薯蓣皂素提取新工艺及相关基础研究
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摘要
薯蓣皂素的生产被誉为“废水之王”，所排污水量大，有机物含量高，酸性强，色素浓，极难治理，对周围环境造成巨大污染，目前尚无成功治理的方法。而生产薯蓣皂素的黄姜加工企业又主要处于南水北调中线工程的水源地，如果不进行改进治理，这些企业将面临关停的命运。
为了改变薯蓣皂素的这种生产现状，对现有的酸水解工艺进行改进，提出了用酶法改进处理以综合利用黄姜中的淀粉发酵燃料乙醇。研究了黄姜的糊化性质及液化、糖化过程，为生产燃料乙醇提供参考。得到了液化糖化的最佳操作条件：粒度为0.28mm以下黄姜粉按1：5(w／w)调浆，加液化酶10u／g，在90℃下液化30分钟即能达到良好的液化效果；调pH 4.0～4.5，加糖化酶60u／g，在60℃下糖化90分钟就可糖化完全。
本文提出一种全新的热分解方法来处理黄姜，并对其进行相关基础研究，为以后的工业生产提供理论依据。新工艺过程中无需酸、碱处理，最重要的是不需对残渣进行清洗，基本无废水产生，从根本上解决了皂素生产中的污水处理问题，可以实现真正意义上的清洁生产。该工艺简称热分解法，现已申请国家发明专利，并获得河南省教育厅自然科学基础研究项目的资助。
研究了影响热分解的各种因素，得到操作的优化条件，回归出相应的数学模型。利用响应面法进行分析可知，压力越高，保压时间越长，加料量适中，物料粒度越细，处理效果越好。操作优化条件为：饱和蒸汽压力1.4MPa，保压时间30min，加料量3.5kg，在此条件下薯蓣皂素的收率为1.745％。在热分解前加入二氧化碳介质，可以提高处理效果，改善物料颜色，但物料呈酸性，保压时间需要适当延长。
用SAS软件对数据进行回归分析，得薯蓣皂素收率与热分解操作参数之间的关系式：Y~(1.4)=1.619992+0.445945*X1+0.436486*X2—0.128199*X3—0.186137*X1*X1+0.180706*X1*X3—0.266779*X2*X2+0.155259*X2*X3，模型的相关系数R~2=0.9753。
本文对热分解物料中的薯蓣皂素进行有机溶剂提取和超临界CO_2萃取的研究，并与水解物进行提取对比。在有机溶剂萃取时，考察了时间、温度、溶剂量及粒度的影响。热分解物的皂素收率为1.75％左右，萃取率约为72.9％；水解物的皂素收率约为10.5％，萃取率为75％左右。从收率看，这两种原料提取的薯蓣皂素量有很大的悬殊，但二者的萃取效果相当。
用SAS软件处理热分解物超临界萃取的数据，得到相应的关系曲线和等收率线。根据误差分析的结果可知，CO_2流量影响最大、其次是操作压力，然后是加料量的影响。优化出热分解物超临界萃取最佳条件为：操作压力35MPa，温度55℃，CO_2流量12kg／h，加料量125g，皂素萃取率为89.96％。
对数据进行回归分析，则薯蓣皂素的萃取率与热分解物超临界萃取操作参数之间的关系可拟合如下：Y=74.68667+7.478333*X1+1.456667*X2+8.560833*X3—4.654167*X4—1.08375*X1*X1+2.9625*X1*X2—2.205*X1*X3+3.5925*X1*X4+0.77125*X2*X2+1.9975*X2*X3—1.405*X2*X4—4.61*X3*X3—1.855*X3*X4—3.365*X4*X4，模型的相关系数R~2=0.9300。
通过对水解物超临界萃取的研究可知，压力的变化对水解物萃取效果的影响最大，其次是CO_2流量和温度的变化。由正交试验法得其最佳操作条件为100g原料，萃取时间4h，萃取压力35MPa，萃取温度45℃，CO_2流量12kg／h，无水乙醇的用量300mL，此时薯蓣皂素萃取率为88.25％。
通过对黄姜热分解物进行扫描电镜、红外光谱、X-射线衍射和热分析的表征，探讨了热分解作用的机理，分析了黄姜中淀粉和纤维素在热分解过程中的变化情况，对由热分解产物提纯的物质进行了结构确证。通过测定熔点、紫外光谱、红外图谱、核磁共振氢谱、质谱与标准品进行比对，谱图基本一致，表明该物质确为薯蓣皂素。用超高效液质联用UPLC-MS对以水解物、热分解产物为原料，有机溶剂和超临界提取的产物进行定量分析，结果表明，用有机溶剂提取时，从水解物中提取的薯蓣皂素含量比从热分解物中提取的薯蓣皂素含量高。但用超，临界萃取的方法却是从热分解物中提取的薯蓣皂素含量高。
酸水解物料为粉状，需用酸回流水解3～6h，产生大量废水；而热分解物料可为5cm以下的块状，处理时间短，只需30min左右，基本无废水。无论是从经济性，还是从环保角度看，热分解法都比酸水解法要优越得多。因此热分解方法可以彻底革新薯蓣皂素的生产工艺，从根本上解决皂素生产中的废水问题，对实现真正的绿色过程，促使皂素生产健康持续发展，具有非常重要的生产实际意义。
The wastewater from diosgenin production is called as the king which is great acidity, thick colour, high organic matter concentration. At present, there isn't an appropriate process that can be used to treat the wastewater successfully in practical engineering. The diosgenin plants mainly lie the upriver of Danjiangkou Reservoir wich is the water source of the middle line of South-to-North water diversion project (MLSWDP). The water pollution will directly effect the water quality of the MLSWDP, and effect the national strategy. If no effective measures adopting, the diosgenin plants will face the fate of closed.
