薯蓣皂素清洁生产关键技术及盾叶薯蓣资源化利用研究
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摘要
薯蓣皂素是合成皮质激素、肾上腺激素、蛋白质同化激素的基础原料，被誉为“20世纪医药工业的第二大发现”。Rothrok法以其工艺简单，设备投资少，成本低而备受生产企业的青睐。近年来，随着环境的不断恶化，Rothrok法造成的污染问题引起人们的极大关注，其工艺受到挑战。本论文以盾叶薯蓣为研究对象，围绕薯蓣皂素生产过程中的污染及薯蓣皂素生产成本，就薯蓣皂素清洁生产关键技术及盾叶薯蓣资源化利用进行研究，主要研究内容如下：
1采用各类分析方法，测定了盾叶薯蓣中的淀粉、纤维素、半纤维素、木质素、薯蓣皂苷、薯蓣皂素的含量，为资源化利用盾叶薯蓣奠定了基础。
2以盾叶薯蓣为原料，以乙醇为萃取剂，以薯蓣皂苷、薯蓣皂素得率为评价指标，采用单因素实验法、正交试验法优化了超声波辅助乙醇萃取薯蓣皂苷的条件。结果表明，当乙醇体积分数为75v/v，料（盾叶薯蓣）液（萃取剂）比为1:5，超声波频率为35.74KHz，超声时间为30min，盾叶薯蓣被连续萃取3次时，薯蓣皂苷、薯蓣皂素的得率为14.49%及3.29%，分别为传统常温浸提法的1.36倍及1.13倍，萃取效率为传统常温浸提法的48倍。
3在超声条件（频率、时间）一定的情况下，研究了表面活性剂类型、结构、亲水亲油平衡值（HLB）、临界胶团浓度（cmc）等对薯蓣皂苷得率的影响。在此基础上，研究了以表面活性剂对薯蓣皂苷摩尔增溶率（MSR）作为薯蓣皂苷萃取时表面活性剂选择标准的可行性，为其它天然产物有效成分萃取时表面活性剂的选择提供理论依据。
4研究了絮凝剂种类、加量、絮凝温度、絮凝时间等对薯蓣皂苷分离因数的影响，确定了薯蓣皂苷最佳絮凝条件，为以絮凝薯蓣皂苷法替代传统热富集薯蓣皂苷法提供理论依据。研究了硫酸加量、硫酸浓度、硫酸回用次数，薯蓣皂苷水解温度、水解时间、薯蓣皂素萃取时间等对薯蓣皂素得率的影响。
5在实验室小试的基础上，以50Kg盾叶薯蓣为原料，进行5次放大实验，对薯蓣皂素生产的原料成本、废水排放量、废水性质进行综合评价，结果表明，该方法能够达到控制污染，降低成本的目标。
6采用现代生物技术，优化了以萃取薯蓣皂苷后的盾叶薯蓣废渣为原料发酵乙醇的条件。在此基础上，以30Kg萃取薯蓣皂苷后的盾叶薯蓣废渣为原料，进行放大实验，此发酵醪的酒精度为10.5v/v，淀粉利用率为90.6%。该技术可资源化地利用盾叶薯蓣中的淀粉资源，进一步地降低了薯蓣皂素的生产成本，符合低碳、环保的发展要求。
本论文的创新之处：
1系统研究了以表面活性剂增溶方法、薯蓣皂苷絮凝方法为核心的薯蓣皂素清洁生产工艺。在实验室小试的基础上，研究了该工艺生产过程中废水排放及废水性质，比较了采用该工艺与传统工艺生产薯蓣皂素时的原料成本，进一步证实该工艺能够达到控制污染，降低成本，实现薯蓣皂素清洁生产的目的。
2采用多种方法研究了表面活性剂结构对薯蓣皂苷萃取的影响，为薯蓣皂苷萃取时科学选择表面活性剂奠定了基础。测试了各表面活性剂对薯蓣皂苷摩尔增溶率（MSR）的大小，在此基础上，分析了超声条件下，以MSR值作为薯蓣皂苷萃取时表面活性剂选择的可行性。
3比较了以盾叶薯蓣、盾叶薯蓣废渣为原料进行乙醇发酵时发酵醪的酒精度、淀粉利用率及酒糟的扫描电镜图（SEM），发现萃取薯蓣皂苷后的盾叶薯蓣废渣更适合乙醇发酵，该技术符合循环经济的发展模式，为其它含淀粉类植物的综合利用奠定了基础。
Diosgenin is the basic raw material of synthesising ofcorticosteroids, the adrenal hormones, protein anabolic hormones,which is known as "the second discovery of the20thcentury inpharmaceutical industry". Rothrok's method process was simple, lessinvestment in equipment, low cost, which drew enterprises's attention ofall ages. In recent years, however, with the worsening of theenvironment, the pollution problems of Rothrok method cause a greatconcern and the process was being challenged. In this paper, withDioscorea Zingiberensis as research object, for the purpose of reducingpollution and cost, key technologies of diosgenin clean production andresources utilization of Dioscorea Zingiberensis were studied, which were described as below:
1All kinds of methods were applied to determine the content ofstarch, cellulose, hemicellulose, lignin, diosgenin in DioscoreaZingiberensis, and laid the foundations for Dioscorea Zingiberensisresources utilization.
