CN1051297C - 从工业上所制得的乙酸中去除醛类及缩醛类的方法 - Google Patents
从工业上所制得的乙酸中去除醛类及缩醛类的方法 Download PDFInfo
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- CN1051297C CN1051297C CN94109035A CN94109035A CN1051297C CN 1051297 C CN1051297 C CN 1051297C CN 94109035 A CN94109035 A CN 94109035A CN 94109035 A CN94109035 A CN 94109035A CN 1051297 C CN1051297 C CN 1051297C
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- acetate
- acid
- acetic acid
- acetals
- aldehydes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种从工业上所制得的乙酸中去除醛类及缩醛类的方法,包括使经污染的乙酸于有布朗斯特酸存在下,与0.05至1%重量的水及,若需要时,3至10当量(以醛及缩醛为计算基准)的高沸点多元醇在50至118℃的温度中反应1至5小时,然后以分馏法由反应产物中分离出纯乙酸;其中该多元醇具有以下的一般结构单元:
其中n为0至3的整数,m为大于3的整数。
Description
本发明涉及从工业上所制得的乙酸中去除醛类及缩醛类的方法,该乙酸特别是来源于乙醛的催化氧化反应及甲醇的羰基化反应。
工业上所制得的乙酸,视其制法而定,会含有一些杂质诸如甲酸,乙酸酯,甲酸酯,乙醛及甲醛。为了达到较高的规格等级,例如“化学纯”的品质,乙酸中这些杂质的含量必须被尽可能地降低。供此目的所用的分析方法为铬酸试验,使用Deutsches Arzneibuch〔Ger-man Pharmacopeia〕10(1991)中所述的分析方法,可定量测定乙酸中可氧化性杂质的含量。
除了可采用蒸馏法分离出的该化合物的外,亦有会在乙酸沸点范围内沸腾的杂质,因此这些杂质无法以蒸馏法去除。这些主要为醛类的加成或缩合反应产物,尤其是可氧化的半缩醛及完整缩醛,例如甲醛甲基乙酰基缩醛(乙酸甲氧基甲酯;沸点117-118℃)或乙醛二乙醛基缩醛(1,1-二乙酰氧基乙烷;沸点169℃)。由于这些化合物亦以铬酸试验测定,故以蒸馏法所得到符合规格的化学纯乙酸的产量不能令人满意。
故为了去除醛类与缩醛类,US-A-4061546中已建议使用重铬酸钾作氧化剂,而DE-A-2104828中已建议用过锰酸钾作氧化剂,然后在下游蒸馏法中获得纯乙酸。
这些方法的缺点为使用昂贵的氧化剂,它们会导致生成含重金属的蒸馏残余物,而它们处置很麻烦。此外,在此种氧化方法中会形成毒性产物,例如来自甲醛的甲酸。
因此,找出能由工业上制得的乙酸中尽可能完全去除醛类与缩醛类的不昂贵方法为一目标,其中必须不形成处置上的难题及毒性产物。
惊人的是,依照本发明方法可达成此目标,即在50至118℃的温度中将乙酸在布朗斯特酸存在下与0.05至1%重量的水及3至10当量(以醛及缩醛为计算基准)具有下列一般结构单元的高沸点多元醇反应1至5小时,其中n为0至3的整数,m为大于3的整数,再以分馏法将纯乙酸由反应产物中分离出来。
此外,本发明方法有下列特点:a)所用的布朗斯特酸为选自硫酸,甲磺酸,甲苯磺酸或磷酸中的物质,其量为每升经污染乙酸用0.005至0.05摩尔;b)所用的高沸点多元醇为选自聚乙烯醇,蔗糖及右旋糖,淀粉或纤维素中的物质。
工业上所制得的乙酸最好与过量的高沸点多元醇反应,以确保尽可能完全去除醛类与缩醛类。
较好可使用由聚乙酸乙烯酯在甲醇中水解所得的多元醇。
若只意欲工业乙酸的部分纯化,则不须加入高沸点多元醇。实施例1显示不加入高沸点多元醇时的清除效果。
以含有下列杂质的工业上所制乙酸来进行实例1,2及比较实例:乙酸含量 99.6(%重)水 0.036(%重)甲醛 57(ppm)乙醛 1.8(ppm)乙酸甲酯 59(ppm)乙酸乙酯 151(ppm)乙酸异丙酯 40(ppm)乙酸甲氧甲酯 130(ppm)铬酸试验依照Schering 80(g的CrO3%kg)(%kg表示“每100kg”)
通过以下实例更详细叙述本发明。实施例1(不加入多元醇)
将5kg工业上所制乙酸与3.5g水及5g甲磺酸一同放在蒸汽挡板塔(具有20块板)的蒸发器中,以350毫巴的塔顶压力回流3小时。然后以350毫巴的塔顶压力对混合物分馏,回流比率逐渐降至终点(10∶1至2∶1)。于0.54kg的低沸点初馏物(包括冷阱产物)后,将全部的各馏份混合,得到铬酸试验具有21g CrO3%kg的乙酸1.68kg(原料的33.6%重)及铬酸试验具有<10g CrO3%kg的乙酸2.73g(原料的54.6%重)。实施例2(有多元醇加入)
将5kg工业上所制乙酸与3.5g水、5g甲磺酸及0.9gMOWIOL10-74(以醛与缩醛计算为10倍当量过量)一同在一个6升玻璃烧瓶中,该烧瓶连接在具有一个20板的蒸气挡板塔上,混合物在350毫巴的塔顶压力及87.5℃的塔底温度中回流3小时。回流比率为10∶1时,分馏产生350g的水性初馏物,该初馏物具有216g CrO3%kg的铬酸试验。塔底温度在90℃与112℃的间(塔的第10板为89℃至90℃,塔顶温度87℃)而回流比率逐渐下降(10∶1至2∶1)时,得4520g乙酸,该乙酸具有7g CrO3%kg的铬酸试验(DAB10品质:<32g的CrO3%kg),且得表1中所列的分析数据。它代表所用乙酸的90%。另23g位于蒸馏冷阱中,而残余物以蒸馏塔底产物形成留下。
表1
经纯化的乙酸乙酸含量 99.8(%)水 0.18(%)甲醛 <10(ppm)乙醛 0.2(ppm)乙酸甲酯 <10(ppm)乙酸乙酯 <10(ppm)乙酸异丙酯 <10(ppm)乙酸甲氧甲酯 <10(ppm)铬酸试验依照Schering 7(g的CrO3%kg)比较实施例(只用蒸馏法来纯化)
将500g工业上所制得乙酸放在具有30块板的塔的蒸发器中。于完全回流条件下,蒸发器内容物以230毫巴的塔顶压力加热至85℃。当塔达平衡时便以6∶1的回流比率进行分馏。取出83g的初馏物后,得167g馏份,其有<32g CrO3%kg的铬酸试验。接着139g的馏出物有10g CrO3%kg的铬酸试验,其纯度被进一步改进。于此馏份的后再得83g,其有<32g CrO3%kg的铬酸试验。有27g以塔底产物形式留下。总而言之,所用乙酸的50.0%被获得而具有<32g CrO3%kg的铬酸试验,且所用乙酸的28.0%被获得而具有<10g CrO3%kg的铬酸试验。
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4327011.5 | 1993-08-12 | ||