In order to changing the situation of diosgenin, we put up the enzymatic hydrolysis method to comprehensive utilize the starch by fermenting fuel ethanol. We study the factors of the Dioscorea zingiberensis C. H. Wright pasting property, liquefaction and saccharification. The optimal operation conditions are achieved: the particle 0.28mm, add water by the rate of 5 (w/w), the amount ofα-amylase 10u/g, at 90℃holding 30min; And then, adjust pH 4.0～4.5, add the amount ofglucoamylase 60u/g, at 60℃holding 90min.
We put forward a new treatment method——heat decomposed technology to improve the situation of diosgenin. Fundamental research is carried in order to provide the theory base. It can predigest the process and avoid the pollution. There is no acid, alkali reagent and wastewater in the whole process. What's the most important is no washing and no wastewater. So it is the real pollution-free technology. Now, we have applied the invention patent. It has been sponsored by the project of Henan Province Education office.
We take the lead in researching the factors of heat-decomposed technics, get the process optimization and the mathematic mold by response method. The effect of heat decomposed is better with high pressure, long holding time, and moderate material amount. The best condition is the steam pressure 1.4 MPa, holding 30min, the material 3.5kg and the product rate 1.745%. The treated material was better with weak color when CO_2 added, but it's acidity was increased slightly, and the holding time needed longer.
We obtain the correlation formula about the product rate and heat-decomposed factors by SAS software: Y~(1.4)=1.619992+0.445945~*X1+0.436486~*X2-0.128199~*X3-0.186137~*X1~*X1+0.180706~*X1~*X3-0.266779~*X2~*X2+0.155259~*X2~*X3, R~2=0.9753.
In this paper, we extract diosgenin from heat-decomposed material by solvent extraction, SFE-CO_2 by contrast with acid-hydrolyzed material. The factors of solvent extraction are investigated about extracting time, temperature, the amount of solvent and granularity. The heat decomposed material: product rate is 1.75%, extraction rate is about 72.9%; The acid hydrolyzed material: product rate is 10.5%, extraction rate is about 75%. The amount of diosgenin is higher from acid-hydrolyzed than from heat-decomposed material. But at the raw material point, their extraction rates are same.
The response surface stereograms and contour plots in SFE-CO_2 extraction with heat decomposed material are gained by SAS software. According to the result of error analysis, the CO_2 flux is the most important, the pressure is the next, and then is the amount of material. The terms of optimization: the pressure 35 MPa, temperature 55℃, CO_2 flux 12 kg/h, the material 125g, and the extracting rate 89.96%.
We obtain the correlation formula about the extracting rate and factors about heat decomposed material with SFE-CO_2 extraction by SAS software: Y=74.68667+7.478333~*X1+1.456667~*X2+8.560833~*X3-4.654167~*X4-1.08375~*X1~*X1+2.9625~*X1~*X2-2.205~*X1~*X3+3.5925~*X1~*X4+0.77125~*X2~*X2+1.9975~*X2~*X3-1.405~*X2~*X4-4.61~*X3~*X3-1.855~*X3~*X4-3.365~*X4~*X4, R~2=0.9300.