2With Dioscorea Zingiberensis as the raw material, ethanol asextraction agent, the yield of dioscin and diosgenin as the evaluationindexes, the single factor and the orthogonal experiment methods wereused to optimize the conditions of ultrasonic extraction of dioscin.When ethanol volume fraction was75v/v, the ration of solid (DioscoreaZingiberensis) to liquid (extractant) was1:5, the ultrasonic frequencywas35.74KHz, ultrasonic time was30min, Dioscorea Zingiberensiswas continuously extracted for3times, the yield of the dioscin anddiosgenin can reach to14.49%and3.2907%, which were1.36times,1.13times of the extraction at room temperature (traditional extractionmethod), respectively. The extraction efficiency was32times of the traditional extraction method.
3Under certain circumstances of ultrasound conditions (frequency,time), the influence of surfactant type, structure, hydrophilic lipophilicbalance (HLB) value, the critical micelle concentration (cmc) ondioscin yield were researched. The feasibility of surfactant selectionprinciple at dioscin extration was studied according to the influence ofsurfactant on dioscin molar solubilizatoin ratio (MSR), serving as atheoretical basis for the choice of surfactant in dioscin extraction.
4The investigation on the influence of flocculant types, dosage,flocculation temperature, flocculation time on the dioscin separationfactor help to determine the optimum flocculation conditions of dioscin,along with the study of the influence of the sulfuric acid dosage, theconcentration of sulfuric acid, the number of times sulfuric acid reuseand hydrolysis temperature of dioscin, hydrolysis time, diosgeninextraction time on the yield of diosgenin.
5On the basis of laboratory experiment, pilot-scale experiments were conducted for5times with50Kg Dioscorea Zingiberensis as rawmaterials. A comprehensive evaluation of production costs of rawmaterials, waste water emissions and properties of waste water weremade, and considered that the process could be achieved the aim ofpollution control and costs reduction in the production of diosgenin.
6Modern biotechnology is adopted to optimize the conditions ofalcoholic fermentation with Dioscorea Zingiberensis residue after theextraction of dioscin as a raw material. With30Kg above-mentionedraw material, pilot-scale experiments demonstrate that alcohol contentof the fermented mash is up to10.5v/v, starch utilization90.6%. Thistechnology makes resource utilization starch in the DioscoreaZingiberensis feasible, and further reduces the cost of production ofdiosgenin in line with the requirements of low-carbon, environmentalfriendly development.
The innovation of this paper.
1The technology of diosgenin clean production was research systematically, With surfactant extraction technology and flocculationtechnology as the core. On the basis of laboratory experiments,wastewater discharge and wastewater properties in the process ofdiosgenin clean production are studied. The costs of raw materials arecompared in the process of diosgenin clean production and thetraditional process. It is found that the clean process helps to controlpollution and reduce costs.
2The effect of surfactant structure on dioscin extraction is studiedin several ways, which paves the way for the scientific surfactantselection principle at dioscin extraction. Besides the test of surfactantson dioscin molar solubilizatoin ratio (MSR), verified feasibility ofsurfactant selection principle at dioscin extraction with the effect ofsurfactant on molar solubilization rate.
