CN86104638A - L-抗坏血酸的提纯方法 - Google Patents
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Abstract
L-抗坏血酸的提纯方法,它包括:对含有无机酸盐的L-抗坏血酸水溶液进行电渗析,以除去其中的盐。本发明特别用于从生产L-抗坏血酸得到的L-抗坏血酸和无机盐的含水混合物中除去无机酸盐,在生产L-抗坏血酸过程中,在无机酸存在下加热双酮-2-酮-L-古洛糖酸或2-酮-L-古洛糖酸,或者在碱存在下,使2-酮-L-古洛糖酸烷基酯烯醇化和内酯化。
Description
本发明是关于L-抗坏血酸的提纯方法,确切地说,是通过从中除去无机酸盐提纯L-抗坏血酸的方法。
迄今为止,L-抗坏血酸主要通过两种方法生产。一种方法是,在无机酸存在下,使双丙酮-2-酮-L-古洛糖酸或2-酮-L-古洛糖酸直接烯醇化和内酯化,以得到L-抗坏血酸和无机酸的含水的混合物,如美国专利2179977,所公开的,其方法以下称作直接法。另一种方法是,在碱存在下,使2-酮-L-古洛糖酸烯醇化和内酯化,以得到L-抗坏血酸的碱金属盐或碱土金属盐,然后用戊基酸使其脱金属或中和,以提供L-抗坏血酸和无机酸盐的含水混合物,如美国专利2265121所公开的,其方法以下称作烷基酯烯醇化法。
已经知道多种方法除去上述L-抗坏血酸的生产中得到的L-抗坏血酸混合物中的无机酸成无机酸盐。在直接法中,用酸与铅或银的碱性化合物反应,除去无机酸,例如盐酸,以形成易除去的不溶于水的化合物,例如氯化铝或氯化银,如美国专利2444087所公开的。适用直接法的另一方法除去无机酸,是用碱例如氢氧化钠中和酸,使酸转变成其碱金属盐例如氯化钠,然后通过例如用结晶法从混合物中分离L-抗坏血酸。而在烷基酯烯醇化法中,L-抗坏血酸的金属盐同样与有机溶剂例如甲醇中的氯化氢气体反应,得到L-抗坏血酸和盐例如氯化钠,后者从L-抗坏血酸中分离出来。又一方法中,用强酸性阳离子交换树脂,使L-抗坏血酸金属盐脱金属。
但是,用上述先有方法,往往很难从直接法产生的反应混合物中有效地除去所用的无机酸,因此,先有方法就不能提供高纯度L-抗坏血酸,在烷基酯烯醇化法中,当L-抗坏血酸脱金属是在有机溶剂中进行时,需要大量的溶剂而使用离子交换树脂进行脱金属时,需要大量的酸,以使离子交换树脂再生。
另一方面,由日本专利号47-18858得知一种方法,该方法是用电渗析法,从L-抗坏血酸和碳水化合物,例如L-山梨糖和L-塔洛糖的混合物中分离L-抗坏血酸,在该方法中,L-抗坏血酸本与通过阴离子交换膜,压入渗析溶液或电解液,因此,如先有技术所描述,此法被限制在从低于1%(按重量计)的稀溶液中分离L-抗坏血酸,并且为了从L-抗坏血酸和无机酸盐的混合物中分离L-抗坏血酸,采用此法可能不实际。
在日本专利号50-111062中也得到另外的方法,在此方法中,L-抗坏血酸的碱金属成碱土金属盐先经过电渗析使之部分脱金属,然后,用强酸性离子交换树脂使残存的盐脱金属。在此方法中,按照先有技术,脱金属需要两步操作,且完全电渗析法缺点在于其电流效率显著减少。
本发明人做了广泛的研究,发现了一种有效的方法,从无机酸如直接法产生的混合物中分离L-抗坏血酸,且发现此法非常有效,它包括加入相当于L-抗坏血酸和无机酸的混合物中无机酸的量的碱,使酸转变成相应的盐,然后对L-抗坏血酸和盐的混合物进行电渗析,以便从混合物中除去盐。经过进一步的研究后,发明人发现,电渗析法能同样有效地应用于通过烷基酯烯醇化法提纯L-抗坏血酸,在电渗析法用于烷基酯烯醇化法产生的反应混合物,其中生成L-抗坏血酸的金属盐时,以相当于反应混合物中L-抗坏血酸的金属盐的量加入无机酸,以便中和盐,成为L-抗坏血酸和无机酸盐混合物的水溶液,从而使所得的水溶液进行电渗析。
因此,本发明的目的是提供L-抗坏血酸的一种提纯方法,特别是提供除去L-抗坏血酸的水溶液中所含的无机酸盐的方法。
本发明的L-抗坏血酸的提纯方法包括:对含有无机酸盐的L-抗坏血酸的酸性水溶液进行电渗析,以除去其中的盐。
本发明的方法适用于任何含有无机酸的L-抗坏血酸的酸性水溶液,而且该溶液可以含有任何浓度和任意比率的L-抗坏血酸和无机酸盐除非它们从溶液中结晶。但是,本发明方法应用于含有以水溶液为基准大约0.1~30%(以重量计)L-抗坏血酸和大约1-25%(以重量计)无机酸盐更为有利,如前所述,无论直接法或烷基脂烯醇化法东提供这样的酸性水溶液,且这些溶液中的无机酸盐是由这些方法生产L-抗坏血酸而产生的。
