟基丁醛、4-羟基丁醛的环状半缩醛2-羟基四氢呋喃和环状全缩醛。4-羟基丁醛与1,4-丁二醛的环状缩醛,即2-(4-羟基丁氧基)四氢呋喃仅用蒸馏法从1,4-丁二醇中分离出来有很大的困难,所以它是用蒸馏法得到的1,4-丁二醇的杂质来源。所以,正在寻找各种方法来降低2-(4-羟基丁氧基)四氢呋喃在要处理的含丁二醇的加氢产物中的含量。
WO97/36846公开了这样一种方法,其中在0.5-5%(重量)水存在下使粗1,4-丁二醇进行催化加氢,以降低其2-(4-羟基丁氧基)四氢呋喃的含量。这样新增的加氢步骤使分离1,4-丁二醇的方法更加复杂,同时使费用有相当大地提高。此外,加入的水还必需再次除去。
JP-A09-59191公开了这样一种方法,其中在固体酸催化剂上2-羟基四氢呋喃与粗1,4-丁二醇中的烷基醇反应,生成可用蒸馏法分离的2-烷氧基四氢呋喃。这一方法的缺点在于,1,4-丁二醇在酸性催化剂上部分被环化成四氢呋喃,造成1,4-丁二醇的产率损失。而且,在1,4-丁二醇的存在下还生成4-羟基丁醛的丁二醇缩醛,后者的生成是完全应该避免的。另一个问题是,由马来酸二烷基酯得到的烷基醇两倍摩尔过量于1,4-丁二醇,就缩醛的生成来说,加入其中后,后者有比较高的官能性。
本发明的一个目的是提供一种蒸馏在马来酸衍生物加氢中得到的含二丁醇的粗混合物,生产有很低2-(4-羟基丁氧基)四氢呋喃的1,4-丁二醇作为蒸馏产物的方法。
我们已经发现,这一目的可用蒸馏分离含有1,4-丁二醇和至少另一种选自4-羟基丁醛、它与至少一种其他醇的环状半缩醛和环状全缩醛的化合物的混合物的方法来实现,该法包括在碱性化合物存在下进行蒸馏。
原则上,本发明的方法适用于任何一种混合物,只要这种要蒸馏分离的混合物含有至少一种选自4-羟基丁醛、它的半缩醛和全缩醛的化合物。例如,有可能4-羟基丁醛是上述存在的化合物的唯一代表。也可能开链的醛、它的环状半缩醛和环状全缩醛一起存在。
本发明的方法优选用于马来酸衍生物催化加氢合成1,4-丁二醇中制得的混合物的蒸馏分离。对于本发明来说,马来酸衍生物为马来酸酐、富马酸、马来酸的单酯和二酯、富马酸的单酯和二酯、琥珀酸、琥珀酸的单酯和二酯、γ-丁内酯以及马来酯本身。所提到的马来酸衍生物可在溶剂例如水或醇中,在液相或气相中单独加氢或作为混合物加氢。加氢产物中含有1,4-丁二醇,其中也可含有四氢呋喃、γ-丁内酯、醇类(例如甲醇、乙醇、丙醇和丁醇)、水和未反应的马来酸衍生物。
一般来说,在制得的混合物中存在4-羟基丁醛、它的环状半缩醛2-羟基四氢呋喃和它的环状全缩醛。
在本发明方法的优选变通方案中,要分离的混合物含有4-羟基丁醛与其他醇的环状全缩醛。优选的其他醇为在马来酸衍生物例如马来酸二烷基酯的催化加氢中作为副产物生成的醇;这样的醇的例子是甲醇、乙醇、正丙醇和正丁醇。特别优选的其他醇是酯醇,它们在通常用作催化加氢原料的马来酸二烷基酯中以键联形式存在,例如甲醇、乙醇、丙醇和正丁醇。
要分离的混合物优选含有4-羟基丁醛与沸点低于1,4-丁二醇的其他醇类的环状全缩醛。例子是甲醇、乙醇、丙醇和正丁醇。
在本发明方法的特别优选的变通方案中,在4-羟基丁醛的环状全缩醛中以键联的形式存在的其他醇也以游离的形式在要分离的混合物中存在。例子是除了甲醇或乙醇外还分别存在2-甲氧基四氢呋喃或2-乙氧基四氢呋喃的混合物。这样的混合物例如在马来酸二甲酯或马来酸二乙酯加氢中制得。
要分离的混合物还可含有2-(4-羟基丁氧基)四氢呋喃。要分离的混合物优选含有后一化合物。
在本发明方法的特别优选的变通方案中,要分离的混合物含有2-(4-羟基丁氧基)四氢呋喃,还有2-甲氧基四氢呋喃或2-乙氧基四氢呋喃和甲醇或乙醇,特别是当马来酸二甲酯或马来酸二乙酯加氢时。
要分离的混合物的蒸馏在碱性化合物存在下进行。对于本发明来说,碱性化合物指抵消涉及的混合物中存在的醇、醛、半缩醛和全缩醛的质子化,因此使对应的质子化物种的浓度下降的化合物。可溶的或不溶的碱性化合物都可用于要分离的混合物。在要分离的混合物中,优选使用可溶的碱性化合物。优选的碱性化合物是氨、胺、碱金属化合物或碱土金属化合物,在每种情况下,优选锂、钠、钾、镁和钙的氧化物、氢氧化物、碳酸盐、醇盐(例如甲醇盐、乙醇盐、丙醇盐和丁醇盐)和羧酸盐(例如甲酸盐、乙酸盐和丙酸盐)。
一般来说,碱性化合物在要蒸馏的混合物中的浓度平均为0.0001-5%(重量)、优选0.001-1%(重量)、特别优选0.01-0.5%(重量)。
碱性组分可以未稀释的形式加入或作为在溶剂例如水或醇中的溶液加入。碱性组分优选作为水溶液、醇水溶液或醇溶液加入。如果本发明的方法用于处理由合成1,4-丁二醇得到的加氢产物,那么一般在加氢步骤以后进行加入步骤。
蒸馏可在一段或多段中进行,例如在一个或多个蒸馏塔中进行,以及可连续进行或间歇进行。蒸馏优选在两段或两段以上中连续进行。如果要蒸馏的混合物除含有1,4-丁二醇外还含有较低沸点的其他醇,如通常在合成1,4-丁二醇得到的加氢产物中的情况,那么蒸馏最好在至少两段中进行,其中其他醇在第一段中蒸出,而1,4-丁二醇在第二段中蒸出。蒸馏也可在两段以上中进行。例如,低沸点组分例如甲醇或乙醇或四氢呋喃可在第一段蒸出,中间沸点组分例如丁内酯和琥珀酯二酯可在第二段蒸出,而1,4-丁二醇可在第三段中从高沸点组分例如琥珀酸丁二醇酯中蒸出。如果蒸馏在多段中进行,那么也可能仅在低沸点组分蒸出以后将至少一部分碱性化合物加入。在最后一蒸馏段以后,可将其中有碱性化合物的作为塔底产物留下的高沸点组分循环至第一蒸馏段。
本发明的方法得到很纯的1,4-丁二醇。在马来酸二烷基酯加氢得到的含丁二醇的反应产物的蒸馏中,可得到2-(4-羟基丁氧基)四氢呋喃的含量小于2000ppm、优选小于1000ppm、特别优选小于500ppm。