3The content of alcohol in fermenting mash, the utilization rate ofstarch and the SEM of distillers' grains are compared with DioscoreaZingiberensis and Dioscorea Zingiberensis residue as raw materials. This technology is in line with the development of recycling economymode, laying the foundation for comprehensive utilization of otherstarch-containing plants.
1采用各类分析方法，测定了盾叶薯蓣中的淀粉、纤维素、半纤维素、木质素、薯蓣皂苷、薯蓣皂素的含量，为资源化利用盾叶薯蓣奠定了基础。
2以盾叶薯蓣为原料，以乙醇为萃取剂，以薯蓣皂苷、薯蓣皂素得率为评价指标，采用单因素实验法、正交试验法优化了超声波辅助乙醇萃取薯蓣皂苷的条件。结果表明，当乙醇体积分数为75v/v，料（盾叶薯蓣）液（萃取剂）比为1:5，超声波频率为35.74KHz，超声时间为30min，盾叶薯蓣被连续萃取3次时，薯蓣皂苷、薯蓣皂素的得率为14.49%及3.29%，分别为传统常温浸提法的1.36倍及1.13倍，萃取效率为传统常温浸提法的48倍。
3在超声条件（频率、时间）一定的情况下，研究了表面活性剂类型、结构、亲水亲油平衡值（HLB）、临界胶团浓度（cmc）等对薯蓣皂苷得率的影响。在此基础上，研究了以表面活性剂对薯蓣皂苷摩尔增溶率（MSR）作为薯蓣皂苷萃取时表面活性剂选择标准的可行性，为其它天然产物有效成分萃取时表面活性剂的选择提供理论依据。
4研究了絮凝剂种类、加量、絮凝温度、絮凝时间等对薯蓣皂苷分离因数的影响，确定了薯蓣皂苷最佳絮凝条件，为以絮凝薯蓣皂苷法替代传统热富集薯蓣皂苷法提供理论依据。研究了硫酸加量、硫酸浓度、硫酸回用次数，薯蓣皂苷水解温度、水解时间、薯蓣皂素萃取时间等对薯蓣皂素得率的影响。
5在实验室小试的基础上，以50Kg盾叶薯蓣为原料，进行5次放大实验，对薯蓣皂素生产的原料成本、废水排放量、废水性质进行综合评价，结果表明，该方法能够达到控制污染，降低成本的目标。
6采用现代生物技术，优化了以萃取薯蓣皂苷后的盾叶薯蓣废渣为原料发酵乙醇的条件。在此基础上，以30Kg萃取薯蓣皂苷后的盾叶薯蓣废渣为原料，进行放大实验，此发酵醪的酒精度为10.5v/v，淀粉利用率为90.6%。该技术可资源化地利用盾叶薯蓣中的淀粉资源，进一步地降低了薯蓣皂素的生产成本，符合低碳、环保的发展要求。
本论文的创新之处：
1系统研究了以表面活性剂增溶方法、薯蓣皂苷絮凝方法为核心的薯蓣皂素清洁生产工艺。在实验室小试的基础上，研究了该工艺生产过程中废水排放及废水性质，比较了采用该工艺与传统工艺生产薯蓣皂素时的原料成本，进一步证实该工艺能够达到控制污染，降低成本，实现薯蓣皂素清洁生产的目的。
2采用多种方法研究了表面活性剂结构对薯蓣皂苷萃取的影响，为薯蓣皂苷萃取时科学选择表面活性剂奠定了基础。测试了各表面活性剂对薯蓣皂苷摩尔增溶率（MSR）的大小，在此基础上，分析了超声条件下，以MSR值作为薯蓣皂苷萃取时表面活性剂选择的可行性。
3比较了以盾叶薯蓣、盾叶薯蓣废渣为原料进行乙醇发酵时发酵醪的酒精度、淀粉利用率及酒糟的扫描电镜图（SEM），发现萃取薯蓣皂苷后的盾叶薯蓣废渣更适合乙醇发酵，该技术符合循环经济的发展模式，为其它含淀粉类植物的综合利用奠定了基础。
Diosgenin is the basic raw material of synthesising ofcorticosteroids, the adrenal hormones, protein anabolic hormones,which is known as "the second discovery of the20thcentury inpharmaceutical industry". Rothrok's method process was simple, lessinvestment in equipment, low cost, which drew enterprises's attention ofall ages. In recent years, however, with the worsening of theenvironment, the pollution problems of Rothrok method cause a greatconcern and the process was being challenged. In this paper, withDioscorea Zingiberensis as research object, for the purpose of reducingpollution and cost, key technologies of diosgenin clean production andresources utilization of Dioscorea Zingiberensis were studied, which were described as below:
1All kinds of methods were applied to determine the content ofstarch, cellulose, hemicellulose, lignin, diosgenin in DioscoreaZingiberensis, and laid the foundations for Dioscorea Zingiberensisresources utilization.