例如根据直接法,在无机酸例如盐酸的催化剂存在下,加热双丙酮-2-酮-L-古洛糖酸或2-酮-L-古洛糖酸,得到L-抗坏血酸和无机酸的含水反应混合物。因此,以相当于反应混合物中无机酸的量的碱加到反应混合物中,生成含有无机酸的碱金属盐。例如氯化钠的L-抗坏血酸的酸性水溶液。这样,得到的水溶液相对于10重量份的L-抗坏血酸来说,通常含有大约1~5重量份的无机酸碱金属盐。在烷基脂烯醇化法情况下,2-酮-L-古洛糖酸烷基脂在碱如甲醇钠的存在下按已知常规方式烯醇化和内酯化,并且用等当量的无机酸如盐酸中和所得的L-抗坏血酸钠,籍此得到含此酸的钠盐例如氯化钠的L-抗坏血酸的酸性水溶液。这样,得到的水溶液相对于10重量份的L-抗坏血酸,通常含有大约3~4重量份的无机酸的碱金属盐,所以,在L-抗坏血酸的生产中生成的L-抗坏血酸酸性水溶液中所含有的无机酸的盐可以是氯化钠,溴化钠或氯化钾,在L-抗坏血酸的工业生产中尤以氯化钠最为普遍。
本发明的方法可使用任何常规的电渗析装置。最简单形式的装置是由渗析室,阳极室和阴极室,二者通过渗析室两侧的离子交换膜与渗析室分离。尽管如此,经改进的装置用于本发明更为有利。
附图是这种电渗析装置的简化图解,它包括渗析室1,和阳极室2与阴极室3,二者位于渗析室两侧,靠离子交换4成其它隔膜分离,以防止进入渗析室和电极室的溶液混合,渗析室具有大量交替的阳离子交换膜5、5和阴离子交换膜6、6,以便分别构成脱盐室7和浓缩室8。含有无机酸盐的L-抗坏血酸水溶液(以下称作料液)引入脱盐室。然后用泵10再循环返回其溶器箱9,通常为盐水的浓缩液同样引入浓缩室,且靠泵12再循环返回到其容器11,而盐水作为电极液在容器13和相应电极室之间靠泵14循环。
料液的电渗析是在脱盐室靠施于电极间电压而进行,即料液中成盐离子根据电荷,穿过各自的离子交换膜进入浓缩液,借此使料液在脱延室脱盐。
需要时,脱盐室或浓缩室在惰性气氛下,例如氮气中密封,以防止L-抗坏血酸的空气氧化。
经电渗析法脱盐的水溶液用活性炭脱色和纯化,在真空中浓缩,使高纯度L-抗坏血酸结晶出来。
按照本发明的方法,虽然任何阴离子交换膜都可同样使用,但最好使用作为阳离子交换膜的选择性一价阳离子渗透膜。“Selemion ASV”膜(Asahi Glass K.K)和“Neosepta ACS”膜(Tokuyama Soda K.K)是用于本发明选择性一价阳离子渗透膜的优选例子。用于普通脱盐的阳离子交换膜也可以用于本发明,但是,由于这种普通类型的膜对一价阳离子缺乏选择性的渗透能力,也就是对氯离子和L-抗坏血酸阴离子都缺乏选择性渗透作用,所以,渗漏到浓缩液中的L-抗坏血酸要大于用选择性一价阳离子渗透膜作阳离子交换膜的电渗析。
按照本发明,含有L-抗坏血酸和无机酸盐的酸性水溶液电渗析最好在脱盐率直到大约80~90%时才进行,尽管最佳脱盐率取决于准备电渗析的水溶液中L-抗坏血酸和无机酸盐的浓度。
用选择性一价阳离子渗透膜使L-抗坏血酸的回收率高达约98%。但是,当高回收率为目的要求时,第一次电渗析得到的浓缩液要经第二次电渗析,而在第二次电渗析中,浓缩液用作料液,这两次电渗析一般使L-抗坏血酸回收率大于99.5%,即几乎全部回收。
本发明的方法能方便地将无机酸盐从直接法或烷基酯烯醇化生产L-抗坏血酸得到的L-抗坏血酸和无机酸盐的含水混合物中除去。按照本发明,无机酸盐能通过一步电渗析,从混合物中有效的除去,从而在高电流效率下,以高回收率回收高纯度L-抗坏血酸。本发明另外的优点是,在电渗析以后,由于离子迁移伴有的电渗水,因此脱盐的溶液中水量减少,这就提高了溶液中L-抗坏血酸的浓度。例如当脱盐液浓缩时,这有利于从溶液中结晶出L-抗坏血酸。
参考下面实施例将更容易理解本发明,但这些实例只打算说明本发明,而不是限制本发明。
实施例1
使用如附图所示的电渗析装置1它的阳极为镀铂的钛板,阴极为不锈钢(SUS316)。装置中有十个选择性一价阴离子渗透膜“Selemion ASU”(Asahi Glass K.K),作为阴离子交换膜和十个“Selemion CMV”(上公司)作为阳离子交换膜,两者交替安装在渗析室中。每一渗透模的有效表面积为2dm2,这样就交替组成脱盐室和浓缩室。
用直接法生产L-抗坏血酸,且向获得的含水反应混合物中加入相当于反应混合物中盐酸的量的氢氧化钠,所得到含水料液组成为900克的L-抗坏血酸和3.5克的氯化钠(总容积为4500ml)。盐水溶液分别作为浓缩液和电极液所用的浓缩液为0.5%(W/V)氯化钠水溶液(总容积为4000ml),使用的电极液为3.0%(W/V)氯化钠的溶液。
室温下,进料液、浓缩液和电极液以4升/分的速率分别从容器中用泵抽到脱盐室、浓缩室和电极室,电极室所施的恒压为10V,以使进料液进行4小时电渗析。
经实测,可得的脱盐溶液含886.5克L-抗坏血酸和11.0克氯化钠(总容积3800ml)而浓缩液含324克氯化钠和13.5克L-抗坏血酸,因此,脱盐率为96.5%,电流效率为90%,L-抗坏血酸渗漏到浓缩液的漏损率为1.5%。
