光皮树果实生物液体燃料绿色制备工艺原理与技术研究
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摘要
我国缺油少气,石油和食用植物油的对外依存度均己高达60%。随着国民经济的快速发展,植物油供需矛盾日益突出,采用可再生的植物油资源制备生物燃料已成为全球关注的热点。而现有植物油脂资源无法满足市场需要。因此,培育特色高含油植物资源,开发高效绿色加工技术意义重大。光皮树(Swida wilsoniana)全果含油高达30%以上,是典型的高含油木本油料植物,其油脂既可作轻化工业的原料,也是理想的生物柴油原料。遵循生态能值原理,采用绿色技术制备能源产品,构建光皮树油料资源能源化绿色转化技术体系,对于促进光皮树等能源油料植物的种植,降低石化能源消耗,维护我国能源安全,实现低碳经济目标有着重要意义。
本论文以湖南省林科院选育出的光皮树良种(湘林G1)的果实为研究对象,以能源化利用为目的,运用生物技术、绿色化学工程技术以及生态经济能值理论进行光皮树果实中油脂的能源化转化研究。全面分析光皮树果实的基本成分,系统研究光皮树果实高效制油和油脂清洁转化制备液体燃料等绿色技术,并开展了光皮树果实能源化过程的能量平衡分析,构建出一套光皮树果能源化利用的绿色转化技术体系,为光皮树果实能源化利用提供了理论基础和技术支持。主要结果如下：
1.系统分析了光皮树(湘林G1)果实的基本组成和脂肪酸分布规律,初步建立了光皮树果实的近红外检测模型及数据库。①光皮树果由果皮(41.32%)、种皮(49.93%)和种仁(8.75%)组成,其含油率分别为55.00%、11.53%和62.14%；不同部位油的脂肪酸组成均以油酸和亚油酸含量为主,其中果皮中油脂的脂肪酸成分主要包括棕榈酸(24.41%)、亚油酸(32.46%)、油酸(30.07%)和硬脂酸(1.64%),种皮中油脂的脂肪酸主要包括棕榈酸(12.48%)、亚油酸(54.79%)、油酸(26.93%)和硬脂酸(2.18%),种仁中油脂的脂肪酸主要包括棕榈酸(6.61%)、亚油酸(58.80%)、油酸(22.32%)和硬脂酸(2.03%)。②光皮树果实的基本质量组成为：油脂(33.95%),纤维素(29.16%)、蛋白质(7.72%)、淀粉(10.60%)、糖(3.22%)、水分(9.36%)、磷脂(0.66%)和其他成分(5.33%)。③针对光皮树果实常用检测指标(含油率、水分和热值),以46个光皮树果实为基础,建立了相应指标的近红外光谱分析模型,其中含油率的相关系数为0.99,水分的相关系数为0.95,粗蛋白的相关系数为0.91,热值的相关系数为0.96。
2.建立了适合光皮树果实制油的“冷榨-正丁醇浸提”绿色制油新工艺,实现了光皮树油和磷脂的同步提取。①采用冷榨制油技术制备光皮树油,控制光皮树果实含水率为9.00%左右,压榨榨轴转速30-40rpm,出饼孔径为4-8mm时,经一次压榨后光皮树饼粕残油率可降低到7.00%;②以正丁醇为溶剂提取光皮树油,在提取油脂的同时,实现油脂中伴随物(如磷脂、维生素E等)的高效浸提；正丁醇提油的最佳工艺参数：浸出次数3次,浸出时间为90min,浸出温度为60℃,液料比为1.2：1,浸提率可达88.62%；③采用“纤维素酶+中性蛋白酶”复合酶体系进行光皮树果实提油,最优组合方案为：先纤维素酶3h再加蛋白酶,加酶量2.5%,酶比例4：1,酶解时间4h,提取的油脂颜色浅、杂质少、流动性好,光皮树油提取率可达80.54%；④“冷榨-正丁醇浸提”制取光皮树油,可以实现提油率达96.73%,磷脂提取率达97.69%。该组合工艺既能降低冷榨制油的能耗,又能减轻后述正丁醇提油的负荷,实现油脂和磷脂等高附加值产物的同步提取,是一种极具开发潜力的绿色制油新工艺。
3.采用悬浮聚合法制备了用于固定化酶的含有环氧基团磁性多孔高分子微球,提高了酶促酯交换过程中酶的活性和稳定性。①采用悬浮聚合法制备了用于固定化酶的含环氧基团的磁性多孔高分子微球,粒径为4μm,粒子分布均匀,表面呈多孔结构；②以GHD(40)为载体优化了脂肪酶的固定化条件：载体/脂肪酶(m/m)=125mg/g,固定化时间为7h,酶的吸附量为118.5mg·g-1,比酶活7.56×105U/g,酶的活力回收率为0.95；③制备了三种不同的环氧值的固定化假丝酵母脂肪酶,采用单分子层吸附模型Langmiur方程拟合GHD吸附光皮树的吸附等温线,相关系数大于0.99；分析聚合物的环氧值和温度对光皮树油吸附量的影响,建立了拟合动力学二级吸附方程,相关系数大于0.999,光皮树油在固定化酶表面吸附活化能为30.44kJ/mol,和游离酶相比,固定化酶催化光皮树油酯交换的最佳反应温度从37℃提高到42℃,最适反应pH从7.2提高到7.5,重复使用12次,固定化酶的活力仍保持在92%以上；④GC-MS分析光皮树油甲酯,其主要成分是油酸甲酯(50.61%),棕榈酸甲酯(14.74%),硬脂酸甲酯(7.11%),是传统石化柴油的良好替代品。
4.建立了催化裂化和酯化降酸相结合的植物油裂解新工艺。①在CaO中加入KF,合成了适合植物油裂解的高效固体催化剂KF/CaO,该催化剂呈层片状多孔状态,比表面积较CaO有较大的提高,同时有效的避免了碱性中心被CO2等酸性气体中和,从而提高了催化剂的活性和稳定性；②以自制KF/CaO为催化剂进行光皮树油催化裂解,最佳工艺条件为：催化剂1.0%,温度494.2℃,反应时间68.6mmin,液相收率高达84.0%以上；③针对裂解产品中具有一定的羧酸化合物,导致产品酸偏高,采用离子液体[Hnmp]+HSO4为催化剂对裂解产物进行酯化降酸,获得了质量稳定的富烃基生物液体燃料,最高酯化率达95.7%,且离子液体重复使用4次后,总体转化率仍保持在90%以上,最佳酯化工艺参数：醇油比30%,反应温度75℃,反应时间100min,催化剂2.0%。
5.基于生态能值原理,结合投入产出模型进行了光皮树果实制备生物液体燃料过程的生命周期能量分析。结果表明：如果不考虑副产品的能量分配效益,甲酯基生物液体燃料和富烃基生物液体燃料的净能值(NEV)分别为31593.38MJ/ha和36924.16MJ,化石能效比(FER)分别为3.94和6.71；如果考虑副产品的能量分配效益,甲酯基生物液体燃料和富烃基生物液体燃料的净能值(NEV)分别为98453.66MJ/ha和99121.2MJ/ha,化石能效比(FER)分别为4.52和7.17。上述结果进一步证明了光皮树果实制备的甲酯基生物液体燃料和富烃基生物液体燃料均具有正能量效益,可以节约部分化石能源。但从能量效益的角度来说,富烃基生物液体燃料更具竞争性,现有的植物油催化裂解技术较现有的酯交换技术更适于生物液体燃料的制备。研究结果也为光皮树油料替代化石燃料的可行性研究以及光皮树能源化产品开发技术路线的选择提供了一定的借鉴作用。
