CN1659140A - 类胡萝卜素晶体的形成和分离方法 - Google Patents
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Abstract
一种由含有类胡萝卜素的植物含油树脂生产类胡萝卜素晶体的方法,它包括:(a)在有机溶剂的回流温度下,将所述含油树脂加入该有机溶剂、醇和碱中以形成皂化反应混合物的第一步骤;(b)保持所述皂化反应混合物一段足以完成所述皂化反应的时间,由此制得皂化产物;(c)将所得的皂化产物分离成为有机相和水相;(d)分离所述两个相,然后萃取水相;(e)蒸馏所述有机相,得到类胡萝卜素晶体。
Description
技术领域
本发明涉及类胡萝卜素化合物的形成和分离方法,具体涉及从金盏花中分离胡萝卜醇晶体。
背景技术
在大自然中有丰富的类胡萝卜素,类胡萝卜素可以在水果、蔬菜、树叶、微生物和海洋生物中找到。类胡萝卜素用作抗氧化剂、食品着色剂,并用于癌症的预防。使用传统的提取方法,如美国专利6191293中公开的方法,可以容易地从这些化合物的天然来源中将它们提取出来。在除去溶剂之后,这种提取产生粗含油树脂。但是,所得的类胡萝卜素的浓度并没有高到足以将所述粗含油树脂直接用于人类的消费。
已知可替换的用于类胡萝卜素的形成、分离和提纯的化学方法,如US5,648,564中公开的方法。当该方法用于工业规模的用途时,所得的胡萝卜醇晶体的量不大,通常是产率为59%,纯度为79%。类似地,WO 01/94279中公开的方法提供了80%的产率和70-51%的纯度。WO 01/28966、ES 2 099 683、WO 99/20587和EP 0732378中公开的方法也有类似的问题。
此外,上述引用的现有技术的方法会产生大量的流出液,该流出液被碱,通常是氢氧化钾,以及与水混溶的有机溶剂,通常是1,3-丙二醇严重地污染。因此,必须对所得的产物进行处理,该处理需要在工业过程中增加昂贵的处理步骤。而且,在这些过程中对结晶的类胡萝卜素进行分离要通过离心步骤来进行,这可能是因为粗反应混合物的粘度较高,而离心步骤需要昂贵的设备和较高的投资。
发明内容
我们开发了一种方法,克服了前述现有技术中存在的问题,因此,本发明提供了一种由含有类胡萝卜素的植物含油树脂生产类胡萝卜素晶体的方法,它包括:(a)在有机溶剂的回流温度下,将所述含油树脂加入该有机溶剂、醇和碱中以形成皂化反应混合物的第一步骤;(b)保持所述皂化反应混合物一段足以完成所述皂化反应的时间,由此制得皂化产物;(c)将所得的皂化产物分离成为有机相和水相;(d)分离所述两个相,然后萃取水相;(e)蒸馏有机相,得到类胡萝卜素晶体。
本发明的方法相对于已知的现有技术的方法具有优势,因为可以更高的产率得到产物,并且产物的纯度更高。也无需提纯所得的晶体。
此外,本发明提供了一种制造纯类胡萝卜素,如呈全反式构造的胡萝卜素和胡萝卜醇的方法。在蒸馏过程中它们的顺式异构体发生异构化。因此,由本发明方法直接制得的产物适合于人类消耗或作为饲料补充剂。本发明的再一个优点是该方法产生的流出液的量比已知方法产生的流出液的量少2-32倍。溶剂在该方法的最后被蒸馏出来,并且可以再次使用,因此提供了一种环境有效的制造类胡萝卜素的手段。此外,用于该方法的设备简单,并且无需离心分离机或冷冻干燥设备,因此提供了一种用于工业规模制造的诱人的选择。
本发明的方法涉及从含有类胡萝卜素的植物中提取类胡萝卜素的晶体。得自本发明方法的类胡萝卜素包括:胡萝卜醇,例如叶黄素、玉米黄质、辣椒玉红素、辣椒红、虾青素和cathaxanthin;胡萝卜素,如β-胡萝卜素和番茄红素。较佳地,所述含有类胡萝卜素的植物是已知的那些含有高浓度的所需类胡萝卜素酯的植物,包括金盏花和浆果。所述含油树脂通过现有技术中已知的方法来提取。
在本发明方法的第一步骤中,用有机溶剂、醇和碱混合所述含油树脂,形成皂化反应混合物。适宜的有机溶剂是与水不混溶的有机溶剂,例如烃,如戊烷、己烷、庚烷和甲苯;醚,如二异丙醚、甲基叔丁基醚(MTBE)、二乙醚;氯化的溶剂,如二氯甲烷、二氯乙烷、一氯苯(MCB)。溶剂的浓度可以是0.5-10l/kg含油树脂,较好是1-4l/kg含油树脂。
关于醇,所述醇可以选自甲醇、乙醇、丙醇、异丙醇、叔丁醇和丁醇。优选的醇是异丙醇或丙醇。所述醇的浓度为0.5-10l/kg含油树脂,较好是1-4l/kg含油树脂。
关于碱,适宜的碱包括碱金属氢氧化物,例如氢氧化锂、氢氧化钠和氢氧化钾;碱金属碳酸盐,例如碳酸锂、碳酸钠和碳酸钾。优选的碱是氢氧化钠和氢氧化钾。
该方法的第一步骤在所述溶剂的回流温度下进行。在回流温度下保持反应物一段足以完成皂化反应的时间。所述的皂化产物包含两个相,即有机相和水相。分离所述两个相,然后将水相从反应体系中除去。然后,蒸馏剩余的有机相以除去微量的溶剂,从而提供所述类胡萝卜素晶体。该方法的这一步骤宜在50-100℃,较好是80-85℃的温度下进行。在蒸馏步骤中,较佳的是将水持续地引入反应体系中以保持液体的量。
