CN108164382B - 一种从啤酒花中综合提取黄酮化合物的方法 - Google Patents
一种从啤酒花中综合提取黄酮化合物的方法 Download PDFInfo
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Abstract
一种从啤酒花中综合提取黄酮化合物的方法,属于精细化工领域,通过甲醇或乙醇浸提、固体和溶液分离、树脂吸附溶液、固体物溶解和尼龙粉柱层析处理溶解的固体物等步骤完成。本发明在提取、提纯黄腐酚的同时富集提纯了异黄腐酚、槲皮素;也富集了去甲基黄腐酚;富集了芦丁、金丝桃苷、紫云英苷等酒花黄酮化合物,初步实现了酒花资源的综合利用。
Description
技术领域
本发明属于精细化工领域,具体涉及一种从酒花残渣中提取、提纯黄酮等化合物的方法。
背景技术
二氧化碳萃取酒花后,残渣可以被用作饲料,但残渣中尚含有大量的多酚、黄酮类化合物,近年来的研究表明这类物质具有广泛的生理和药理活性,包括利胆、抗溃疡、护肝、利尿、抗病毒、防癌抗癌、***作用等。其中含量较多且被广泛关注的是黄腐酚,近年来的研究表明,黄腐酚通过抑制前致癌物向致癌物转变的酶活性,诱导致癌剂解毒酶的催化活性,禁止癌细胞在早期的生长从而起到有效预防癌症的作用;黄腐酚还具有抑制癌细胞扩增的作用;预防、治疗糖尿病和动脉硬化的作用;具有抗氧化作用;具有***的作用能够改善妇女更年期综合症,因而有着极高的开发价值。酒花是目前发现的天然黄腐酚的唯一来源。
酒花中的黄酮类化合物还包括异黄腐酚、6-异戊烯基柚皮素、8-异戊烯基柚皮素、去甲基黄腐酚、黄腐酚B、黄腐酚D、槲皮素、芦丁、金丝桃苷、紫云英苷等黄酮类化合物。
本申请人申请的中国专利200910117234.3采用吸附树脂富集黄腐酚;本申请人申请的中国专利201010167119.X制备得到高***腐酚,该方法适合小规模生产;本申请人申请的中国专利201110063773.0制备得到高***腐酚,且生产成本有所降低,产品已在市场上销售。
为了充分利用啤酒花资源,本发明在提取、提纯黄腐酚的同时富集提纯了异黄腐酚、槲皮素;也富集了去甲基黄腐酚;富集了芦丁、金丝桃苷、紫云英苷等酒花黄酮化合物,初步实现了酒花资源的综合利用。
发明内容
本发明目的在于提供一种从啤酒花中综合提取黄酮化合物的方法。
为实现上述目的,本发明采取的技术方案为:
①浸提:用40~80%体积百分比浓度的甲醇或乙醇浸提二氧化碳萃取后的酒花残渣,优选使用50~70%的酒精;溶剂用量是酒花残渣量的3~10倍,优选5~7倍;使酒花残渣中的黄酮化合物充分溶解,浸提时间为0.5~3小时,浸提温度为室温~60℃,同等条件下浸提1~3次;
②分离:浸提后过滤收集溶液,残渣舍弃,-0.06~-0.09MPa下减压蒸馏回收甲醇或乙醇,剩余的溶液经过0℃~10℃澄清后,分离固体和溶液;
③树脂吸附溶液:将步骤②得到的溶液用吸附树脂柱处理,吸附树脂为中极性吸附树脂,优选AB-8吸附树脂;吸附树脂柱经过水洗后用酒精溶液洗脱,洗脱得到的酒精溶液经过-0.06~-0.09MPa下减压蒸馏回收酒精后剩余水相,喷雾干燥得到棕色粉末,含有芦丁、金丝桃苷、紫云英苷等。
