CN1048755C - 制备烷基糖苷脂肪酸酯的方法 - Google Patents
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- C12P19/00—Preparation of compounds containing saccharide radicals
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Abstract
由脂肪酸、烷基糖苷和非离子或阴离子表面活性剂形成的微滴乳状液,经酶促制备烷基糖苷的脂肪酸酯。微滴乳状液的粘度由叔丁醇、2-甲基-2-丁醇、丙酮或2-丁酮调节。在完成酶促酯化后,反应混合物经全蒸发处理。
Description
本发明涉及一种酶促反应制备烷基糖苷脂肪酸酯的方法。
国际专利申请WO-A-8901480(Novo Industri)告知一种方法,其中含有一个2-6个碳原子烷基的烷基糖苷与一个含有C4-C22(优选C6-C22)脂肪酸或其低级烷基酯反应,该反应发生于水解酶存在下,优选酯酶,水解酶产自Rhizomucor、腐质霉属(Humicola)、假单胞菌属(Pseudomonas)、或假丝酵母属(Candida)的种。该酶可在可溶状态或以固定化形式应用。结果表明优选不使用溶剂,但如果使用有机溶剂,溶剂应对酶无破坏作用。推荐的溶剂有酮类(如2-丁酮)、烃类(如戊烷、己烷或庚烷)和酯类。在两个实施例中,作为溶剂的2-丁酮的量大大超过反应剂的总重量。在工业规模下,本方法的技术实施中存在一个问题,即烷基糖苷具有高粘度,需要掺入熔化的脂肪酸,然而即使可能的话,做到这点也非常困难。如果增加与烷基糖苷相关的脂肪酸的量以增加反应的效率,则倾向于形成一定量的诸如二酯类的副产物。
因此,在国际专利申请WO-A-941575(Unilever)中已提出,首先将做为反应物的烷基糖苷和脂肪酸通过表面活性剂作用制成稳定的微滴乳状液,并优选使用阴离子或非离子表面活性剂,在优选的实施方案中,已形成的一部分烷基糖苷脂肪酸酯被循环进行反应而作为表面活性剂以形成微滴乳状液。接着,使用脂酶、特别是固定化脂酶,对微滴乳状液进行酶促酯化反应。
然而,已发现,即使是微滴乳状液仍可能存在过高的粘度而无法通过固定床酶催化剂。尽管如此,如果在烷基糖苷脂肪酸酯酶法生产中采取一系列相联的步骤,仍可得到因使用微滴乳状液而带来的便利。这是由于已发现可通过将微滴乳状液与有效量特定的降粘剂结合而使微滴乳状液的粘度有效地降低,然后在加压条件下将微滴乳状液通过固定床水解酶催化剂,并在最后将反应产物进行全蒸发,通过这一方法,可获得一种便利的方法,使通常高粘度的烷基糖苷混合物的生产成为可能,并以经济、富有吸引力的方式获得高产量的烷基糖苷脂肪酸酯类。
因此,本发明涉及一种酶促方法,用于制备烷基糖苷脂肪酸酯,其中包括一种微滴乳状液,它以一种饱和或不饱和的、直链或支链的、6至22个碳原子的脂肪酸、一种非离子或阴离子表面活性剂和一种烷基为饱和的、直链或支链的、含1至8个碳原子的烷基糖苷形成,其特征在于:
(a)将获得的微滴乳状液与有效量的降粘剂结合,降粘剂选自叔丁醇、2-甲基-2-丁醇、丙酮、2-丁酮及其混合物,
(b)在温度35℃至85℃和压力达到20巴时,经粘度调节后的微滴乳状液至少与脂酶接触一次,
(c)在温度65℃至100℃和压力至少1个巴时,将所得的反应混合物进行全蒸发处理。
优选的脂肪酸为饱和或不饱和的、直链或支链的、含8至20个碳原子的脂肪酸。还可使用脂肪酸的混合物以及工业级的脂肪酸,脂肪酸也可含有功能基团,如羟基、氨基以及其它基团。
烷基糖苷的烷基为饱和的、直链或支链的、含有1至8个碳原子、并优选1至4个碳原子的烷基。
烷基糖苷的糖苷部分含1至3个单糖单位。这些单糖单位优选戊糖或己糖形式(特别是呋喃糖或吡喃糖类)。合适的单糖有阿拉伯糖、核糖、木糖、木酮糖、来苏糖、核酮糖、2-脱氧核糖、葡萄糖、果糖、半乳糖、甘露糖、山梨糖、塔罗糖和脱氧糖如2-脱氧半乳糖。优选的二糖为麦芽糖、异麦芽糖、纤维二糖、乳糖和槐二糖。同样可使用各种庚糖和庚酮糖、如萄萄庚糖和甘露庚糖。也可使用烷基糖苷的混合物。
