CN104257882A - 一种从枸杞渣粕同时提取分离油脂、绿原酸和总黄酮的方法 - Google Patents
一种从枸杞渣粕同时提取分离油脂、绿原酸和总黄酮的方法 Download PDFInfo
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Abstract
从枸杞渣粕中同时提取分离油脂、绿原酸和总黄酮的方法,其特征在于:它包括如下操作步骤:(1)取枸杞渣粕,采用超临界二氧化碳萃取技术提取,即可得到枸杞油;(2)取提油后的枸杞渣粕,以乙醇为夹带剂进行超临界二氧化碳萃取,提取物备用;(3)将超临界二氧化碳萃取提取物上大孔吸附树脂,优选使用D101型大孔树脂,依次用水、10~15%(v/v)(优选15%)和65~75%(v/v)(优选70%)乙醇洗脱,分别收集各浓度乙醇洗脱部位,浓缩,干燥,依次得到绿原酸和总黄酮。由于本发明采用的原料为枸杞渣粕,是对工业废料的再利用,不仅成本低廉,而且大大提高了枸杞的附加值,因此,本发明大大提高了对枸杞资源的综合利用率。
Description
技术领域
本发明涉及通过枸杞渣粕中同时提取分离油脂、绿原酸和总黄酮的方法。
背景技术
枸杞渣粕(又称枸杞渣),是枸杞榨汁后剩余的废弃料,其回收成本低廉,当前有研究人员从其中分离提取了枸杞油脂类成分,如专利申请号:200510071543.3,使得枸杞资源得到了有效的利用,增加了经济效益。
枸杞籽中均含油量为18.56%,其中含有大量的不饱和脂肪酸,主要为亚油酸(63.05%)、油酸(21.13%)、亚麻酸(3.83%)等。亚麻酸对心脑血管疾病患者及高血脂的预防和治疗均有良好的效果,尤其是消退动脉粥样硬化疾病和抗血栓形成方面;亚油酸对预防和辅助治疗心脏疾病、动脉硬化、肥胖症、糖尿病和高血压等具有较好的功效,同时有益于婴儿大脑和幼儿心脏发育及组织细胞生长发育。此外,枸杞油中还含有多种微量元素,其中硒的含量为0.093ug/g,是人体必需的微量元素之一,具有维持人体免疫能力,保护眼组织和皮肤等重要功能;枸杞油中富含各种维生素,其中VE的含量为42.02mg/100g,具有较好的抗衰老和防止心血管疾病的功效;含磷脂约0.25%,可以降血脂、预防脂肪肝和抗衰老等功能。枸杞油现已被广泛应用于食品添加剂、饮料营养、医药行业和化妆品行业等,市场的需求量巨大。
但是,对枸杞渣粕的利用也仅仅限于直接从枸杞渣粕中分离油脂或玉米黄质提取物,目前还未见其他方面的进一步研究和利用报道。
发明内容
本发明所要解决的问题是提供一种能够有效利用枸杞渣粕这一废弃物的方法。
绿原酸,又名咖啡鞣酸,是咖啡酸与奎尼酸形成的缩酚酸,属于苯丙素类化合物,广泛存在于植物中,其中金银花、杜仲中的含量较高,具有广泛的生物活性。研究表明,绿原酸可作为一种自由基清除剂及抗氧化剂,对心血管系统的预防保护作用较好;绿原酸对胃癌和结肠癌的发生具有预防及抑制作用,可能与它的促氧化作用、增强芳烃羟化酶活性和抑制8-羟基脱氧鸟苷的形成有关。此外,绿原酸还具有抗菌及抗病毒作用、降脂作用、抗白血病作用、降糖作用和免疫调节作用。
黄酮类化合物是一类存在于自然界中具有2-苯基色原酮结构的化合物,在多数植物体内都含有,它在植物的生长、发育以及抗菌防病等方面起着重要的作用。目前已知枸杞中富含黄酮类成分,枸杞黄酮可止咳、平喘、祛痰、扩张冠状动脉及降低血胆固醇,增强心脏收缩,减少心脏搏动数及清除自由基等作用。
因此,对枸杞渣粕中的枸杞油、绿原酸和黄酮类等各成分进行提取分离研究,具有重要的意义。本发明拟从枸杞渣粕中同时分离提取油脂、绿原酸和黄酮类成分,从而再次增加对枸杞渣粕的利用率,进一步增加枸杞的附加值。
本发明经过大量的前期调研和试验考察,最终成功地首次从枸杞渣粕中同时提取分离得到了高纯度的油脂、绿原酸和黄酮类成分,为此,本发明提供了从枸杞渣粕中同时提取分离油脂、绿原酸和总黄酮的方法,它包括如下操作步骤:
(1)取枸杞渣粕,采用超临界二氧化碳萃取技术提取,即可得到枸杞油;
(2)取提油后的枸杞渣粕,以乙醇为夹带剂进行超临界二氧化碳萃取,提取物备用;
(3)将超临界二氧化碳萃取提取物上大孔吸附树脂,优选使用D101型大孔树脂(另外大孔树脂D140、HPD100、HPD300、AB-8、DM130、DM130和ADS-17也可以适用),依次用水、10~15%(v/v)和65~75%(v/v)乙醇洗脱, 分别收集各浓度乙醇洗脱部位,浓缩,干燥,依次得到绿原酸和总黄酮。
进一步地,步骤(2)中,乙醇的浓度为55~85%(v/v),其用量为2~5ml/g(每g枸杞渣粕2~5mL相应浓度的乙醇),优选用量为2ml/g;
超临界萃取条件为:萃取温度为40~60℃,第一次分离温度为40~50℃,第二次分离温度为30~40℃,萃取压力为25~35MPa,二氧化碳流速为20~80L/h,接收产物的频率为每次20~60min,提取时间为2~6h。
更进一步地,步骤(2)中,所述超临界二氧化碳萃取条件如下:萃取温度为40~50℃,第一次分离温度为40~45℃,第二次分离温度为30~35℃,萃取压力为30~35MPa,二氧化碳流速为20~40L/h,接收产物的频率为每次20~40min,提取时间为2~3h。
其中,所述乙醇浓度为55~65%(v/v),优选为60%(v/v)。
更进一步地,步骤(2)中,所述超临界二氧化碳萃取条件如下:萃取温度为50~60℃,第一次分离温度为45~50℃,第二次分离温度为35~40℃,萃取压力为25~30MPa,二氧化碳流速为40~80L/h,接收产物的频率为每次40~60min,提取时间为3~6h。
其中,所述乙醇浓度为75~85%(v/v),优选为80%(v/v)。
进一步地,步骤(3)中,用水洗脱至无色,用10~15%(v/v)(优选15%)乙醇洗脱至无绿原酸检出,用65~75%(v/v)(优选70%)乙醇洗脱至无黄酮类化合物检出。
进一步地,步骤(1)中,提油所用超临界二氧化碳萃取条件如下:萃取温度为40~60℃,第一次分离温度为40~50℃,第二次分离温度为30~40℃,萃取压力为30MPa,二氧化碳流速为20~80L/h,接收产物的频率为1次/20min,提取时间为2~6h。
更进一步地,步骤(1)中,提油所用超临界二氧化碳萃取条件如下之一:
A、萃取温度为40~50℃,第一次分离温度为40~45℃,第二次分离温度为30~35℃,萃取压力为30~35MPa,二氧化碳流速为20~40L/h,接收产物 的频率为每次20~40min,提取时间为2~3h;
B、萃取温度为50~60℃,第一次分离温度为45~50℃,第二次分离温度为35~40℃,萃取压力为25~30MPa,二氧化碳流速为40~80L/h,接收产物的频率为每次40~60min,提取时间为3~6h。
本发明的优势:
1、由于本发明采用的原料为枸杞渣粕,是对工业废料的再利用,不仅成本低廉,而且大大提高了枸杞的附加值,因此,本发明大大提高了对枸杞资源的综合利用率;
2、本发明可一次性从枸杞渣粕中,同时实现对枸杞油、绿原酸和总黄酮的提取分离,大大降低了生产成本,而且得到的产物安全无毒;
3、本发明方法提取分离得到的绿原酸、总黄酮纯度在85%以上,其优选工艺更是能够将纯度提高至90%以上,可满足各种对含有绿原酸或/和黄酮类成分的食品、保健品和药物的开发需求,亦可作为药物中间体使用。
具体实施方式
本发明中枸杞油出油率、绿原酸和总黄酮纯度等相关成分按相关国家标准进行测定。
实施例1:一种枸杞渣粕中同时提取分离油脂、绿原酸和总黄酮的方法
1、将枸杞渣粕干燥、粉碎后过60目筛,称取200g,装入2L的超临界二氧化碳萃取釜中,萃取温度为40~50℃,分离1(即一次分离,下同)温度为40~45℃,分离2(即二次分离,下同)温度为30~35℃,萃取压力为30~35MPa,二氧化碳流速为20~40L/h,接收产物的频率为每次20~40min,提取时间为2~3h,计算出油率(w/w)为22.45%,其中不饱和脂肪酸相对含量为90.14%。
