文冠果的生物炼制工艺与技术经济分析
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摘要
文冠果作为一种优质的非粮木本油料植物,被国家确定为重点开发的生物柴油原料资源之一。在用文冠果种仁油生产生物柴油的同时,将会产生大量的果壳、种皮、油渣和副产物甘油,这些副产资源都具有较高的潜在经济价值,如果得不到合理的开发利用,会造成巨大的资源浪费。本文针对目前文冠果利用中存在的问题,在利用文冠果生产生物柴油的同时,考虑其它副产物资源的充分利用,对文冠果生物炼制多产物联产的工艺和方法做了探索性研究,以期为文冠果资源的综合开发利用提供科学指导与技术支撑。
首先,测定了文冠果各部位主要成分的含量,并根据各主要成分潜在的应用价值,实验验证了果壳、种仁皂苷的提取、以果壳、种皮为原料的纤维素乙醇生产、以种仁油和乙醇为原料的生物柴油生产和以生物柴油副产物甘油为原料的1,3-丙二醇生产等几个关键技术过程是可行的,在此基础上提出一种生物柴油与其它生物基化学品和中药有效成分联产的生物炼制工艺。通过对生物炼制过程的物料衡算,得出纤维素乙醇生产与生物柴油生产、皂苷提取和1,3-丙二醇的乙醇/硫酸铵双水相萃取存在过程集成的可能性。
其次,对利用正已烷/乙醇/硫酸铵/水三液相萃取体系同时分离文冠果种仁中的油脂、皂苷和蛋白质的多产物联产方法进行初步探索,考察了不同的乙醇/硫酸铵双水相配比、不同的正已烷浓度和不同的三液相体系组成成分添加顺序对分离效果的影响。最后得出当操作条件为25%(w/w)正已烷/30%(w/w)乙醇/7.5%(w/w)硫酸铵/37.5%(w/w)水时,三液相萃取达到了油脂、皂苷和蛋白质三者较好的分离效果,油脂主要集中在上相,提油率为87%,种仁总皂苷集中在中相,回收率为83.5%,蛋白质富集在中相和下相的相界面处,可通过过滤得到。实验结果表明,三液相萃取一步操作可实现种仁中三种成分的同时分离,简化了工艺,是一种有效的多产物联产方法。
再次,以文冠果生物炼制工艺可行性实验验证为基础,结合生物炼制工艺各关键过程现阶段的发展现状,对年处理30万吨文冠果的生物炼制工艺的物耗和能耗进行计算,获得了影响文冠果生物炼制工艺成本的主要因素及其影响规律。分析表明,从成本构成要素来看,原辅材料成本、公用工程成本是多产物联产过程成本的决定因素,两者占总成本的80%以上；从过程成本要素来看,纤维素乙醇生产成本是决定多产物联产过程成本的决定因素,将近占总成本的50%。敏感性分析表明,纤维素乙醇生产成本对利润的影响最为敏感,公用工程成本次之。对工艺中各个过程之间进行能量集成有望降低成本,同时,随着纤维素乙醇产业化进程的推进,生物炼制过程的成本可进一步降低。
Xanthoceras sorbifolia, a good woody oil plant in Northern China, has been determined as one of the most promising raw materials of biodiesel and taken priority to develop by the goverment. Producing biodiesel using Xanthoceras sorbifolia leads to formation of several by-products with economical potentials, such as husk, seed coat, kernel residues, crude glycerol. If those by-products are not developed and utilized rationally, it will cause a huge waste of resources. In this paper, in order to solve the current problems of utilization of Xanthoceras sorbifolia, the biorefinery and multi-product coproduction processes which give full consideration to the use of other by-products in addition to biodiesel production was explored and investigated to provide some scientific guidances and technical supports for the comprehensive development and utilization of Xanthoceras sorbifolia.
