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CN1079795C - 稳定和回收生育三烯酚和生育酚产物的方法 - Google Patents

稳定和回收生育三烯酚和生育酚产物的方法 Download PDF

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CN1079795C
CN1079795C CN91103963A CN91103963A CN1079795C CN 1079795 C CN1079795 C CN 1079795C CN 91103963 A CN91103963 A CN 91103963A CN 91103963 A CN91103963 A CN 91103963A CN 1079795 C CN1079795 C CN 1079795C
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tocol
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肯尼斯·W·贝克尔
丹·迈克尔·韦尔斯
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Abstract

一种从植物原料中以高产率稳定和回收生育酚和生育三烯酚产物的方法，该方法包括加热植物原料以使破坏性的酶失活的稳定过程，再萃取生育三烯酚和生育酚产物。

Description

稳定和回收生育三烯酚和生育酚产物的方法
本发明申请涉及从植物原料中有价值物质的萃取过程，特别是涉及稳定和回收生育三烯酚和生育酚产物的方法。
生育三烯酚(T3)和生育酚(T)(即，2，5，7，8-四甲基-2-4＇，8＇，12＇-三甲基十三烷基-6-苯并二氢吡喃醇))在谷物和其它植物原料中天然存在的数量很小，如在米糠，燕麦糠，棕榈油、和大麦中。由于T3可以降低血清胆甾醇从而可作为降高血压的药(见A.A.Qureshi等人，J.Am.Clin.Natr.，1991，pp.1021s-46s)，因此人们对T3有着特殊的兴趣。此外，它还可能具有其它医药应用价值，如增加胰岛素的产生治疗糖尿病(II)型。
过去人们已经知道，当人类或其它动物食用米糠时，料糠包含的物质显示出可以降低胆甾醇。然而，许多科学家均认为能使胆甾醇降低的物质为可溶解或不溶解的纤维(见D.Kritchevsky等人，Lipids，1978，pp.366-69.)。近来已经发现，是米糠中的T3和类似T3的化合物起着降低胆甾醇的作用(见A.A.Qureshi等人，J.Biol.Chem，1986，pp.10544-50)。人们尝试用常规的方法从米糠中萃取T3和类似T3的化合物，但结果仅能回收很少量所希望的化合物(见，加拿大专利No.480,484)。
现已发现了一种方法可以使相当大量的T3和类似T3的化合物从米糠和其它原料中萃取出来。
本发明的主要目的是提供一种新方法，用来从植物原料中稳定和回收相当大量的T、T3和类似T3的化合物。
本发明的从植物原料中稳定和回收T、T3的化合物的新方法包括：在约150℃～约180℃下干稳定植物原料以使酶失活，这些酶可以是脂肪酶、过氧化物酶和催化酶。植物原料在约100℃～约140℃下进一步使之湿稳定(优选10％～30％的水分)以使任何残留的破坏性的酶(如过氧化物酶)失活。然后在低温下使用如溶剂萃取等技术从稳定了的植物原料中提取和回收所希望的化合物，接着进行脱溶剂、脱臭、脱色和精制等过程。
在两步稳定过程中，必须保持一定条件使确定的酶失活而不破坏T3和T产物。此外，为了避免稳定及随后的冷却过程中高的过氧化值(PV)的出现，应采用过热蒸汽或其它惰性气体如用氮气对米糠进行掩蔽。稳定过的米糠可以用超临界二氧化碳萃取，或采用诸如戊烷、己烷、乙醇等溶剂进行萃取，从而分离出含有T、T3和类似T3产物的油。低温萃取增加T3和T产物的收率，并使大部分的蜡残留在米糠中。如果使用了溶剂，米糠最好在汽提脱溶剂一脱臭器中进行脱溶剂处理，其中脱臭器段在低于1个大气压下操作以避免诸如赖氨酸、半胱氨酸和维生素B等有价值的成份的损失。可以采用漂白和物理精制过程从油中回收作为留出物的T3、T及游离脂肪酸的混合物。用分子蒸馏或用一种溶剂如乙醇或甲醇将游离脂肪酸与T3和T的混合物分离。