2、取提油后的枸杞渣粕,添加60%乙醇作为超临界二氧化碳萃取夹带剂, 用量为2mL/g,超临界条件为:2L萃取釜,萃取温度为40~50℃,分离1温度为40~45℃,分离2温度为30~35℃,萃取压力为30~35MPa,二氧化碳流速为20~40L/h,接收产物的频率为每次20~40min,提取时间为2~3h,接收的产物备用;
3、将接收所得产物用青岛海洋化工厂生产的D101型大孔树脂吸附后,先用水洗脱至无色后,用15%(v/v)的乙醇溶液洗脱至未能检测出绿原酸,然后用70%(v/v)的乙醇洗脱至不能检测出黄酮类化合物时停止洗脱,分别收集各浓度乙醇洗脱液,进行减压浓缩,回收乙醇和水后,置于冷冻干燥机中,在-50℃下预冻2h后,进行真空干燥24h后,依次得绿原酸1.27g、黄酮类化合物1.62g,经测定,得到的产物含量分别为92.8%和90.7%。
实施例2:一种枸杞渣粕中同时提取分离油脂、绿原酸和总黄酮的方法
1、将枸杞渣粕干燥、粉碎后过60目筛,称取7500g,装入10L的超临界二氧化碳萃取釜中,萃取温度为50~60℃,分离1温度为45~50℃,分离2温度为35~40℃,萃取压力为25~30MPa,二氧化碳流速为40~80L/h,接收产物的频率为每次40~60min,提取时间为3~6h,计算出油率(w/w)为20.61%,其中不饱和脂肪酸相对含量为86.49%。
2、添加80%乙醇作为超临界二氧化碳萃取夹带剂,用量为5mL/g,超临界条件为:10L萃取釜,萃取温度为50~60℃,分离1温度为45~50℃,分离2温度为35~40℃,萃取压力为25~30MPa,二氧化碳流速为40~80L/h,接收产物的频率为每次20~40min,提取时间为3~6h,接收的产物备用;
3、将接收所得产物用青岛海洋化工厂生产的D101型大孔树脂吸附后,先用水洗脱至无色后,用15%的乙醇溶液洗脱至未能检测出绿原酸,然后用70%的乙醇洗脱至不能检测出黄酮类化合物时停止洗脱,收集各浓度乙醇洗脱液,进行减压浓缩,回收乙醇和水后,置于冷冻干燥机中,在-50℃下预冻2h后,进行真空干燥24h后,得绿原酸干燥粉末48.26g和总黄酮51.84g。 经测定,得到的产物含量分别为89.31%和88.04%。
对比例:一种枸杞渣粕中同时提取分离油脂、绿原酸和总黄酮的方法
1、将枸杞渣粕干燥、粉碎后过60目筛,称取200g,装入2L的超临界二氧化碳萃取釜中,萃取温度为30~40℃,分离1(即一次分离,下同)温度为40~45℃,分离2(即二次分离,下同)温度为30~35℃,萃取压力为20~25MPa,二氧化碳流速为20~40L/h,接收产物的频率为每次20~40min,提取时间为2~3h,计算出油率(w/w)为14.97%,其中不饱和脂肪酸相对含量为72.39%。
2、取提油后的枸杞渣粕,添加40%乙醇作为超临界二氧化碳萃取夹带剂,用量为2mL/g,超临界条件为:2L萃取釜,萃取温度为30~40℃,分离1温度为40~45℃,分离2温度为30~35℃,萃取压力为20~25MPa,二氧化碳流速为20~40L/h,接收产物的频率为每次20~40min,提取时间为2~3h,接收的产物备用;
3、将接收所得产物用青岛海洋化工厂生产的D101型大孔树脂吸附后,先用水洗脱至无色后,用25%(v/v)的乙醇溶液洗脱至未能检测出绿原酸,然后用90%(v/v)的乙醇洗脱至不能检测出总黄酮时停止洗脱,分别收集各浓度乙醇洗脱液,进行减压浓缩,回收乙醇和水后,冷冻干燥,依次得绿原酸1.02g、总黄酮1.35g,经测定,得到的产物含量分别为66.3%和70.7% 。
Claims (9)
1.从枸杞渣粕中同时提取分离油脂、绿原酸和总黄酮的方法,其特征在于:它包括如下操作步骤:
(1)取枸杞渣粕,采用超临界二氧化碳萃取技术提取,即可得到枸杞油;
(2)取提油后的枸杞渣粕,以乙醇为夹带剂进行超临界二氧化碳萃取,提取物备用;
(3)将超临界二氧化碳萃取物上大孔吸附树脂,优选使用D101型大孔树脂(另外大孔树脂D140、HPD100、HPD300、AB-8、DM130、DM130和ADS-17也可以适用),依次用水、10~15%(v/v)和65~75%(v/v)乙醇洗脱,分别收集各乙醇洗脱部位,浓缩,干燥,依次得到绿原酸和总黄酮。
2.根据权利要求1所述的方法,其特征在于:步骤(2)中,乙醇的浓度为55~85%(v/v),其用量为2~5ml每g枸杞渣粕;
超临界萃取条件为:萃取温度为40~60℃,第一次分离温度为40~50℃,第二次分离温度为30~40℃,萃取压力为25~35MPa,二氧化碳流速为20~80L/h,接收产物的频率为每次20~60min,提取时间为2~6h。
3.根据权利要求2所述的方法,其特征在于:步骤(2)中,所述超临界二氧化碳萃取条件如下:萃取温度为40~50℃,第一次分离温度为40~45℃,第二次分离温度为30~35℃,萃取压力为30~35MPa,二氧化碳流速为20~40L/h,接收产物的频率为每次20~40min,提取时间为2~3h。
4.根据权利要求2或3所述的方法,其特征在于:所述乙醇浓度为55-65%(v/v),优选为60%(v/v)。
5.根据权利要求2所述的方法,其特征在于:步骤(2)中,所述超临界二氧化碳萃取条件如下:萃取温度为50~60℃,第一次分离温度为45~50℃,第二次分离温度为35~40℃,萃取压力为25~30MPa,二氧化碳流速为40~80L/h,接收产物的频率为每次40~60min,提取时间为3~6h。
6.根据权利要求2或3所述的方法,其特征在于:所述乙醇浓度为75-85%(v/v),优选为80%(v/v)。
7.根据权利要求1所述的方法,其特征在于:步骤(3)中,用水洗脱至无色,用10~15%(v/v)(优选15%)乙醇洗脱至无绿原酸检出,用65~75%(v/v)(优选70%)乙醇洗脱至无黄酮类化合物检出。
8.根据权利要求1所述的方法,其特征在于:步骤(1)中,提油所用超临界二氧化碳萃取条件如下:萃取温度为40~60℃,第一次分离温度为40~50℃,第二次分离温度为30~40℃,萃取压力为25~35MPa,二氧化碳流速为20~80L/h,接收产物的频率为每次20~60min,提取时间为2~6h。
9.根据权利要求8所述的方法,其特征在于:步骤(1)中,提油所用超临界二氧化碳萃取条件如下之一:
A、萃取温度为40~50℃,第一次分离温度为40~45℃,第二次分离温度为30~35℃,萃取压力为30~35MPa,二氧化碳流速为20~40L/h,接收产物的频率为每次20~40min,提取时间为2~3h;
B、萃取温度为50~60℃,第一次分离温度为45~50℃,第二次分离温度为35-40℃,萃取压力为25~30MPa,二氧化碳流速为40~80L/h,接收产物的频率为每次40~60min,提取时间为3~6h。
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CN108689849A (zh) * | 2018-07-13 | 2018-10-23 | 鲁东大学 | 山楂叶粗提物中同时分离黄酮类和绿原酸类化合物的方法 |
CN108689849B (zh) * | 2018-07-13 | 2021-08-31 | 鲁东大学 | 山楂叶粗提物中同时分离黄酮类和绿原酸类化合物的方法 |
CN109363969A (zh) * | 2018-10-08 | 2019-02-22 | 广东暨晴生物医药科技有限公司 | 一种艾草有效成分的综合利用方法 |
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