Firstly, the composition of different parts of Xanthoceras sorbifolia fruit was determined. The possibilities for production of biodiesel from kernel oil of Xanthoceras sorbifolia and production of medicinal saponins, cellulosic ethanol,1,3-propanediol, crude proteins from residues of Xanthoceras sorbifolia and by-product glycerol of biodiesel were explored through preliminary experiments. It showed that those key processes were feasible. On the basis, a process flowsheet of biorefinery using Xanthoceras sorbifolia was proposed, through which biodiesel, bio-based chemicals and saponins were coproduced. The feasibility of integration among the processes for production of cellulosic ethanol, production of biodiesel, extraction of saponins and aqueous two-phase extraction of 1,3-propanediol was verified through material balance analysis for the biorefinery process.
Secondly, a three-liquid-phase extraction system (TLPS) composed of n-hexane /ethanol/ammonium sulfate/water was investigated to separate saponins, oil and proteins in kernel of Xanthoceras sorbifolia simultaneously. The effects of the radio of ethanol and ammonium sulfate, concentration of n-hexane and adding order of the different components of TLPS were investigated. A better condition of TLPS was obtained:25%(w/w) n-hexane, 25%(w/w) ethanol,25%(w/w) ammonium sulfate and 25%(w/w) water. In this system, kernel oil was enriched in the top phase (n-hexane phase) with a yield of 87%, while kernel saponins were mainly in the middle phase (ethanol phase) with a recovery of 83.5%, proteins were enriched in the interface between the top and middle phase, which could be recovered by filtration. The results revealed that TLPS of n-hexane/ethanol/ammonium sulfate/water could simultaneously separate three components of Xanthoceras sorbifolia kernel. This simple process is a effective method for multi-product coproduction.
Finally, the technical and economic analysis of the biorefinery process which was based on 300,000 tons Xanthoceras sorbifolia per year design was investigated through calculation of the material and energy consumption on the basis of feasible experiments and developmental status of the key process in biorefinery and multi-product coproduction. And the main factors and laws which affected the biorefinery cost were obtained. The analysis showed that raw material costs and utility costs were the most important factor for the multi-product coproduction process, which accounted for over 80% of the total cost in total. Breakdown of the costs according to production process, the cost of cellulosic ethanol production was the most important process costs, nearly 50% of the total cost. The sensitivity ananlysis showed that the cost of cellulosic ethanol production was the key factor influencing the profit, followed by the cost of utility. Energy integration among the various processes of the biorefinery and multi-product coproduction is expected to reduce costs, while the costs can be further reduced when the technology for cellulosic ethanol production reaches such a perfect degree.
首先,测定了文冠果各部位主要成分的含量,并根据各主要成分潜在的应用价值,实验验证了果壳、种仁皂苷的提取、以果壳、种皮为原料的纤维素乙醇生产、以种仁油和乙醇为原料的生物柴油生产和以生物柴油副产物甘油为原料的1,3-丙二醇生产等几个关键技术过程是可行的,在此基础上提出一种生物柴油与其它生物基化学品和中药有效成分联产的生物炼制工艺。通过对生物炼制过程的物料衡算,得出纤维素乙醇生产与生物柴油生产、皂苷提取和1,3-丙二醇的乙醇/硫酸铵双水相萃取存在过程集成的可能性。
其次,对利用正已烷/乙醇/硫酸铵/水三液相萃取体系同时分离文冠果种仁中的油脂、皂苷和蛋白质的多产物联产方法进行初步探索,考察了不同的乙醇/硫酸铵双水相配比、不同的正已烷浓度和不同的三液相体系组成成分添加顺序对分离效果的影响。最后得出当操作条件为25%(w/w)正已烷/30%(w/w)乙醇/7.5%(w/w)硫酸铵/37.5%(w/w)水时,三液相萃取达到了油脂、皂苷和蛋白质三者较好的分离效果,油脂主要集中在上相,提油率为87%,种仁总皂苷集中在中相,回收率为83.5%,蛋白质富集在中相和下相的相界面处,可通过过滤得到。实验结果表明,三液相萃取一步操作可实现种仁中三种成分的同时分离,简化了工艺,是一种有效的多产物联产方法。
再次,以文冠果生物炼制工艺可行性实验验证为基础,结合生物炼制工艺各关键过程现阶段的发展现状,对年处理30万吨文冠果的生物炼制工艺的物耗和能耗进行计算,获得了影响文冠果生物炼制工艺成本的主要因素及其影响规律。分析表明,从成本构成要素来看,原辅材料成本、公用工程成本是多产物联产过程成本的决定因素,两者占总成本的80%以上；从过程成本要素来看,纤维素乙醇生产成本是决定多产物联产过程成本的决定因素,将近占总成本的50%。敏感性分析表明,纤维素乙醇生产成本对利润的影响最为敏感,公用工程成本次之。对工艺中各个过程之间进行能量集成有望降低成本,同时,随着纤维素乙醇产业化进程的推进,生物炼制过程的成本可进一步降低。