本发明的方法较传统方法制得的有价值的产物如T(生育酚)和T3(生育三烯酚)具有更大的浓度。T/T3混合物统称为母育酚(Tocol)。该混合物也包含较之T3更具药物活性的类似T3的化合物。由本方法制得的产品为稳定了的高母育酚米糠、脱脂高母育酚米糠、高母育酚油、母育酚、游离脂肪酸、一般的米糠油、一般的脱脂米糠。动物试验表明：38％的血清胆甾醇的降低对20％～30％的处方药剂和7％的可溶或不可溶纤维。初步的人体试验表明：在一个比较基础上胆甾酵降低同样的比例。使用50～100mg/天的母育酚进行的人体试验可降低血清胆甾醇而没有嗜睡、胃痉挛、恶心、头痛等付作用。有限的人体测试还表明葡萄糖含量显著的降低和血压的降低，但没有付作用。
在优选方案中，植物原料为米糠，将米糖在150℃～180℃干加热约10～50秒钟，从而使脂肪酶和催化酶失活。下一步增加水分约10～约30％，使混合物在约100～140℃下加热约20～50秒以使米糠(稻壳)开裂(collets)并使任一种过氧化物酶失活。
在稳定原料中的油和T、T3及类似T3的化合物最好在低于常规温度(如在35℃或低于35℃下)下进行萃取以减少T和T3的损失。在该条件下，该粗粉中也可以含有残留的腊，但腊中没有所希望得到的T3。进而，该粗粉用一种汽提脱溶剂——脱臭机或一种闪蒸脱溶剂——脱臭机或其它的类似设备在一个大气压下(或在脱色机中低于1个大气压以降低温度)进行脱溶剂处理。可采用过热循环的己烷以蒸出粗粉中大多数的溶剂。可以引入惰性气体(如氮气)以从最后的粗粉中脱除溶剂。也可以引入喷射蒸汽以脱除粗粉中的己烷或其它溶剂至可以接受的浓度。最后，在绝对压力较低(6mmHg～约50μmHg)下采用物理精制和/或分子蒸馏来脱出T、T3及类似T3的化合物和FFA(游离脂肪酸)。物理精制是采用干喷射蒸气以脱除以下的组分。采用物理精制时，用分子蒸馏的方法使FFA与T3/T混合物分开。也可以采用乙醇或甲醇等溶剂来分离FFA与T3/T混合物。
按照本发明，提供了一种方法及其替换方法，使用该方法可以较按传统的方法或其它米糠加工方法获得的T和T3(母育酚)生产的产率得到显著的提高。未稳定米糠生产的油包含25ppm的母育酚产物，而本发明方法稳定过的冷萃的米糠包含4179ppm母育酚产物(T3为2394ppm，T为1785ppm)。该值较其它谷物产品的T含量高几倍，也较其它稻米加工过程生产的T3高几倍。例如，棕榈油的母育酚含量为1000ppm(T3为800ppm，T为200ppm)；麦胚的母育酚含量为890ppm(T3为144ppm，T为746ppm)。半煮大米的T含量为291ppm，T3含量为1045ppm。
在米糠中存在脂肪酶I和II、催化酶、过氧化物酶等酶。只要稻壳依然在稻米上，这些酶就是没有活性的。然而，脂肪酶和催化酶变为活性的并且脂肪酸的产生均非常快，特别是在潮湿而高热的环境条件下。此外，过氧化物酶在低温时也破坏T和T3产物。
因而，在稻壳被脱除后，立即实施本方法是很重要的，米糠应该立即进行碾磨，然后进行稳定作用。对第一步的稳定过程，在挤压机中在150℃1～180℃下进行干热稳定约20～50秒，从而使一些酶(如脂肪酶、过氧化物酶、催化酶)失活，但不破坏母育酚产物。第一步在挤压机中的稳定过程必须在干热升温下在很短的时间内进行以实现以下的双重目的：破坏酶和增加米糠中的母育酚产物。有时，最好在挤压前或挤压后对米糠进行微波处理以增加萃取率并减少在萃取器中的停留时间，从而实现所希望的产物的回收。第二步或湿稳定过程中，水分含量为约10～30％，温度为约100～140℃，停留时间约10～50秒，从而使其它的酶(如残留的过氧化物酶)失活。在第二步稳定过程中，米糠(稻壳)开裂不仅有助于油的萃取，同时显著地减少油中的微粒。这些微粒不仅会引起产物损失，而且也增加了脱除它们时分离的难度。如果在存在空气中的氧时加热米糠，油的过氧化植将增加。为了排除O2，应使用过热蒸汽(或其它惰性气体，如N2)以掩蔽被稳定的米糠。第一和第二稳定过程优选过热蒸汽，因为过热蒸汽在工厂通常易于得到，是一种可靠的供应来源，此外，它对设备提供均匀的热源。在米糠冷却时，米糖也应排除空气(氧气)以避免油的PV值增加。这个要求可由下述过程满足，在冷却器的管路中用冷水冷却米糠，同时用惰性气体(如氮气)掩蔽冷却器。
稳定和冷却过的米糠用溶剂萃取以提取出油和母育酚(T和T3)产物。大豆、棉籽或棉籽饼、麦胚芽、玉米胚芽和米糠的溶剂萃取常采用的溶剂为己烷，而使用戊烷更具优点。己烷的沸点约为60℃，在低于50℃下操作而不允许空气进入萃取器是不实际的，因而会有爆炸的危险。戊烷的沸点为约35℃，在约25℃下操作而不至造成爆炸危险是可行的。冷萃取(21℃)时的母育酚产物的收率较之热萃取(60℃)时更大。其它的溶剂如95％的乙醇也可以在低于25℃下用于萃取油和母育酚产物。在低温下减少回收母育酚产物消费的措施是首先使用一种螺杆压榨机经冷压使油从15～20％脱除至3.5～8.5％，随后用冷的乙醇进行洗涤(低于25℃)。在蒸汽提脱溶剂一脱臭机或闪蒸脱溶剂——脱臭机中，用循环的过热蒸汽在脱溶剂步骤中去除米糠中超过95％的溶剂。在脱臭步骤中，系统在1个大气压或更低压力下操作，使用饱和蒸汽以脱除溶剂至可以接收的浓度(最好溶剂低于600ppm)。脱臭机中优选1个大气压以减低脱臭机的温度，因而可避免或减少在脱脂的米糠中赖氨酸、半胱氨酸、维生素B等的破坏。脱溶剂后的米糠用常规手段冷却，如用空气与之接触。混合油(油和己烷的混合物)中的溶剂用常规手段回收，而油被转移至脱色和精制过程。