用于制备稳定微滴乳状液的非离子和(或)阴离子表面活性剂可以是甘油、多聚甘油、糖、糖醇或烷基糖苷,C6-C22脂肪酸的碱性金属盐,双2-乙基己基磺基琥珀酸钠盐,烷基多聚糖苷及其混合物的C6-C22的脂肪酸酯。优选在反应中形成的烷基糖苷脂肪酸酯作为非离子表面活性剂。已发现,当用作非离子表面活性剂的烷基糖苷酯中脂肪酸平均链长度与作为反应剂的脂肪酸的平均链长度一致时,可获得特别好的结果。
如果使用烷基糖苷脂肪酸酯作为非离子表面活性剂,形成稳定微滴乳状液所需的最小量随酯中脂肪酸的链长增加而增加,例如,如果使用乙基6-O-月桂酰葡萄糖苷,重量3%的量已足够形成稳定的微滴乳状液。通常,为形成稳定微滴乳状液所需的非离子或阴离子表面活性剂的量约为重量的1%至10%,有可能使用更大的量,但在经济上不可取。有时可能使用更小的量。
以任何一种合适的方式都可将降粘剂与微滴乳状液结合,例如,往微滴乳状液中定量给料所需的降粘剂,并将该混合物通过in-line staticmixer。已发现对于各种降粘剂存在一定的最佳值,2-丁酮的最佳值为重量的20%至25%,丙酮为20%至35%,叔丁酮为25%至50%。通常,所用降粘剂的量使得微滴乳状液的粘度调至60℃时为10mPas至100mPas,并优选60℃时为25mPas至40mPas。
在温度35℃至85℃和压力20巴下,已调节至所需粘度的微滴乳状液接着至少与酯酶接触一次。优选将脂酶置于载体上以形成固定床酶催化剂,并使微滴乳状液能够多次通过这一固定床。
在载体上固定化的脂酶优选产自如Rhizomucor miehei(Lipozyme;Trake Mark,ex.Novo,DenmarR),Candida antarctica和Candidacylindracea菌株的脂酶,而其它霉菌、酵母或细菌的脂酶亦可使用,例如可产自腐质霉属,假单胞菌属等的脂酶。
可通过载体结合技术-一种交联技术,实现载体上脂酶的固定化。载体可以是无机物如活性炭、多孔玻璃、具疏水性的大孔二氧化硅(macroporous silica rendered hydrophobic),如XWP-1500(Trademark;ex W.R.Grace,USA;平均颗粒大小为0.5-1mm;平均孔径150nm),及其类似物;天然化合物,如淀粉;以及合成的化合物,优选大孔的多聚物,如聚烯烃,象Accurel EP-100(Trade Mark;ex AKZO,The Netherlands,颗粒大小为100μm-1000μm,优选200-500μm和孔径约100nm);阴离子交换树脂,如Duolite ES-568N(Trade Mark,ex.Rohm and Haas,Germany);丙烯树脂,及其类似物。优选使用大孔的聚烯烃类树脂,如Accurel EP-100。对多聚物的选择应遵循在使用过程中不被溶剂破坏(例如膨胀和/或断裂)。
一旦达到充分程度的酯化,反应的混合物在65℃至100℃下经过一个全蒸发的处理,并优选70℃至95℃和压力至少一个巴。作为已知的技术,全蒸发用于酶催化酯化反应在欧洲专利EP-A-506,159(Unichema Chemie BV)中已有描述。
在全蒸发中,一种液体进料(含有高渗透性和低渗透性的组份)保持与一渗透性膜接触,并在膜上维持一定的压力降。液体进料中待移取的组分穿过膜。透出膜的渗出物以蒸气的形式可经冷凝作用在低温下被回收或者是用流动气流带走。优选在透出物一侧膜的压力保持在大小为5mmHg(0.5=67KPa)。留在分离器中残余的进料,称为滞流物或浓缩物。在蒸气渗透过程中,加入的混合物首先蒸发然后蒸气通过渗透膜。
全蒸发的方法在W.S.Winston Ho和K.K.sirkar的“膜工具”,VanNostrand Reinhold Publishing Corp.,New York,1992 on pages 105-109,中已有更详细的描述。