④溶解固体物:将步骤②得到的固体在80℃以下充分干燥,优选在60℃以下干燥。干燥后的固体用2~20倍重量的二氯甲烷溶解,优选用2-4倍固体重量的二氯甲烷溶解;经过滤得到澄清溶液;
⑤尼龙粉柱层析处理:将步骤④得到二氯甲烷溶液用尼龙粉柱层析处理,尼龙粉柱体积为二氯甲烷溶液体积的1~4倍,优选1.5~2倍;二氯甲烷溶液上尼龙粉柱后先用二氯甲烷洗脱,洗去绿色色带,收集二氯甲烷流出液,流出液体积为柱体积的2~3倍;再用乙酸乙酯洗脱尼龙粉柱,收集乙酸乙酯洗脱液,至流出液颜色由黄色变为接近无色,乙酸乙酯流出液体积为柱体积的2~3倍;再用甲醇洗脱尼龙粉柱,有明显的色带,收集色带部分洗脱液,流出液体积为柱体积的20%~50%;继续收集甲醇洗脱色带后的前部分流出液,流出液为黄色,收集流出液体积为0.8~1.2倍柱体积;继续收集甲醇洗脱色带后的后部分浅黄色流出液,收集流出液体积为1~1.5倍柱体积;共得到五部分洗脱液;所述尼龙粉为尼龙66或尼龙6的粉末,优选尼龙6;尼龙粉粒度为50~300目,使用上并无差别,粒度细则比表面积大,则吸附容量大,但洗脱时流速慢;
⑥浓缩处理:将步骤⑤得到的五部分洗脱液分别浓缩处理,二氯甲烷洗脱液完全回收二氯甲烷溶剂,剩余深绿色油状物,经分析其中含有叶绿素等;乙酸乙酯洗脱液浓缩至1%~2%体积,静置后析出大量结晶,经分析为黄腐酚,纯度达到90%以上;甲醇洗脱色带部分溶液浓缩蒸干,得到棕色固体粉末,经分析其中含有异黄腐酚、黄腐酚;甲醇洗脱色带后的前部分流出液浓缩蒸干,得到棕色固体粉末,经分析其中含有去甲基黄腐酚、异黄腐酚、黄腐酚等;甲醇洗脱色带后的后部分浅黄色流出液,浓缩至0.03%~0.2%体积,经过静置,析出绿色结晶,经分析为槲皮素;
⑦将步骤⑥得到甲醇色带部分固体及甲醇色带后的前部分的固体分别处理,经二至五次硅胶柱层析,硅胶柱乙酸乙酯洗脱液得到异黄腐酚;硅胶柱乙酸乙酯洗脱也能富集去甲基黄腐酚,但由于稳定性不好,得不到高纯度的去甲基黄腐酚。
硅胶柱层析是天然产物分离研究中常用的方法,行业中的专业人员都能熟练掌握,本发明中不再对这一多次硅胶层析的过程详细叙述。
本发明优点在于初步实现了啤酒花黄酮化合物的综合提取,充分利用了啤酒花资源,工艺过程简单,适合小规模生产。
附图说明
图1为本发明的流程图;
图2为黄腐酚结晶色谱图;
图3-1:甲醇洗脱色带部分分析色谱图(检测波长370nm);
图3-2:甲醇洗脱色带部分分析色谱图(检测波长288nm);
图4-1:甲醇洗脱色带后第1部分分析色谱图(检测波长370nm);
图4-2:甲醇洗脱色带后第1部分分析色谱图(检测波长288nm);
图5为提纯的异黄腐酚色谱图;
图6为提纯富集的去甲基黄腐酚色谱图。
具体实施方式
下面通过具体实施例进一步详细阐述本发明的技术方案及其实施步骤:
实施例1
①向100升体积百分比浓度70%的乙醇溶液中加入二氧化碳萃取酒花后的残渣,残渣加入量15千克,当溶液中加满残渣后开始加热萃取,加热温度为50℃,同时以超声的方法加速浸提过程,超声功率3000瓦,提取时间为1小时。滤出溶液,在同样的条件下再加入50升体积百分比浓度70%的乙醇溶液提取第二次;
②合并两次浸提过滤收集的溶液120升,-0.085MPa下减压蒸馏回收乙醇。将回收乙醇后的浑浊水相约11升在5℃下静置澄清。取出沉淀出来的膏状物,使固体与溶液分离;