对于精制和脱色过的油和母育酚产物的回收，首先使油脱色，然后进行物理精制。脱色从油中除去发色体，物理精制提取出含生育酚生育三烯酚和游离脂肪酸的馏出液。脱色和精制过程采用常规的条件。从脂肪酸中分离母育酚(T和T3)产物，可以使用乙醇或甲醇以实现相分离，然后蒸出乙醇或甲醇，从而使脂肪酸与母育酚产物分离。但由于乙醇或甲醇回收昂贵，回收母育酚产物的优选途经为分子蒸馏。
本发明在某些部分和其设置以及在某些步骤和其设置中可以采取实用形式，优选和替换实施方案在说明书中将作进一步详细的描述，并结合附图进行说明如下：
图1为一个方框流程图，表明了按照本发明从完整的稻谷制备高母育酚含量稳定和冷却过的米糠的方法的几个步骤。
图2为另一个方框流程图，表明了按照本发明从含母育酚的谷物或其它原料中萃取含高母育酚的油并减少赖氨酸，半脱氨酸、维生素B和其它有价值的温敏组分的方法的几个步骤。
图3为另一个方框流程图，表明了按照本发明处理高母育酚含量的油并将这种油分离成经精制和脱色的米糠油，母育酚(T+T3)产物和游离的脂肪酸。
图1中，本发明显示了米糠的应用。图1表明了制备高母育酚含量稳定的米糠的步骤。第一步，将整个稻谷进行脱壳。第二步，脱糠而得到糙米和米糠。在本发明的条件下，第三步进行过热蒸汽掩蔽下的干稳定过程。第四步，也在过热蒸汽掩蔽下实施湿稳定过程。最后第五步中，在惰性气体掩蔽下冷却稳定了的半糠，从而得到稳定且冷却了的米糠。
图2显示了在低温下通过溶剂萃取从稳定后的米糠中制备高母育酚油并同时将大多数的蜡留在脱脂的米糠中的步骤，低温可避免母育酚的破坏。从溶剂中分离油是从混合油中脱除溶剂，从而回收高母育酚油。汽提脱溶剂表明使用过热蒸汽从米糠中去除95％或更多的溶剂从而维持米糠中溶剂的低含量。在1个大气压或更低的压力下在脱臭器中用过热蒸汽脱除最后的溶剂。脱脂米糠的冷却采用空气冷却或在冷却器的管路里用水冷却。
图3中，母育酚产物和游离脂肪酸作为馏出物从精制且脱色了的油中分离出来。脱色过程用于去除发色体。采用物理精制用以从精制和脱色的油中脱出含游离脂肪酸和T、T3的馏出物。采用分子蒸馏使T和T3产物与游离脂肪酸分离。
               米糠的实例
以下给出的是小规模或实验室进行的实例。探测生育酚和生育三烯酚的实验室分析工作是按Dr.Asaf A.Qureshi在Ad-vanced Medical Research(Madison，Wisconsin)中指出的方法进行，使用现有技术中已经得到证实的色谱法。实例         条件                  在油中T＋T3ppm1.    162℃干稳定，持续少于60秒，           331
  稳定前延迟超过12小时。2.    96℃干稳定，持续50秒，                 74
  稳定前延迟超过12小时。3.    湿稳定，15％水分，持续30秒，           73
  稳定前延迟超过12小时。4.    无稳定过程。                           265.    立即在121℃干稳定，持续少于       2512
  60秒，用己烷在60℃萃取。6.    立即在160℃干稳定，持续少于       4179
  60秒，在21℃用己烷萃取7.    第一步在160℃干稳定，持续         2497
  时间少于60秒。
  6周后，在113℃约20％水分
  下湿稳定，在60℃下用己烷
  萃取。8.    蜡                          338(仅有T)
所显示的数字表明：·稳定前的延迟显著地减少在油中的T＋T3产物的ppm量。·干稳定温度为160℃比96℃或121℃更优越。·未稳定过的米糠仅在油中有约26ppmT＋T3。·在第一步和第二步稳定之间6个星期的延迟使得较低活性的酶如过氧化物酶的酶活性导致油中T＋T3的降低。
已参考优选方案来描述了本发明。很明显，在阅读和理解了本发明申请后可以对此进行改进和代换。所有的这些改进和代换均在本发明的权利要求或其等效内容的范围之内。