脱盐液按常规方法浓缩,以结晶出L-抗坏血酸。经实测,它基本上不含氯化钠。
4600ml上述浓缩液按如上同样方法电渗析3小时,以得到实测含有13.2克L-抗坏血酸和3.0克氯化钠(总容积3500ml)和含0.3克含L-抗坏血酸的浓缩液(总容积4700ml)。因此,脱盐率为99%。电流效率为99%。L-抗坏血酸渗漏到浓缩液的漏损率为2.2%。结果,经过第一次和第二次电渗析,L-抗坏血酸的总漏损率为0.003%。L-抗坏血酸总回收率大于99.9%。
同时,按第一次电渗析同样方法进行另一次的电渗析,只是将普通脱盐膜“Selemion AMV”(Asahi Glass K.K)用作阴离子交换模,取代选择性一价阳离子渗透膜。当脱盐率到达96%时,L-抗坏血酸漏损率为6.5%。
实施例2
使用有选择性一价阴离子渗透膜的电渗析装置,并且“Neosepta ACS”(To Kuyama Sodo K.K)和“Neosepa CL-25 T”(Tokuyama Soda K.K)分别作为阴离子交换膜和阳离子交换膜,其余如实施例1。
用烷基酯烯醇化法得到含1750克L-抗坏血酸的水溶液。向溶液中添加922克35%(按重量计)的盐酸,得到7000ml的进料液,经实测,它含有1556克L-抗坏血酸和517克氯化钠,PH值为1.9。1.0%(W/V)盐水溶液(总容积为7000ml)用作浓缩液,3.0%(W/V)盐水溶液作用电极液。按实施例1同样方式对进料液电渗析5小时。
经实测,得到的脱盐溶液含1525克L-抗坏血酸和15.5克氯化钠(总容积为5950ml),测得浓缩液含31克L-抗坏血酸和571克氯化钠(总容积为8050ml)因此,脱盐率为97%,电流效率为91%。渗漏到浓缩液中L-抗坏血酸的漏损率为2.0%。
Claims (4)
1、L-抗坏血酸的提纯方法,它包括:对含有机酸盐的L-抗坏血酸的酸性水溶液进行电渗析1,以除其中的盐。
2、根据权利要求1所述的方法,其中酸性水溶液的电渗析是通过选择性一价阴离子渗透膜作为阴离子交换膜进行的。
3、根据权利要求1所述的方法,其中酸性水溶液的制备是在无机酸存在下,通过加热双酮-2-酮-L-古洛糖酸或2-酮-L-古洛糖酸来进行的,然后向所得的反应混合物中添加相当于反应混合物中无机酸含量的碱,使无机酸转化成它的盐。
4、根据权利要求1所述的方法,其中酸性水溶液的制备是在碱金属或碱土金属盐形成的碱的存在下通过对2-酮-L-古洛糖酸的烷基酯的烯醇化和内酯化来进行的,然后向所得反应混合物中添加相当于反应混合物中L-抗坏血酸金属盐的量的无机酸,以得到L-抗坏血酸和无机酸金属盐的混合物。
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JP (1) | JPH0720949B2 (zh) |
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CN1081188C (zh) * | 1995-12-14 | 2002-03-20 | 弗·哈夫曼-拉罗切有限公司 | 抗坏血酸的制造方法 |
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DE4026787A1 (de) * | 1990-08-24 | 1992-02-27 | Basf Ag | Verfahren zur herstellung von kaliummagnesium-l-ascorbat-2-phosphat |
JP3134236B2 (ja) * | 1992-01-30 | 2001-02-13 | 株式会社林原生物化学研究所 | α−グリコシル−L−アスコルビン酸高含有物の製造方法とその製造のための分離システム |
JPH08176133A (ja) * | 1994-12-26 | 1996-07-09 | Takeda Chem Ind Ltd | L−アスコルビン酸の精製法 |
DE19505957A1 (de) * | 1995-02-21 | 1996-08-22 | Huels Chemische Werke Ag | Verfahren zur Herstellung von Ketoverbindungen |
US6004445A (en) * | 1997-06-30 | 1999-12-21 | Electrosynthesis Company, Inc. | Electrochemical methods for recovery of ascorbic acid |