DE4327011A DE4327011A1 (de) | 1993-08-12 | 1993-08-12 | Verfahren zur Entfernung von Aldehyden und Acetalen aus technisch hergestellter Essigsäure |
Publications (2)
Publication Number | Publication Date |
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CN1108235A CN1108235A (zh) | 1995-09-13 |
CN1051297C true CN1051297C (zh) | 2000-04-12 |
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Application Number | Title | Priority Date | Filing Date |
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CN94109035A Expired - Fee Related CN1051297C (zh) | 1993-08-12 | 1994-08-10 | 从工业上所制得的乙酸中去除醛类及缩醛类的方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US5620567A (zh) |
EP (1) | EP0638538B1 (zh) |
JP (1) | JPH07145103A (zh) |
KR (1) | KR950005794A (zh) |
CN (1) | CN1051297C (zh) |
CA (1) | CA2128548A1 (zh) |
DE (2) | DE4327011A1 (zh) |
MY (1) | MY111014A (zh) |
SG (1) | SG54085A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102378807A (zh) * | 2009-03-31 | 2012-03-14 | 通用电气公司 | 在烃加工中抑制污垢的方法中还原性糖的用途 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG44317A1 (en) * | 1994-06-15 | 1997-12-19 | Daicel Chem | Process for producing high purity acetic acid |
IN192600B (zh) * | 1996-10-18 | 2004-05-08 | Hoechst Celanese Corp | |
US7524988B2 (en) | 2006-08-01 | 2009-04-28 | Lyondell Chemical Technology, L.P. | Preparation of acetic acid |
US7485749B2 (en) * | 2006-08-22 | 2009-02-03 | Lyondell Chemical Technology, L.P. | Preparation of acetic acid |
US7345197B1 (en) | 2007-06-05 | 2008-03-18 | Lyondell Chemical Technology, L.P. | Preparation of acetic acid |
US7390919B1 (en) | 2007-10-01 | 2008-06-24 | Lyondell Chemical Technology, L.P. | Methyl acetate purification and carbonylation |
US8076512B2 (en) * | 2009-08-27 | 2011-12-13 | Equistar Chemicals, L.P. | Preparation of acetic acid |
US8969613B2 (en) | 2012-10-31 | 2015-03-03 | Lyondellbasell Acetyls, Llc | Removal of aldehydes in acetic acid production |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2273459A (en) * | 1938-11-25 | 1942-02-17 | Dow Chemical Co | Purification of acetic acid |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE307550C (zh) * | ||||
US2295618A (en) * | 1937-05-29 | 1942-09-15 | Gen Aniline & Film Corp | Recovery of aliphatic polyhydroxy compounds |
US2382181A (en) * | 1941-06-17 | 1945-08-14 | Distillers Co Yeast Ltd | Concentration of aqueous acetic acid |
US2651604A (en) * | 1949-09-02 | 1953-09-08 | Courtaulds Ltd | Recovery of acetic acid from aqueous acetic acid solutions by extractive distillation |
DE892894C (de) * | 1950-04-27 | 1953-10-12 | Melle Usines Sa | Verfahren zur Gewinnung von Essigsaeure und Methanol aus methylacetathaltigen Gemischen |
US2703309A (en) * | 1951-08-28 | 1955-03-01 | Eastman Kodak Co | Purification of acids from the manufacture of anhydrides |
US2867655A (en) * | 1957-02-20 | 1959-01-06 | Donald F Othmer | Process for recovering volatile aliphatic acids |
US3196176A (en) * | 1962-03-07 | 1965-07-20 | Celanese Corp | Purification of acetic acid |