In SFE-CO_2 extraction process with the acid-hydrolyzed material, the pressure is the most important, the CO_2 flux is the next, and then is the temperature. The best terms obtained by Orthogonal test are the material 100g, time 4h, the pressure 35 MPa, temperature 45℃, CO_2 flux 12 kg/h, and ethanol 300mL, the extracting rate 88.25%.
We discuss the mechanism, characteristic of original and the treated material by meanas of SEM, FT-IR, X-ray diffraction and thermal analysis. The change of amylum and cellulose in the tubers among the heat-decomposed process are discussed. The results show that heat-decomposed technology can break up the supermolecule structure of amylum and cellulose. Diosgenin can be directly extracted from the heat-decomposed material. The product extracting from the heat-decomposed material is identified as diosgenin by melting point, UV, FT-IR, ~1HNMR, UPLC-MS. The extracts from different material with different extraction methods are quantitated by UPLC-MS. The results show that the content of diosgenin extracting from acid-hydrolyzed residue is higher than that from heat decomposed material by solvent extraction. While the content from heat decomposed material is higher than that from acid-hydrolyzed residue by SFE-CO_2.
The powder material is acid hydrolysis with circumfluence time 3～6h. There are a lot of wastewater produced in acid hydrolysis procedure. But, the material about 5cm is treated 30min in the heat decomposed method, and there is no wastewater in the whole process. Whatever the economy or environment protection, the heat decomposed method is more preponderance than acid hydrolysis. So, the heat decomposed technology is a simple method without acid-hydrolysis and no wastewater produced. It is a revolution of diosgenin and can solve the pollution problem root and branch. It is significant to improve the market competition capacity of diosgenin.
为了改变薯蓣皂素的这种生产现状，对现有的酸水解工艺进行改进，提出了用酶法改进处理以综合利用黄姜中的淀粉发酵燃料乙醇。研究了黄姜的糊化性质及液化、糖化过程，为生产燃料乙醇提供参考。得到了液化糖化的最佳操作条件：粒度为0.28mm以下黄姜粉按1：5(w／w)调浆，加液化酶10u／g，在90℃下液化30分钟即能达到良好的液化效果；调pH 4.0～4.5，加糖化酶60u／g，在60℃下糖化90分钟就可糖化完全。
本文提出一种全新的热分解方法来处理黄姜，并对其进行相关基础研究，为以后的工业生产提供理论依据。新工艺过程中无需酸、碱处理，最重要的是不需对残渣进行清洗，基本无废水产生，从根本上解决了皂素生产中的污水处理问题，可以实现真正意义上的清洁生产。该工艺简称热分解法，现已申请国家发明专利，并获得河南省教育厅自然科学基础研究项目的资助。
研究了影响热分解的各种因素，得到操作的优化条件，回归出相应的数学模型。利用响应面法进行分析可知，压力越高，保压时间越长，加料量适中，物料粒度越细，处理效果越好。操作优化条件为：饱和蒸汽压力1.4MPa，保压时间30min，加料量3.5kg，在此条件下薯蓣皂素的收率为1.745％。在热分解前加入二氧化碳介质，可以提高处理效果，改善物料颜色，但物料呈酸性，保压时间需要适当延长。
用SAS软件对数据进行回归分析，得薯蓣皂素收率与热分解操作参数之间的关系式：Y~(1.4)=1.619992+0.445945*X1+0.436486*X2—0.128199*X3—0.186137*X1*X1+0.180706*X1*X3—0.266779*X2*X2+0.155259*X2*X3，模型的相关系数R~2=0.9753。
本文对热分解物料中的薯蓣皂素进行有机溶剂提取和超临界CO_2萃取的研究，并与水解物进行提取对比。在有机溶剂萃取时，考察了时间、温度、溶剂量及粒度的影响。热分解物的皂素收率为1.75％左右，萃取率约为72.9％；水解物的皂素收率约为10.5％，萃取率为75％左右。从收率看，这两种原料提取的薯蓣皂素量有很大的悬殊，但二者的萃取效果相当。
用SAS软件处理热分解物超临界萃取的数据，得到相应的关系曲线和等收率线。根据误差分析的结果可知，CO_2流量影响最大、其次是操作压力，然后是加料量的影响。优化出热分解物超临界萃取最佳条件为：操作压力35MPa，温度55℃，CO_2流量12kg／h，加料量125g，皂素萃取率为89.96％。