所得的晶体可以通过过滤来分离。过滤可以在50-100℃的温度下进行。然后,可以将分离的晶体洗涤。所述清洗可以用水,或者适宜的溶剂如乙腈或醇(甲醇、乙醇、丙醇、异丙醇等)来进行。其中,需要使用水时,该步骤可以在50-100℃,较好是80-85℃的温度下进行;需要使用溶剂如乙腈或醇时,该步骤可以在零下5-40℃,较好是零下20-25℃的温度下进行。
水的量宜为1-20l/kg,较好是5-10l/kg。
所得的晶体具有较高的纯度,一般为85-99%,通常大于95%。产物的产率一般为40-90%,通常是70-80%。
具体实施方式
以下,将参照下述实施例详细地描述本发明。
实施例1
在回流下将72.8g金盏花含油树脂(得自法国Naturex公司,每kg含油树脂含有128g类胡萝卜素)溶解在150ml己烷和150ml异丙醇中。然后,引入150ml氢氧化钠水溶液(30重量%),并在回流下,在强烈的搅拌及氮气氛下保持粗反应混合物,直到皂化完成(2.5小时,由高性能液体色谱(HPLC)测得的完成率大于97%)。此时,停止搅拌,并迅速将混合物分离成为两个相(上层有机相和下层水相)。除去下层的水相。蒸馏除去所述有机溶剂(己烷和异丙醇),同时用约等于输出流量的输入流量引入500ml预处理的水(90℃),使得液相的总体积不超过600ml。在蒸馏的最后阶段,过滤含有水性液相和结晶类胡萝卜素的粗混合物,用以分离结晶的类胡萝卜素。先后用3等分试样的150ml温水、3等分试样的150ml室温乙腈和3等分试样的150ml室温己烷清洗滤饼。在室温下,于减压下除去残余的微量溶剂。收集到6.76g橙色/红色的纯胡萝卜醇晶体(产率:72.3%,以总的类胡萝卜素计)。用HPLC分析所得的晶体(91.2%全反式叶黄素,8.8%全反式玉米黄质,未测得顺式异构体和其它类胡萝卜素,总的类胡萝卜素产率超过95%)。
实施例2
在回流下将82.5g金盏花含油树脂(得自印度Plant Lipids Limited公司,每kg含油树脂含有100g类胡萝卜素)溶解在150ml己烷和150ml异丙醇中。然后,引入150ml氢氧化钠水溶液(30重量%),并在回流下,在强烈的搅拌及氮气氛下保持粗反应混合物,直到皂化完成(2.5小时,由HPLC测得的完成率大于97%)。此时,停止搅拌,并迅速将混合物分离成为两个相(上层相:有机相;下层相:水相)。除去下层相(水相)。蒸馏除去所述有机溶剂(即,己烷和异丙醇),同时用约等于输出流量的输入流量引入500ml预处理的水(90℃),使得液相的总体积不超过600ml。在蒸馏的最后阶段,过滤含有水性液相和结晶类胡萝卜素的粗混合物,用以分离结晶的类胡萝卜素。先后用3等分试样的150ml温水和3等分试样的150ml室温乙醇清洗滤饼。在室温下,于减压下除去残余的微量溶剂。收集到6.45g橙色/红色的纯胡萝卜醇晶体(产率:78.2%,以总的类胡萝卜素计)。用HPLC分析所得的晶体(91.2%全反式叶黄素,8.8%全反式玉米黄质,未测得顺式异构体和其它类胡萝卜素,总的类胡萝卜素产率超过95%)。
实施例3
在回流下将56.1g金盏花含油树脂(得自法国Naturex公司,每kg含油树脂含有128g类胡萝卜素)溶解在150ml己烷和150ml异丙醇中。然后,引入150ml氢氧化钠水溶液(30重量%),并在回流下,在强烈的搅拌及氮气氛下保持粗反应混合物,直到皂化完成(2.5小时,由HPLC测得的完成率大于97%)。此时,停止搅拌,并迅速将混合物分离成为两个相(上层有机相和下层水相)。除去下层的水相。将有机溶剂缓慢地倒入500ml预处理的水(95℃)中,然后立即蒸馏除去所述有机溶剂,调节输入流量以将内部容积保持在低于600ml。在添加的最后阶段,保持加热状态,直到有机溶剂的蒸馏完成,然后,通过过滤来收集类胡萝卜素晶体。先后用3等分试样的150ml温水和3等分试样的150ml室温己烷清洗滤饼。在室温下,于减压下除去残余的微量溶剂。收集到3.5g橙色/红色的纯胡萝卜醇晶体(产率:51%,以总的类胡萝卜素计)。用HPLC分析所得的晶体(93%全反式叶黄素,7%全反式玉米黄质,未测得顺式异构体和其它类胡萝卜素,总的类胡萝卜素产率超过95%)。
实施例4-17
在45℃,将市售的金盏花含油树脂溶解在10ml己烷、2.5ml丁醇和2ml氢氧化钠水溶液(30重量%)中。在搅拌下,于惰性气氛下保持反应混合物5小时。然后,停止搅拌,将混合物迅速分离成为两个相。按实施例1所述分离所述两个相,并进行随后的处理。产物的产率列于下表1中。
表 1
实施例 | 质量(mg) | 转化率%(5小时) | 类胡萝卜素的用量(mg) | 反式/顺式的比例 | 产率%(含油树脂) | 产率%(/总的类胡萝卜素的量) |
4 | 97.3 | >97 | 110.5 | 87/13 | 11.4% | 88.2% |
5 | >97 | 111.3 | 87/13 | |||
6 | 111.6 | >97 | 119.2 | 90/10 | 10.6% | 92.2% |
7 | >97 | 118.4 | 90/10 | |||
8 | 120.8 | >97 | 126.2 | 83/17 | 10.4% | 87.5% |