③将步骤②得到的水溶液过滤,清液约10升,用AB-8吸附树脂柱处理,吸附树脂柱ф90mm,总高度800mm,树脂体积约5升,经过10升水洗后,用10升80%酒精溶液洗脱,洗脱得到的酒精溶液经过-0.06~-0.09MPa下减压蒸馏回收酒精后剩余浑浊的水相,喷雾干燥得到棕色粉末,含有芦丁、金丝桃苷、紫云英苷等。
④将步骤②得到的膏状物在60℃下充分干燥,得到深绿色固体650克。干燥后的固体用1300毫升(约1720克)二氯甲烷溶解,经过滤得到澄清溶液,溶液约1900毫升;
⑤将步骤③得到1900毫升二氯甲烷溶液用装有尼龙6粉的层析柱处理,层析柱ф60mm,尼龙粉高度750mm,柱层体积约2120毫升,尼龙粉粒度为50~100目。二氯甲烷溶液上尼龙柱后先用二氯甲烷洗脱,有绿色色带,收集二氯甲烷流出液,流出液体积3900毫升时绿色色带完全洗出来;改用乙酸乙酯洗脱尼龙柱,有不易观察的浅黄色色带,收集乙酸乙酯洗脱液3900毫升时,流出液颜色由黄色变为接近无色;改用甲醇洗脱尼龙柱,有深棕色色带,收集色带部分洗脱液约400毫升;更换接收瓶继续收集甲醇洗脱色带后部分第1部分流出液,流出液为黄色,收集流出液体积为1800毫升;更换接收瓶继续收集甲醇洗脱色带后第2部分浅黄色流出液,收集流出液体积为2500毫升;
⑥将步骤⑤得到的5部分洗脱液分别浓缩处理,二氯甲烷洗脱液完全回收二氯甲烷溶剂,剩余深绿色油状物,经分析其中含有叶绿素等;乙酸乙酯洗脱液浓缩至约70毫升,静置后析出大量橙黄色针状结晶,经分析为黄腐酚,纯度大于92%(色谱图见说明书附图2);甲醇洗脱色带部分溶液浓缩蒸干,得到棕色固体粉末,经分析其中含有异黄腐酚、黄腐酚等(色谱图见说明书附图3);甲醇洗脱色带后部分第1部分流出液浓缩蒸干,得到棕色固体粉末,经分析其中含有去甲基黄腐酚、异黄腐酚、黄腐酚等(色谱图见说明书附图4);甲醇洗脱色带后第2部分浅黄色流出液,浓缩至1.5毫升,经过静置,析出绿色结晶,经分析为槲皮素,纯度95%;
⑦将步骤⑥得到甲醇色带部分固体及甲醇色带后第一部分的固体分别处理,经多次硅胶柱层析,硅胶柱乙酸乙酯洗脱液浓缩后结晶得到异黄腐酚(色谱图见说明书附图5);硅胶柱乙酸乙酯洗脱也能富集去甲基黄腐酚,但由于稳定性不好,得不到高纯度的去甲基黄腐酚(色谱图见说明书附图6)。
实施例2
①向100升体积百分比浓度60%的乙醇溶液中加入二氧化碳萃取酒花后的残渣,残渣加入量15千克,当溶液中加满残渣后开始加热萃取,加热温度为50℃,提取时间为3小时。滤出溶液,在同样的条件下再加入50升体积百分比浓度60%的乙醇溶液提取第二次;
②合并两次浸提过滤收集的溶液115升,-0.085MPa下减压蒸馏回收乙醇。将回收乙醇后的浑浊水相约16升在0℃下静置澄清。取出沉淀出来的膏状物,使固体与溶液分离;
③将步骤②得到的水溶液过滤,清液约14升,用AB-8吸附树脂柱处理,吸附树脂柱ф90mm,总高度800mm,树脂体积约5升,经过10升水洗后,用10升80%酒精溶液洗脱,洗脱得到的酒精溶液经过-0.06~-0.09MPa下减压蒸馏回收酒精后剩余浑浊的水相,喷雾干燥得到棕色粉末,含有芦丁、金丝桃苷、紫云英苷等。