Xanthoceras sorbifolia, a good woody oil plant in Northern China, has been determined as one of the most promising raw materials of biodiesel and taken priority to develop by the goverment. Producing biodiesel using Xanthoceras sorbifolia leads to formation of several by-products with economical potentials, such as husk, seed coat, kernel residues, crude glycerol. If those by-products are not developed and utilized rationally, it will cause a huge waste of resources. In this paper, in order to solve the current problems of utilization of Xanthoceras sorbifolia, the biorefinery and multi-product coproduction processes which give full consideration to the use of other by-products in addition to biodiesel production was explored and investigated to provide some scientific guidances and technical supports for the comprehensive development and utilization of Xanthoceras sorbifolia.
Firstly, the composition of different parts of Xanthoceras sorbifolia fruit was determined. The possibilities for production of biodiesel from kernel oil of Xanthoceras sorbifolia and production of medicinal saponins, cellulosic ethanol,1,3-propanediol, crude proteins from residues of Xanthoceras sorbifolia and by-product glycerol of biodiesel were explored through preliminary experiments. It showed that those key processes were feasible. On the basis, a process flowsheet of biorefinery using Xanthoceras sorbifolia was proposed, through which biodiesel, bio-based chemicals and saponins were coproduced. The feasibility of integration among the processes for production of cellulosic ethanol, production of biodiesel, extraction of saponins and aqueous two-phase extraction of 1,3-propanediol was verified through material balance analysis for the biorefinery process.
Secondly, a three-liquid-phase extraction system (TLPS) composed of n-hexane /ethanol/ammonium sulfate/water was investigated to separate saponins, oil and proteins in kernel of Xanthoceras sorbifolia simultaneously. The effects of the radio of ethanol and ammonium sulfate, concentration of n-hexane and adding order of the different components of TLPS were investigated. A better condition of TLPS was obtained:25%(w/w) n-hexane, 25%(w/w) ethanol,25%(w/w) ammonium sulfate and 25%(w/w) water. In this system, kernel oil was enriched in the top phase (n-hexane phase) with a yield of 87%, while kernel saponins were mainly in the middle phase (ethanol phase) with a recovery of 83.5%, proteins were enriched in the interface between the top and middle phase, which could be recovered by filtration. The results revealed that TLPS of n-hexane/ethanol/ammonium sulfate/water could simultaneously separate three components of Xanthoceras sorbifolia kernel. This simple process is a effective method for multi-product coproduction.
Finally, the technical and economic analysis of the biorefinery process which was based on 300,000 tons Xanthoceras sorbifolia per year design was investigated through calculation of the material and energy consumption on the basis of feasible experiments and developmental status of the key process in biorefinery and multi-product coproduction. And the main factors and laws which affected the biorefinery cost were obtained. The analysis showed that raw material costs and utility costs were the most important factor for the multi-product coproduction process, which accounted for over 80% of the total cost in total. Breakdown of the costs according to production process, the cost of cellulosic ethanol production was the most important process costs, nearly 50% of the total cost. The sensitivity ananlysis showed that the cost of cellulosic ethanol production was the key factor influencing the profit, followed by the cost of utility. Energy integration among the various processes of the biorefinery and multi-product coproduction is expected to reduce costs, while the costs can be further reduced when the technology for cellulosic ethanol production reaches such a perfect degree.
引文
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