9 | >97 | 124.7 | 84/16 | |||
10 | 108.8 | >97 | 137.2 | 94/6 | 12.7% | 93.6% |
11 | >97 | 138.4 | 94/6 | |||
12 | 112.1 | >97 | 114.9 | 82/18 | 10.2% | 86.5% |
13 | >97 | 113.4 | 82/18 | |||
14 | 132.4 | >97 | 146.6 | 91/9 | 11.1% | 84.9% |
15 | >97 | 146.0 | 92/8 | |||
16 | 131.9 | >97 | 139.4 | 89/11 | 10.6% | 86.9% |
17 | >97 | 139.0 | 90/10 |
实施例18-23
将1g含油树脂(得自Plant Lipids Limited公司,每kg含油树脂含有100g类胡萝卜素)溶解在下表2中详细列出的各种溶剂中,然后加入醇,再加入3ml碱金属氢氧化物。在搅拌下,于惰性气氛下保持反应混合物,直到反应完成。
表 2
实施例 | 溶剂 | 醇 | 碱(30重量%) | 温度℃ | 时间(小时) | 转化率(%) |
18 | MTBE | 丁醇 | KOH | 50 | 3 | >95 |
19 | 甲苯 | 丁醇 | NaOH | 60 | 5 | >95 |
20 | C2H4Cl2 | 异丙醇 | NaOH | 60 | 3 | >95 |
21 | 叔丁醇 | KOH | 60 | 3 | >95 | |
22 | MCB | 丙醇 | KOH | 60 | 3 | >95 |
23 | 2-丁醇 | NaOH | 60 | 3 | >95 |
Claims (8)
1.一种由含有类胡萝卜素的植物含油树脂生产类胡萝卜素晶体的方法,它包括:(a)在有机溶剂的回流温度下,将所述含油树脂加入该有机溶剂、醇和碱中以形成皂化反应混合物的第一步骤;(b)保持所述皂化反应混合物一段足以完成所述皂化反应的时间,制得皂化产物;(c)将所得的皂化产物分离成为有机相和水相;(d)分离所述两个相,然后萃取水相;(e)蒸馏所述有机相,得到类胡萝卜素晶体。
2.如权利要求1所述的方法,其特征在于,所述有机溶剂是与水不混溶的有机溶剂。
3.如权利要求2所述的方法,其特征在于,所述有机溶剂是烃、醚或氯化的溶剂。
4.如权利要求3所述的方法,其特征在于,所述有机溶剂是烃,它选自戊烷、己烷、庚烷和甲苯。
5.如前述任一权利要求所述的方法,其特征在于,所述醇选自甲醇、乙醇、丙醇、叔丁醇和丁醇。
6.如前述任一权利要求所述的方法,其特征在于,所述碱选自碱金属氢氧化物或碱金属碳酸盐。
7.如权利要求6所述的方法,其特征在于,所述碱是氢氧化锂、氢氧化钠或氢氧化钾。
8.如前述任一权利要求所述的方法,其特征在于,在所述有机相的蒸馏过程中,将水持续地引入反应体系中。
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EP02356104A EP1371641A1 (en) | 2002-06-10 | 2002-06-10 | Process for the formation and isolation of carotenoid crystals |
EP02356104.6 | 2002-06-10 |
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CN1659140A true CN1659140A (zh) | 2005-08-24 |
CN1283623C CN1283623C (zh) | 2006-11-08 |
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CNB038133989A Expired - Fee Related CN1283623C (zh) | 2002-06-10 | 2003-06-04 | 类胡萝卜素晶体的形成和分离方法 |
Country Status (14)
Country | Link |
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US (1) | US20050139145A1 (zh) |
EP (2) | EP1371641A1 (zh) |
JP (1) | JP2005535609A (zh) |
CN (1) | CN1283623C (zh) |
AU (1) | AU2003240153A1 (zh) |
BR (1) | BR0311688A (zh) |
CA (1) | CA2487013A1 (zh) |
MX (1) | MXPA04012134A (zh) |
PE (1) | PE20040141A1 (zh) |
PL (1) | PL372759A1 (zh) |
RU (1) | RU2004138796A (zh) |
UA (1) | UA77308C2 (zh) |