全蒸发在穿过全蒸发膜时发生。该渗透膜可以是任何可获得的商业性产品,并保证能够耐受反应混合物。典型的全蒸发膜为多层膜,包括一个活性的聚乙烯醇(已修饰)的外层、一个可为聚丙烯腈的多孔衬层和一个非织物的聚酯如聚乙烯对苯二酸酯的支持层。全蒸发容器内实施的压力大小可依据填充床酶催化剂中完成反应的压力,但是通常,压力条件的选择取决于获得最大的产出率。
在下面的实施例中将对本发明作进一步的阐述。
实施例一
在50℃下,将在31.9千克乙醇中的17.2千克乙基葡萄糖苷与20.0千克的月桂酸(PRIFAC 2922;Trademark,ex Unichema ChemieBV,Gouda The Netherlands;酸值278-282,滴定度43-43.7℃,碘值0.2)和2.8千克的乙基6-O-月桂酰-葡萄糖苷混合,然后在85℃和90毫巴下通过一个扫膜蒸发器(wiped film evaporator),以蒸去大量的乙醇。
离开薄膜蒸发器之后,形成了在60℃具有960mPa粘度的微滴乳状液(用Brookfield旋转粘度仪测得)。将微滴乳状液和10.0kg丙酮混合,使微滴乳状液粘度调至30mPa(60℃时)。然后将微滴乳状液通过固定床酶催化剂,它由固定化在Accurel EP-100(Trade Mark;Ex AKZO,Arnhem,The Netherlands)上的Candida antarctica脂酶构成。所用脂酶的量是进料的重量的2%,固定化酶被负荷在量为1kg,置于巴氏消毒桶(holding vessel)中的填充床上,微滴乳状液借助于闭合环路连接于巴氏消毒桶的泵在固定床脂酶催化剂上循环。容纳填充床的巴氏消毒桶的压力为5巴。巴氏消毒桶的下游装有具有4.1m2CM Celfa-A膜的TypeCelfa T-1型板框式全蒸发部件(Trade Mark;ex CELFAMembrantrennechnik AG,Switzerland)反应混合物在85℃通过该全蒸发部件,入口压为4.5巴,出口压为4.0巴。
在12小时,有95%转换为乙基6-O-月桂酰葡萄糖苷(以乙基葡萄糖苷进料计算)。产物的组成为90%重量的单酯、2%重量的双酯,而剩余物为过量的月桂酸和未转化的乙基葡萄糖苷,产物的颜色低于Gardner63标度的1号值。
实验例2
重复实施例1,但在60℃下加入10千克的叔丁醇将微滴乳状液的粘度调节至70mPas。接着在支持管道入口压力为3帕、出口压力2.5帕条件下将微滴乳状液通过酶催化剂填充床,反应在60℃下完成。全蒸发在95℃有效进行,入口压力为25帕,出口压力为2帕。
在20小时,有96%转换为乙基6-O-月桂酰葡萄糖苷(以乙基葡萄糖苷进料计算)。产物的组成为91%重量的单酯、2%重量的双酯,而剩余物为过量的月桂酸和未转化的乙基葡萄糖苷,产物的颜色低于Gardner63标度的1号值。
实验例3
在50℃下,将在32.6千克乙醇中的11.4千克乙基葡萄糖苷与18.6千克的油酸和10千克乙基6-O-油酰葡萄糖苷混合,然后在85℃和90毫巴下通过一个扫膜蒸发器,以蒸去大量的乙醇。
取走蒸发膜后,在60℃时通过加入10千克的丙酮,将稳定微滴乳状液的粘度调至50mPas。然后,如实施例1所述,将该微滴乳状液作进一步处理,并在12小时时,有94%转化为乙基6-O-油酰葡萄糖苷(以乙基葡萄糖苷进料计算)。产物的组成为90.5%重量的单酯、1.8%重量的双酯,而剩余物为过量的油酸和未转化的乙基葡萄糖苷,产物的颜色低于Gardner63标度的3-4号值。
Claims (17)
1.一种酶促反应制备烷基糖苷脂肪酸烷基酯的方法,其中由一种饱和的或非饱和的、直链的或支链的、含6至22个碳原子的脂肪酸,一种非离子或阴离子表面活性剂,以及一种烷基为饱和的、直链或支链烷基的、含1至8个碳原子的烷基糖苷形成微滴乳状液,其特征在于:
(a)将获得的微滴乳状液与有效量的降粘剂结合,降粘剂选自叔丁醇、2-甲基-2-丁醇、丙酮、2-丁酮及其混合物,
(b)在温度35℃至85℃和压力最高为20巴时,经粘度调节后的微滴乳状液至少与固定化在载体上并形成固定床催化剂的脂酶接触一次。和
(c)在温度65℃至100℃,压力至少1个巴时,将所得的反应混合物进行全蒸发处理。