Claims (14)

1.从谷物中稳定和回收生育酚和生育三烯酚的方法，该方法包括：
(a)于惰性气体中在150℃-180℃干热处理谷物以使存在的过氧化物酶和脂肪酶失活，和
(b)在35℃以下用选自戊烷，己烷或乙醇的溶剂提取回收至少一种生育酚和生育三烯酚。
2.按权利要求1的方法，其中在干热处理过的谷物中加入水分并再次在惰性气体中、于100℃-140℃下加热以使存在的任何其它破坏性的酶失活。
3.按权利要求2的方法，其中加入的水分为10重量％-30重量％。
4.按权利要求1的方法，其中溶剂为己烷。
5.按权利要求1的方法，其中溶剂为戊烷。
6.按权利要求1的方法，其中在回收所希望的产物前对热处理的材料进行微波处理。
7.按权利要求1的方法，其中从热处理过的谷物中回收生育和生育三烯酚是在25℃或可获得合所要产品的油的更低温度下将该物料以如螺杆压的压力进行冷压以获得含所希望产物的油。
8.按权利要求1的方法，其中得到包括生育三烯酚的混合物。
9.按权利要求2的方法，其中物料首先在150℃-180℃加热40-60秒。
10.按权利要求1的方法，其中惰性气体是在谷物中不会冷凝的蒸汽。
11.按权利要求1的方法，其中惰性气体是氮气。
12.按权利要求1的方法，其中溶剂为95％的乙醇。
13.按权利要求1的方法，其中谷物是稻米。
14.按权利要求13的方法，其中稻米是米糠。
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MY108071A (en) 1996-08-15
BR9106474A (pt) 1993-05-18
JPH06502844A (ja) 1994-03-31
OA09680A (en) 1993-05-15
CA2083512A1 (en) 1991-11-24
AU666464B2 (en) 1996-02-15
CN1059522A (zh) 1992-03-18
EP0530320A1 (en) 1993-03-10
HU9203648D0 (en) 1993-04-28
HUT63158A (en) 1993-07-28
WO1991017985A1 (en) 1991-11-28
AU8073491A (en) 1991-12-10
SG69971A1 (en) 2000-01-25

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