WO (1) | WO2003104190A1 (zh) |
ZA (1) | ZA200409355B (zh) |
Cited By (4)
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WO2009027850A2 (en) * | 2007-06-06 | 2009-03-05 | Multi-Tech Specialty Chemicals Co., Ltd. | Process for the preparation of xanthophyll crystals |
CN101260071B (zh) * | 2008-04-15 | 2010-06-09 | 中国日用化学工业研究院 | 叶黄素的分离与纯化方法 |
CN104447464A (zh) * | 2013-09-24 | 2015-03-25 | 浙江医药股份有限公司新昌制药厂 | 一种植物来源含天然虾青素的类胡萝卜素化合物及其制备方法和组合物 |
CN106280542A (zh) * | 2016-08-15 | 2017-01-04 | 晨光生物科技集团股份有限公司 | 一种提高番茄红素油树脂品质的生产方法 |
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US7622599B2 (en) * | 2005-04-25 | 2009-11-24 | Katra Phytochem Private Limited | Isolation and purification of carotenoids from marigold flowers |
ES2265787B1 (es) * | 2005-08-09 | 2007-11-16 | Carotenoid Technologies, S.A. | Procedimiento para la preparacion de un pigmento a partir de oleorresinas naturales ricas en esteres de xantofilas. |
US7875751B2 (en) * | 2008-11-07 | 2011-01-25 | Allied Biotech Corporation | Method for the purification of carotenoids from plant extracts and the products so obtained |
EP2196207B1 (en) * | 2008-12-12 | 2012-09-05 | Allied Biotech Corporation | Method for the purification of carotenoids from plant extracts and the products so obtained |
CN101828693B (zh) * | 2009-03-09 | 2013-01-02 | 浙江医药股份有限公司新昌制药厂 | 制备低粘度高流动性类胡萝卜素油悬浮液的方法及其应用 |
US8716533B2 (en) | 2009-05-29 | 2014-05-06 | Kalamazoo Holdings, Inc. | Methods of saponifying xanthophyll esters and isolating xanthophylls |
US8247615B2 (en) | 2010-05-14 | 2012-08-21 | Kalamazoo Holdings, Inc. | Process of converting esterified xanthophylls from Capsicum to non-esterified xanthophylls in high yields and purities |
US8008532B2 (en) * | 2009-09-15 | 2011-08-30 | Unibar Corporation | Processes and methods for extraction and purification of lutein from marigold esters |
EP2571942B1 (en) | 2010-05-17 | 2014-05-21 | Dynadis Biotehc (India) Private Limited | Process for isolation and purification of carotenoids |
CN102139877A (zh) * | 2011-01-26 | 2011-08-03 | 山东盛华光伏材料有限公司 | 一种采用含铁化合物去除工业硅中硼磷杂质的方法 |