China is a country short in supplies of petroleum and natural gases. The percentage of imported petrols and edible vegetable oil in China has gone up to60%in recent years. Along with the rapid development of national economy and fast depletion in fossil energy resources, however, the conflict between the supply and demand in biofuel and edible vegetable oil has become one of the key issues. As an alternative solution to energy shortage crisis, use of biofuel as a green energy resource has been received worldwide attention.To fulfill the further need in biofuel production it is thus of high importance to promote the cultivation of oil-rich plants and to develope new green technologies for biofuel processing with high efficiency. Swida wilsoniana is one of the typical plant species for biodiesel feedstock. The oil content in the whole fruit of Swida wilsoniana is higher than30%. Its oil can be converted into products in light industry and biodiesel production. Based on the principle of ecological energy value, the present study is focused on the establishment of a new green bio-energy transform technology system using the fruit of Swida wilsoniana as raw material. The results obtained from the present work will be useful with respect to the enhancement of oil-plant cultivation, reduction of fossil energy consumption, ensurence of national energy-safty and promotion of low carbon Economy.
Along with the rapid development of national economy and fast depletion in fossil energy resources, however, the conflict between the supply and demand in biofuel and edible vegetable oil has become one of the key issues. The consumption of the edible vegetable oil in China has been increasing significantly and the proportion of the edible vegetable oil imported from overseas has amounted up to more than60%. China is a country short in supplies of petroleum and natural gases and the percentage of imported petrols in China has gone up to60%in recent years. As an alternative solution to energy shortage crisis, use of biofuel as a green energy resource has been received worldwide attention. To fulfill the further need in biofuel production it is thus of high importance to promote the cultivation of oil-rich plants and to develope new green technologies for biofuel processing with high efficiency. Swida wilsoniana is one of the typical plant species for biodiesel feedstock. The oil content in the whole fruit of Swida wilsoniana is higher than30%. Its oil can be converted into products in light industry and biodiesel production. Based on the principle of ecological energy value, the present study is focused on the establishment of a new green bio-energy transform technology system using the fruit of Swida wilsoniana as raw material. The results obtained from the present work will be useful with respect to the enhancement of oil-plant cultivation, reduction of fossil energy consumption, ensurence of national energy-safty and promotion of low carbon Economy.