US6187570B1 (en) * | 1998-05-26 | 2001-02-13 | The Electrosynthesis Company, Inc. | Electrodialysis methods for purification and recovery of gluconic acid derivatives |
EP1368329B1 (en) | 2000-12-22 | 2005-08-31 | Eastman Chemical Company | Process for producing ascorbic acid in the presence of a sulfit |
US6610863B2 (en) | 2000-12-22 | 2003-08-26 | Eastman Chemical Company | Continuous process for producing L-ascorbic acid |
JP4430869B2 (ja) | 2001-04-04 | 2010-03-10 | ジェネンコー・インターナショナル・インク | 宿主細胞の分離した生産及び異化経路 |
KR20080113283A (ko) | 2001-04-04 | 2008-12-29 | 제넨코 인터내셔날 인코포레이티드 | 숙주 세포에서의 생산물의 생산 방법 |
US6740762B2 (en) | 2001-08-24 | 2004-05-25 | Eastman Chemical Company | Process for ascorbic acids using alkaline earth silicate catalysts |
WO2003031427A1 (en) * | 2001-10-09 | 2003-04-17 | Eastman Chemical Company | Systems and methods for generation of ascorbic acid with reduced color |
US6716997B1 (en) | 2001-10-09 | 2004-04-06 | Eastman Chemical Company | Systems and methods for generation of ascorbic acid with reduced color |
CN108613305B (zh) * | 2018-06-26 | 2023-10-17 | 北京建筑大学 | 一种液化天然气冷能综合利用系统和方法 |
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US2265121A (en) * | 1933-10-25 | 1941-12-02 | Hoffmann La Roche | Process for the manufacture of levoascorbic acid |
US2179977A (en) * | 1935-11-26 | 1939-11-14 | Hoffmann La Roche | Process for the manufacture of levo-ascorbic acid |
GB760575A (en) * | 1953-03-27 | 1956-11-07 | Nat Res Dev | Improvements in and relating to the recovery of ascorbic acid |
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- 1986-06-28 DE DE19863621781 patent/DE3621781A1/de not_active Withdrawn
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CN1006793B (zh) | 1990-02-14 |
GB2179353B (en) | 1989-07-12 |
JPH0720949B2 (ja) | 1995-03-08 |
DE3621781A1 (de) | 1987-01-15 |
US4767870A (en) | 1988-08-30 |
DK175066B1 (da) | 2004-05-17 |
GB2179353A (en) | 1987-03-04 |
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