用以下实施例来说明本发明。
马来酸二甲酯在Cu/Mn/Al催化剂上(T4489,Süd Chemie AG,慕尼黑,德国),在60巴、190℃下气相加氢制得的反应产物作为要蒸馏分离的混合物。该加氢产物含有约51%(重量)1,4-丁二醇、41%(重量)甲醇、约0.05%(重量)2-甲氧基四氢呋喃、约0.05%(重量)2-羟基四氢呋喃、约0.05%(重量)2-(4-羟基丁氧基)四氢呋喃和1%(重量)四氢呋喃、3%(重量)γ-丁内酯、1%(重量)丁醇和1%(重量)水。反应产生在本发明的实施例中和在对比例中分离。
实施例
将0.8克KOH溶于745克反应产物中。随后,在常压下主要蒸出甲醇和四氢呋喃。然后用带有回流分配器的填料塔(回流比为10)在40毫巴下分馏剩余的混合物。在塔底温度146℃和塔顶温度136℃下,在塔顶得到2-(4-羟基丁氧基)四氢呋喃含量为300-400ppm的1,4-丁二醇。
对比例
在不加KOH的条件下重复本发明实施例的步骤。得到的1,4-丁二醇的2-(4-羟基丁氧基)四氢呋喃的含量为900-1000ppm。
Claims (7)
1.一种蒸馏分离混合物的方法,该混合物含有1,4-丁二醇和至少一种选自4-羟基丁醛、它与至少另一种醇的环状半缩醛和环状全缩醛的化合物,该法包括在碱性化合物存在下进行蒸馏。
2.根据权利要求1的方法,其中待分离的混合物含有4-羟基丁醛与沸点低于丁二醇的其他醇的环状全缩醛。
3.根据权利要求2的方法,其中其他醇还以游离形式在待分离的混合物中存在。
4.根据权利要求3的方法,其中在至少两个蒸馏段中,其他醇在第一段中蒸出,而丁二醇在第二段中蒸出。
5.根据权利要求1-4中任一项的方法,其中碱性化合物可溶于待分离的混合物中。
6.根据权利要求1-5中任一项的方法,其中碱性化合物选自锂、钠、钾、镁和钙的氧化物、氢氧化物、碳酸盐、羧酸盐和醇盐。
7.根据权利要求1-6中任一项的方法,其中用蒸馏法分离马来酸衍生物加氢中生成的混合物。
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DE19809493.0 | 1998-03-05 | ||
DE19809493A DE19809493A1 (de) | 1998-03-05 | 1998-03-05 | Verfahren zur Destillation Butandiol-haltiger Gemische |
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US (1) | US6387224B1 (zh) |
EP (1) | EP1060155B1 (zh) |
KR (1) | KR100580422B1 (zh) |
CN (1) | CN1132806C (zh) |
CA (1) | CA2322746C (zh) |
DE (2) | DE19809493A1 (zh) |
ES (1) | ES2200506T3 (zh) |
MY (1) | MY121420A (zh) |
WO (1) | WO1999044975A1 (zh) |
Cited By (2)
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CN102531834A (zh) * | 2011-12-15 | 2012-07-04 | 中国科学院过程工程研究所 | 一种1,4-丁二醇生产过程中的废液回收系统及工艺 |
TWI423947B (zh) * | 2007-07-30 | 2014-01-21 | Dow Global Technologies Llc | 精製c6-c16脂肪族二醇之方法 |
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EP1433774A1 (en) * | 2002-12-27 | 2004-06-30 | Koninklijke DSM N.V. | Process for reducing the aldehyde concentration in a mixture comprising cyclohexanone and one or more aldehydes |
GB0421928D0 (en) * | 2004-10-01 | 2004-11-03 | Davy Process Techn Ltd | Process |
JP6040597B2 (ja) * | 2011-07-04 | 2016-12-07 | 三菱化学株式会社 | 1,4−ブタンジオールの製造方法 |
KR101886473B1 (ko) * | 2011-07-04 | 2018-08-07 | 미쯔비시 케미컬 주식회사 | 테트라하이드로푸란의 제조 방법 |
WO2013012047A1 (ja) | 2011-07-20 | 2013-01-24 | 三菱化学株式会社 | 炭素原子数4の不飽和化合物を原料とする水素化物の製造方法 |
US9533931B2 (en) | 2013-04-12 | 2017-01-03 | Toray Industries, Inc. | Process of producing 1,4-butanediol |
CN107216237A (zh) * | 2017-07-19 | 2017-09-29 | 三惠(福建)工贸有限公司 | 一种低浓度1,4‑丁二醇的综合利用方法 |