对数据进行回归分析，则薯蓣皂素的萃取率与热分解物超临界萃取操作参数之间的关系可拟合如下：Y=74.68667+7.478333*X1+1.456667*X2+8.560833*X3—4.654167*X4—1.08375*X1*X1+2.9625*X1*X2—2.205*X1*X3+3.5925*X1*X4+0.77125*X2*X2+1.9975*X2*X3—1.405*X2*X4—4.61*X3*X3—1.855*X3*X4—3.365*X4*X4，模型的相关系数R~2=0.9300。
通过对水解物超临界萃取的研究可知，压力的变化对水解物萃取效果的影响最大，其次是CO_2流量和温度的变化。由正交试验法得其最佳操作条件为100g原料，萃取时间4h，萃取压力35MPa，萃取温度45℃，CO_2流量12kg／h，无水乙醇的用量300mL，此时薯蓣皂素萃取率为88.25％。
通过对黄姜热分解物进行扫描电镜、红外光谱、X-射线衍射和热分析的表征，探讨了热分解作用的机理，分析了黄姜中淀粉和纤维素在热分解过程中的变化情况，对由热分解产物提纯的物质进行了结构确证。通过测定熔点、紫外光谱、红外图谱、核磁共振氢谱、质谱与标准品进行比对，谱图基本一致，表明该物质确为薯蓣皂素。用超高效液质联用UPLC-MS对以水解物、热分解产物为原料，有机溶剂和超临界提取的产物进行定量分析，结果表明，用有机溶剂提取时，从水解物中提取的薯蓣皂素含量比从热分解物中提取的薯蓣皂素含量高。但用超，临界萃取的方法却是从热分解物中提取的薯蓣皂素含量高。
酸水解物料为粉状，需用酸回流水解3～6h，产生大量废水；而热分解物料可为5cm以下的块状，处理时间短，只需30min左右，基本无废水。无论是从经济性，还是从环保角度看，热分解法都比酸水解法要优越得多。因此热分解方法可以彻底革新薯蓣皂素的生产工艺，从根本上解决皂素生产中的废水问题，对实现真正的绿色过程，促使皂素生产健康持续发展，具有非常重要的生产实际意义。
The wastewater from diosgenin production is called as the king which is great acidity, thick colour, high organic matter concentration. At present, there isn't an appropriate process that can be used to treat the wastewater successfully in practical engineering. The diosgenin plants mainly lie the upriver of Danjiangkou Reservoir wich is the water source of the middle line of South-to-North water diversion project (MLSWDP). The water pollution will directly effect the water quality of the MLSWDP, and effect the national strategy. If no effective measures adopting, the diosgenin plants will face the fate of closed.
In order to changing the situation of diosgenin, we put up the enzymatic hydrolysis method to comprehensive utilize the starch by fermenting fuel ethanol. We study the factors of the Dioscorea zingiberensis C. H. Wright pasting property, liquefaction and saccharification. The optimal operation conditions are achieved: the particle 0.28mm, add water by the rate of 5 (w/w), the amount ofα-amylase 10u/g, at 90℃holding 30min; And then, adjust pH 4.0～4.5, add the amount ofglucoamylase 60u/g, at 60℃holding 90min.
We put forward a new treatment method——heat decomposed technology to improve the situation of diosgenin. Fundamental research is carried in order to provide the theory base. It can predigest the process and avoid the pollution. There is no acid, alkali reagent and wastewater in the whole process. What's the most important is no washing and no wastewater. So it is the real pollution-free technology. Now, we have applied the invention patent. It has been sponsored by the project of Henan Province Education office.
We take the lead in researching the factors of heat-decomposed technics, get the process optimization and the mathematic mold by response method. The effect of heat decomposed is better with high pressure, long holding time, and moderate material amount. The best condition is the steam pressure 1.4 MPa, holding 30min, the material 3.5kg and the product rate 1.745%. The treated material was better with weak color when CO_2 added, but it's acidity was increased slightly, and the holding time needed longer.