BR112015014187B8 (pt) | 2012-12-19 | 2022-08-30 | Novus Int Inc | Composição de xantofila, seu uso, ração animal e métodos de aumento da eficácia de pigmentação e do teor de carotenoide da ração |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2572467A (en) * | 1949-08-04 | 1951-10-23 | Colgate Palmolive Peet Co | Concentration and recovery of carotenoid pigments from palm oil |
US5382714A (en) * | 1994-03-17 | 1995-01-17 | The Catholic University Of America | Process for isolation, purification, and recrystallization of lutein from saponified marigold oleoresin and uses thereof |
JP3398248B2 (ja) * | 1995-03-16 | 2003-04-21 | 新日本石油株式会社 | キサントフィル化合物の精製方法 |
US5648564A (en) * | 1995-12-21 | 1997-07-15 | Kemin Industries, Inc. | Process for the formation, isolation and purification of comestible xanthophyll crystals from plants |
AU1271999A (en) * | 1997-10-21 | 1999-05-10 | Office Of Technology Liaison | Process for extraction and purification of lutein, zeaxanthin and rare carotenoids from marigold flowers and plants |
US6191293B1 (en) * | 1998-04-20 | 2001-02-20 | Inexa, Industria Extractora C.A. | Trans-xanthophyll ester concentrates of enhanced purity and methods of making same |
RU2256651C2 (ru) * | 2000-01-27 | 2005-07-20 | ДСМ Ай Пи АССЕТС Б.В. | Выделение каротиноидных кристаллов |
US7119238B2 (en) * | 2000-07-12 | 2006-10-10 | University Of Maryland | Process for purification and crystallization of palm oil carotenoids |
EP1253131A1 (en) * | 2001-04-24 | 2002-10-30 | Aventis Animal Nutrition S.A. | Process for the preparation of an xanthophyll |
US6380442B1 (en) * | 2001-10-10 | 2002-04-30 | Bioactives, Llc | Process for the isolation of mixed carotenoids from plants |
-
2002
- 2002-06-10 EP EP02356104A patent/EP1371641A1/en not_active Withdrawn
-
2003
- 2003-04-06 UA UA20041210601A patent/UA77308C2/uk unknown
- 2003-06-04 JP JP2004511260A patent/JP2005535609A/ja active Pending
- 2003-06-04 MX MXPA04012134A patent/MXPA04012134A/es not_active Application Discontinuation
- 2003-06-04 CN CNB038133989A patent/CN1283623C/zh not_active Expired - Fee Related
- 2003-06-04 EP EP03732768A patent/EP1515948A1/en not_active Withdrawn
- 2003-06-04 WO PCT/IB2003/002101 patent/WO2003104190A1/en not_active Application Discontinuation