2.权利要求1的方法,其中脂肪酸为饱和或不饱和、直链或支链、含有8至20个碳原子的脂肪酸。
3.权利要求1的方法,其中烷基糖苷含有一个饱和、直链或支链的、有1至4个碳原子的烷基。
4.权利要求1的方法,其中烷基糖苷含有1至3个单糖单位。
5.权利要求1的方法其中非离子或阴离子表面活性剂选自甘油、多聚甘油、糖、糖醇和烷基糖苷的C6-C22脂肪酸酯;C6-C22脂肪酸的碱性金属盐;双(2-乙基己基)磺基琥珀酸钠,烷基多聚糖苷及其混合物。
6.权利要求1的方法,用作非离子表面活性剂的烷基糖苷酯中脂肪酸基团的平均链长度与脂肪酸反应剂平均链长度一致。
7.权利要求1的方法,其中使用了占微滴乳状液重量的1%至10%的非离子或阴离子表面活性剂。
8.权利要求1的方法,其步骤(a)中使用了占微滴乳状液重量的20%至25%的2-丁酮。
9.权利要求1的方法,其步骤(a)中使用了占微滴乳状液重量的20%至35%的丙酮。
10.权利要求1的方法,其步骤(a)使用了占微滴乳状液重量的25%至50%的叔丁醇或2-甲基-2-丁醇。
11.权利要求1的方法,其步骤(a)中在60℃下将微滴乳状液的粘度调至10mPas至100mPas。
12.权利要求1的方法,其步骤(a)中在60℃下将微滴乳状液的粘度调至25mPas至40mPas。
13.权利要求1的方法,其步骤(b)中的温度为45℃至65℃。
14.权利要求1的方法,其步骤(b)中的压力最高为10巴。
15.权利要求1的方法,其步骤(b)中脂酶固定化于载体上,载体选自具疏水性的大孔二氧化硅(macroporous silica renderedhydrophobic)、大孔聚链烯和大孔的阴离子交换树脂。
16.权利要求1的方法,其脂酶选自Candida antarctica、Candidacylindracea和Rhizomucor miehei产生的脂酶。
17.权利要求1的方法,其步骤(c)中的温度为70℃至95℃。
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EP0507323A2 (en) * | 1991-04-05 | 1992-10-07 | Lion Corporation | Process for preparing fatty acid esters of saccharides |
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WO1989001480A1 (en) * | 1987-08-21 | 1989-02-23 | Novo-Nordisk A/S | Esters of glycosides and a process for enzymatic preparation thereof |
WO1990009451A1 (en) * | 1989-02-17 | 1990-08-23 | Novo Nordisk A/S | A process for producing glycoside esters and compositions comprising glycoside esters |
EP0506159A1 (en) * | 1991-03-19 | 1992-09-30 | Unichema Chemie B.V. | Esterification process |
EP0507323A2 (en) * | 1991-04-05 | 1992-10-07 | Lion Corporation | Process for preparing fatty acid esters of saccharides |
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ZA951385B (en) | 1996-08-20 |
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