We obtain the correlation formula about the product rate and heat-decomposed factors by SAS software: Y~(1.4)=1.619992+0.445945~*X1+0.436486~*X2-0.128199~*X3-0.186137~*X1~*X1+0.180706~*X1~*X3-0.266779~*X2~*X2+0.155259~*X2~*X3, R~2=0.9753.
In this paper, we extract diosgenin from heat-decomposed material by solvent extraction, SFE-CO_2 by contrast with acid-hydrolyzed material. The factors of solvent extraction are investigated about extracting time, temperature, the amount of solvent and granularity. The heat decomposed material: product rate is 1.75%, extraction rate is about 72.9%; The acid hydrolyzed material: product rate is 10.5%, extraction rate is about 75%. The amount of diosgenin is higher from acid-hydrolyzed than from heat-decomposed material. But at the raw material point, their extraction rates are same.
The response surface stereograms and contour plots in SFE-CO_2 extraction with heat decomposed material are gained by SAS software. According to the result of error analysis, the CO_2 flux is the most important, the pressure is the next, and then is the amount of material. The terms of optimization: the pressure 35 MPa, temperature 55℃, CO_2 flux 12 kg/h, the material 125g, and the extracting rate 89.96%.
We obtain the correlation formula about the extracting rate and factors about heat decomposed material with SFE-CO_2 extraction by SAS software: Y=74.68667+7.478333~*X1+1.456667~*X2+8.560833~*X3-4.654167~*X4-1.08375~*X1~*X1+2.9625~*X1~*X2-2.205~*X1~*X3+3.5925~*X1~*X4+0.77125~*X2~*X2+1.9975~*X2~*X3-1.405~*X2~*X4-4.61~*X3~*X3-1.855~*X3~*X4-3.365~*X4~*X4, R~2=0.9300.
In SFE-CO_2 extraction process with the acid-hydrolyzed material, the pressure is the most important, the CO_2 flux is the next, and then is the temperature. The best terms obtained by Orthogonal test are the material 100g, time 4h, the pressure 35 MPa, temperature 45℃, CO_2 flux 12 kg/h, and ethanol 300mL, the extracting rate 88.25%.
We discuss the mechanism, characteristic of original and the treated material by meanas of SEM, FT-IR, X-ray diffraction and thermal analysis. The change of amylum and cellulose in the tubers among the heat-decomposed process are discussed. The results show that heat-decomposed technology can break up the supermolecule structure of amylum and cellulose. Diosgenin can be directly extracted from the heat-decomposed material. The product extracting from the heat-decomposed material is identified as diosgenin by melting point, UV, FT-IR, ~1HNMR, UPLC-MS. The extracts from different material with different extraction methods are quantitated by UPLC-MS. The results show that the content of diosgenin extracting from acid-hydrolyzed residue is higher than that from heat decomposed material by solvent extraction. While the content from heat decomposed material is higher than that from acid-hydrolyzed residue by SFE-CO_2.
The powder material is acid hydrolysis with circumfluence time 3～6h. There are a lot of wastewater produced in acid hydrolysis procedure. But, the material about 5cm is treated 30min in the heat decomposed method, and there is no wastewater in the whole process. Whatever the economy or environment protection, the heat decomposed method is more preponderance than acid hydrolysis. So, the heat decomposed technology is a simple method without acid-hydrolysis and no wastewater produced. It is a revolution of diosgenin and can solve the pollution problem root and branch. It is significant to improve the market competition capacity of diosgenin.
引文
[1] 《全国中草药汇编》编写组编．全国中草药汇编(上册)[M]．人民卫生出版社，第一版，1973：633-634
[2] 江苏新医学院编．中药大辞典(下册)[M]．上海科学技术出版社，第一版，1986：1698
[3] Benghuzzi, Hamed;Tucci, Michelle; Eckie, Rebecca et al.The effects of sustained delivery of diosgenin on the adrenal gland of female rats [J]. Biomedical Sciences Instrumentation, 2003, 39: 335-340
[4] Tucci,Michelle; Benghuzzi,Hamed. Structural changes in the kidney associated with ovariectomyand diosgenin replacement therapy in adult female rats [J]. Biomedical Sciences Instrumentation, 2003, 39:341-346
[5] Roman, I. D.; Thewles, A.; Coleman, R. Fractionation of livers following diosgenin treatment to elevate biliary cholesterol [J]. B B A-Biomembranes, 1995, 1255(1): 77
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