④以下步骤同实施例1。 图2中保留时间14.7分的色谱峰为黄腐酚,含量92.4%;图3-1中保留时间14.7分的色谱峰为黄腐酚; 图3-2中保留时间12.5分的色谱峰为异黄腐酚; 图4-1中保留时间14.7分的色谱峰为黄腐酚,保留时间12.5分的色谱峰为异黄腐酚;图4-2保留时间14.0分的色谱峰为去甲基黄腐酚,保留时间11.6分的色谱峰为槲皮素; 图5中保留时间12.5分的色谱峰为异黄腐酚,含量95%; 图6中保留时间14.0分的色谱峰为去甲基黄腐酚,含量71%。
Claims (6)
1.一种从啤酒花中综合提取黄酮化合物的方法,包括以下步骤完成:
①浸提:用40~80%体积百分比浓度的甲醇或乙醇浸提二氧化碳萃取后的酒花残渣,溶剂用量是酒花残渣量的3~10倍,浸提时间为0.5~3小时,浸提温度为室温~60℃,同等条件下浸提1~3次;
②分离:浸提后过滤收集溶液,-0.06~-0.09MPa下减压蒸馏回收甲醇或乙醇,剩余的溶液经过0℃~10℃澄清后,分离固体和溶液;
③树脂吸附溶液:将步骤②得到的溶液用吸附树脂柱处理,吸附树脂为中极性吸附树脂,吸附树脂柱经过水洗后用酒精溶液洗脱,洗脱得到的酒精溶液经过-0.06~-0.09MPa下减压蒸馏回收酒精后剩余水相,喷雾干燥得到棕色粉末,含有芦丁、金丝桃苷、紫云英苷;
④溶解固体物:将步骤②得到的固体在80℃以下充分干燥,干燥后的固体用2~20倍重量的二氯甲烷溶解,经过滤得到澄清溶液;
⑤尼龙粉柱层析处理:将步骤④得到二氯甲烷溶液用尼龙粉柱层析处理,尼龙粉柱体积为二氯甲烷溶液体积的1~4倍,二氯甲烷溶液上尼龙粉柱后先用二氯甲烷洗脱,收集二氯甲烷流出液,流出液体积为柱体积的2~3倍;再用乙酸乙酯洗脱尼龙粉柱,收集乙酸乙酯洗脱液,乙酸乙酯流出液体积为柱体积的2~3倍;再用甲醇洗脱尼龙粉柱,收集色带部分洗脱液,流出液体积为柱体积的20%~50%;继续收集甲醇洗脱色带后的前部分流出液,收集流出液体积为0.8~1.2倍柱体积;继续收集甲醇洗脱色带后的后部分,收集流出液体积为1~1.5倍柱体积;共得到五部分洗脱液;
⑥浓缩处理:将步骤⑤得到的五部分洗脱液分别浓缩处理,二氯甲烷洗脱液完全回收二氯甲烷溶剂;乙酸乙酯洗脱液浓缩至1%~2%体积;甲醇洗脱色带部分溶液浓缩蒸干;甲醇洗脱色带后的前部分流出液浓缩蒸干;甲醇洗脱色带后的后部分流出液,浓缩至0.03%~0.2%体积,经过静置,析出绿色结晶;
⑦将步骤⑥得到甲醇色带部分固体及甲醇色带后的前部分的固体分别处理,经二至五次硅胶柱层析,硅胶柱乙酸乙酯洗脱液得到异黄腐酚;硅胶柱乙酸乙酯洗脱富集去甲基黄腐酚。
2.根据权利要求1所述的的方法,其特征在于:步骤①中浸提二氧化碳萃取后的酒花残渣使用50~70%体积百分比浓度的酒精;溶剂用量是酒花残渣量的5~7倍。
3.根据权利要求1所述的方法,其特征在于:步骤②得到的固体干燥温度在60℃以下干燥,干燥后的固体用2-4倍固体重量的二氯甲烷溶解。
4.根据权利要求1所述的方法,其特征在于:步骤③所用中极性吸附树脂为AB-8吸附树脂。
5.根据权利要求1所述的方法,其特征在于:步骤⑤所用尼龙粉为尼龙66或尼龙6的粉末,所述尼龙粉粒度为50~300目;尼龙柱体积为二氯甲烷溶液体积的1.5~2倍。
6.根据权利要求5所述的方法,其特征在于:所用尼龙粉为尼龙6的粉末。
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