IT202000031979A1 (it) * | 2020-12-22 | 2022-06-22 | Novamont Spa | Processo di purificazione di una miscela comprendente dioli e acetali |
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US4200501A (en) * | 1978-03-24 | 1980-04-29 | Basf Wyandotte Corporation | Silicate fouling control during dihydric alcohol distillation |
JPS56104881A (en) * | 1980-01-25 | 1981-08-20 | Toray Ind Inc | Preparation of tetrahydrofuran for polytetramethylene glycol |
US4879420A (en) * | 1988-05-06 | 1989-11-07 | E.I. Du Pont De Nemours And Company | Preparation of mixtures of butanediols |
DE4205471A1 (de) | 1992-02-22 | 1993-08-26 | Basf Ag | Verfahren zur abtrennung von 1,4-butandiol aus hydriergemischen |
DE19506280A1 (de) * | 1995-02-23 | 1996-08-29 | Hoechst Ag | Verfahren zur Destillation von Alkoholen |
JP2934173B2 (ja) | 1995-08-25 | 1999-08-16 | 東燃化学株式会社 | 高純度1,4−ブタンジオールの製造方法 |
ZA972614B (en) * | 1996-03-29 | 1997-12-22 | Kvaerner Process Tech Ltd | Process for the production of butane-1,4-diol. |
-
1998
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1999
- 1999-02-26 DE DE59905643T patent/DE59905643D1/de not_active Expired - Lifetime
- 1999-02-26 CA CA002322746A patent/CA2322746C/en not_active Expired - Fee Related
- 1999-02-26 WO PCT/EP1999/001250 patent/WO1999044975A1/de active IP Right Grant
- 1999-02-26 CN CN998036900A patent/CN1132806C/zh not_active Expired - Lifetime
- 1999-02-26 EP EP99910290A patent/EP1060155B1/de not_active Expired - Lifetime
- 1999-02-26 ES ES99910290T patent/ES2200506T3/es not_active Expired - Lifetime
- 1999-02-26 US US09/623,109 patent/US6387224B1/en not_active Expired - Lifetime
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Cited By (2)
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TWI423947B (zh) * | 2007-07-30 | 2014-01-21 | Dow Global Technologies Llc | 精製c6-c16脂肪族二醇之方法 |
CN102531834A (zh) * | 2011-12-15 | 2012-07-04 | 中国科学院过程工程研究所 | 一种1,4-丁二醇生产过程中的废液回收系统及工艺 |
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KR100580422B1 (ko) | 2006-05-16 |
DE19809493A1 (de) | 1999-09-09 |
DE59905643D1 (de) | 2003-06-26 |
MY121420A (en) | 2006-01-28 |
EP1060155A1 (de) | 2000-12-20 |
WO1999044975A1 (de) | 1999-09-10 |
CA2322746C (en) | 2008-05-13 |
ES2200506T3 (es) | 2004-03-01 |
KR20010041585A (ko) | 2001-05-25 |
EP1060155B1 (de) | 2003-05-21 |
CN1132806C (zh) | 2003-12-31 |
CA2322746A1 (en) | 1999-09-10 |
US6387224B1 (en) | 2002-05-14 |
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