US3709795A (en) * | 1970-02-02 | 1973-01-09 | Monsanto Co | Purification of carboxylic acids by chemical treatment and distillation |
BE791577A (fr) * | 1971-11-19 | 1973-05-17 | Monsanto Co | Purification de courants d'acide carboxylique |
BE791831A (fr) * | 1971-11-26 | 1973-03-16 | Degussa | Procede d'obtention de 3-methylmercaptopropionaldehyde pur |
US4110372A (en) * | 1972-11-29 | 1978-08-29 | Hoechst Aktiengesellschaft | Process for the purification of carboxylic acids |
US4061546A (en) * | 1976-03-29 | 1977-12-06 | Monsanto Company | Purification of acetic acid |
US4230887A (en) * | 1978-02-16 | 1980-10-28 | Celanese Corporation | Recovery of anhydrous acids |
DE3019765A1 (de) * | 1980-05-23 | 1981-12-10 | Basf Ag, 6700 Ludwigshafen | Verfahren zur gewinnung von acetaldehyd und methanol aus reaktionsgemischen der methanol-homologisierung |
DE3019766A1 (de) * | 1980-05-23 | 1981-12-03 | Basf Ag, 6700 Ludwigshafen | Verfahren zur destillativen zerlegung von aliphatische alkohole enthaltenden fluessigkeitsgemischen |
SU1699950A1 (ru) * | 1990-01-26 | 1991-12-23 | Всесоюзный Комплексный Научно-Исследовательский И Конструкторско-Технологический Институт Водоснабжения, Канализации, Гидротехнических Сооружений И Инженерной Гидрогеологии "Водгео" | Способ очистки сточных вод, содержащих формальдегид и метанол |
-
1993
- 1993-08-12 DE DE4327011A patent/DE4327011A1/de not_active Withdrawn
-
1994
- 1994-07-09 SG SG1995001379A patent/SG54085A1/en unknown
- 1994-07-09 DE DE59407171T patent/DE59407171D1/de not_active Expired - Fee Related
- 1994-07-09 EP EP94110715A patent/EP0638538B1/de not_active Expired - Lifetime
- 1994-07-21 CA CA002128548A patent/CA2128548A1/en not_active Abandoned
- 1994-07-29 US US08/283,280 patent/US5620567A/en not_active Expired - Fee Related
- 1994-08-05 MY MYPI94002049A patent/MY111014A/en unknown
- 1994-08-05 KR KR1019940019315A patent/KR950005794A/ko not_active Application Discontinuation
- 1994-08-10 JP JP6188470A patent/JPH07145103A/ja not_active Withdrawn
- 1994-08-10 CN CN94109035A patent/CN1051297C/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2273459A (en) * | 1938-11-25 | 1942-02-17 | Dow Chemical Co | Purification of acetic acid |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102378807A (zh) * | 2009-03-31 | 2012-03-14 | 通用电气公司 | 在烃加工中抑制污垢的方法中还原性糖的用途 |
CN102378807B (zh) * | 2009-03-31 | 2014-12-10 | 通用电气公司 | 在烃加工中抑制污垢的方法中还原性糖的用途 |
TWI488956B (zh) * | 2009-03-31 | 2015-06-21 | Gen Electric | 用於抑制碳氫化合物加工中之污染的方法 |
Also Published As
Publication number | Publication date |
---|---|
SG54085A1 (en) | 1998-11-16 |
CN1108235A (zh) | 1995-09-13 |
MY111014A (en) | 1999-07-31 |
DE59407171D1 (de) | 1998-12-03 |
DE4327011A1 (de) | 1995-02-16 |
EP0638538B1 (de) | 1998-10-28 |
US5620567A (en) | 1997-04-15 |
JPH07145103A (ja) | 1995-06-06 |
KR950005794A (ko) | 1995-03-20 |
CA2128548A1 (en) | 1995-02-13 |
EP0638538A1 (de) | 1995-02-15 |
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