- 2003-06-04 PL PL03372759A patent/PL372759A1/xx not_active Application Discontinuation
- 2003-06-04 CA CA002487013A patent/CA2487013A1/en not_active Abandoned
- 2003-06-04 US US10/514,044 patent/US20050139145A1/en not_active Abandoned
- 2003-06-04 BR BRPI0311688-3A patent/BR0311688A/pt not_active IP Right Cessation
- 2003-06-04 AU AU2003240153A patent/AU2003240153A1/en not_active Abandoned
- 2003-06-04 RU RU2004138796/04A patent/RU2004138796A/ru not_active Application Discontinuation
- 2003-06-06 PE PE2003000568A patent/PE20040141A1/es not_active Application Discontinuation
-
2004
- 2004-11-19 ZA ZA200409355A patent/ZA200409355B/en unknown
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009027850A2 (en) * | 2007-06-06 | 2009-03-05 | Multi-Tech Specialty Chemicals Co., Ltd. | Process for the preparation of xanthophyll crystals |
WO2009027850A3 (en) * | 2007-06-06 | 2009-06-18 | Multi Tech Specialty Chemicals | Process for the preparation of xanthophyll crystals |
US8034983B2 (en) | 2007-06-06 | 2011-10-11 | Multi-Tech Specialty Chemicals, Co., Ltd. | Process for the preparation of xanthophyll crystals |
CN101260071B (zh) * | 2008-04-15 | 2010-06-09 | 中国日用化学工业研究院 | 叶黄素的分离与纯化方法 |
CN104447464A (zh) * | 2013-09-24 | 2015-03-25 | 浙江医药股份有限公司新昌制药厂 | 一种植物来源含天然虾青素的类胡萝卜素化合物及其制备方法和组合物 |
CN104447464B (zh) * | 2013-09-24 | 2016-11-23 | 浙江医药股份有限公司新昌制药厂 | 一种植物来源含天然虾青素的类胡萝卜素化合物及其制备方法和组合物 |
CN106280542A (zh) * | 2016-08-15 | 2017-01-04 | 晨光生物科技集团股份有限公司 | 一种提高番茄红素油树脂品质的生产方法 |
CN106280542B (zh) * | 2016-08-15 | 2017-11-17 | 晨光生物科技集团股份有限公司 | 一种提高番茄红素油树脂品质的生产方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2005535609A (ja) | 2005-11-24 |
US20050139145A1 (en) | 2005-06-30 |
PL372759A1 (en) | 2005-08-08 |
EP1371641A1 (en) | 2003-12-17 |
WO2003104190A1 (en) | 2003-12-18 |
ZA200409355B (en) | 2005-05-19 |
CA2487013A1 (en) | 2003-12-18 |
PE20040141A1 (es) | 2004-05-04 |
UA77308C2 (en) | 2006-11-15 |
BR0311688A (pt) | 2008-01-15 |
AU2003240153A1 (en) | 2003-12-22 |
EP1515948A1 (en) | 2005-03-23 |
CN1283623C (zh) | 2006-11-08 |
RU2004138796A (ru) | 2005-06-27 |
MXPA04012134A (es) | 2005-04-19 |
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