2With Dioscorea Zingiberensis as the raw material, ethanol asextraction agent, the yield of dioscin and diosgenin as the evaluationindexes, the single factor and the orthogonal experiment methods wereused to optimize the conditions of ultrasonic extraction of dioscin.When ethanol volume fraction was75v/v, the ration of solid (DioscoreaZingiberensis) to liquid (extractant) was1:5, the ultrasonic frequencywas35.74KHz, ultrasonic time was30min, Dioscorea Zingiberensiswas continuously extracted for3times, the yield of the dioscin anddiosgenin can reach to14.49%and3.2907%, which were1.36times,1.13times of the extraction at room temperature (traditional extractionmethod), respectively. The extraction efficiency was32times of the traditional extraction method.
3Under certain circumstances of ultrasound conditions (frequency,time), the influence of surfactant type, structure, hydrophilic lipophilicbalance (HLB) value, the critical micelle concentration (cmc) ondioscin yield were researched. The feasibility of surfactant selectionprinciple at dioscin extration was studied according to the influence ofsurfactant on dioscin molar solubilizatoin ratio (MSR), serving as atheoretical basis for the choice of surfactant in dioscin extraction.
4The investigation on the influence of flocculant types, dosage,flocculation temperature, flocculation time on the dioscin separationfactor help to determine the optimum flocculation conditions of dioscin,along with the study of the influence of the sulfuric acid dosage, theconcentration of sulfuric acid, the number of times sulfuric acid reuseand hydrolysis temperature of dioscin, hydrolysis time, diosgeninextraction time on the yield of diosgenin.
5On the basis of laboratory experiment, pilot-scale experiments were conducted for5times with50Kg Dioscorea Zingiberensis as rawmaterials. A comprehensive evaluation of production costs of rawmaterials, waste water emissions and properties of waste water weremade, and considered that the process could be achieved the aim ofpollution control and costs reduction in the production of diosgenin.
6Modern biotechnology is adopted to optimize the conditions ofalcoholic fermentation with Dioscorea Zingiberensis residue after theextraction of dioscin as a raw material. With30Kg above-mentionedraw material, pilot-scale experiments demonstrate that alcohol contentof the fermented mash is up to10.5v/v, starch utilization90.6%. Thistechnology makes resource utilization starch in the DioscoreaZingiberensis feasible, and further reduces the cost of production ofdiosgenin in line with the requirements of low-carbon, environmentalfriendly development.
The innovation of this paper.
1The technology of diosgenin clean production was research systematically, With surfactant extraction technology and flocculationtechnology as the core. On the basis of laboratory experiments,wastewater discharge and wastewater properties in the process ofdiosgenin clean production are studied. The costs of raw materials arecompared in the process of diosgenin clean production and thetraditional process. It is found that the clean process helps to controlpollution and reduce costs.
2The effect of surfactant structure on dioscin extraction is studiedin several ways, which paves the way for the scientific surfactantselection principle at dioscin extraction. Besides the test of surfactantson dioscin molar solubilizatoin ratio (MSR), verified feasibility ofsurfactant selection principle at dioscin extraction with the effect ofsurfactant on molar solubilization rate.
3The content of alcohol in fermenting mash, the utilization rate ofstarch and the SEM of distillers' grains are compared with DioscoreaZingiberensis and Dioscorea Zingiberensis residue as raw materials. This technology is in line with the development of recycling economymode, laying the foundation for comprehensive utilization of otherstarch-containing plants.
引文
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