In this work, the Swida wilsoniana fruits of the improved varieties (Xianglin Gl) cultivated by the Hunan Academy of Forestry (HAF) were selected as the raw material, to explore the bio-transformation of the Swida wilsoniana fruit on the basis of bio-techniques, green chemical engineering technology and emergy theory. Grounded on the comprehensive analysis of the composition of Swida fruits, the thesis probed into the green technologies of efficient oil extraction and clean liquid fuel bioconversion. In addition, life cycle assessment of the whole procedure was carried out. A set of green conversion technology system on Swida wilsoniana fruit was build up, which provided a theoretical ground and technology support for energy-application of Swida wilsoniana fruit. The results were summerized as follows:
1. The compounds and distribution of fatty acids in Swida wilsoniana fruit (Xianglin G1) were systematically investigated, and the near infrared NIR model and database of Swida wilsoniana fruit were built.①The whole fruit was included sarcocarp (41.32%), testa (49.93%) and kernel (8.75%). The oil content varied in the different part of fruit, which was shown as55.00%,11.53%and62.14%in sarcocarp, pit and kernel, respectively. Oleic acid and linoleic acid were the main fatty acids in fruit. The main fatty acid compounds in sarcocarp were cetylic acid (24.41%), linoleic acid (32.46%), oleic acid (30.07%) and octadecanoic acid (1.64%), respectively. The main fatty acid compounds in testa were cetylic acid (12.48%), linoleic acid (54.79%), oleic acid (26.93%) and octadecanoic acid (2.18%), respectively. The main fatty acid compounds in testa were cetylic acid (6.61%), linoleic acid (58.80%), oleic acid (22.32%) and octadecanoic acid (2.03%), respectively.②The Swida wilsoniana fruit (Xianglin G1) was composed of oil of33.95%, cellulose of29.16%, protein of7.72%, starch of10.60%, sugar of3.22%, water of9.36%, phospholipid of0.66%, and some other of5.33%.③Based on46samples of fruit, the Near Infrared Spectroscopy (NIRS) model was established with the convention properties of fruit including oil content, moisture and calorific value. The correlation coefficients of oil content, moisture, protein and calorific value were0.99,0.95,0.91and0.96, respectively.
2. The new "cold pression-n-butyl alcohol extraction" procedure was built up in the present work.①That procedure can be carried out without preheating, which simplifying process with lower energy requirement. In addition, protein inside would be applied as an industrially feedstock. The residual oil content of once-pressing was lower than7%, when the operation condition was fruit moisture9%, pressing axle rotation speed30-40rpm, and exit diameter4-8mm.②The by-products can be extracted by n-butyl alcohol with higher efficiency during cold compressing. The optimal condition was shown as:extraction3times, extraction time90min, extraction temperature60℃and liquid/solid ratio1.2:1, in which the oil extraction rate achieved around88.62%.③The compound enzyme of "cellulose enzyme+neutral protease" was adopted to realize oil extraction from Swida wilsoniana fruit in this study. The optimal operation process was described as following:adding2.5%of protease into system after the treatment of cellulose enzyme3h with the mixing ratio of enzyme of4:1and enzymolysis time of4h. The color of extracted oil was lighter. That process is better than the other processes with less impurity and better fluidity. However, the oil extraction rate reached80.54%.④The energy consumptions of cold-pressing were decreased by "cold pression-rc-butyl alcohol extraction" with96.73%of oil extraction rate and97.69%phospholipid extraction rate, while the load of n-butyl alcohol extraction was also reduced with simultaneous extraction of oil and phospholipid. Therefore, the "cold pression-n-butyl alcohol extraction" is a promising green processing technology.
3. The mechanism of methoxycarbonyl bio-diesel catalytically produced from Swida wilsoniana oil by CRL was studied in this work.①Porous magnetic polymer particles with epoxy group were produced for immobilized enzyme with particle diameter4μm. The surface of particles was porous with uniform distribution.②The immobilization condition of lipase was optimized with GHD(40) as carrier:lipase125mg/g, immobilization time7h, enzyme absorption118.5mg·-1, specific enzyme acitivity7.56×105U/g, and activity recovery0.95.③Three kinds of immobilized CRL with different epoxide number were made. The adsorption isotherm line was fitted by Langmiur equation of monomolecular layer, which correlation coefficient was higher than0.99. The effects of epoxide number and temperature on adsorption of Swida wilsoniana oil were researched. The fitting pseudo-second-order kinetic equation was built up with correlation coefficient higher than0.99. And for the oil of Swida wilsoniana, the surface of the immobile lipase has30.44kJ/mol activation energy of adsorption.④Compared with isolated enzyme, the optimal reaction temperature of interesterification catalyzed by immobilized enzyme was enhanced from37℃to42℃, while optimal pH was increased from7.2to7.5. After recovering12times, the acitivity of immobilized enzyme was kept over92%. However, the similar catalyzing trends were found between immobilized and isolated enzymes. That trend was shown as increasing in the initial process and then decreasing with moisture increasing.⑤As depicted by GC-MS, The main compounds in Swida wilsoniana oil methyl ester were methyloleate (50.61%), methyl hexadecanoate (14.74%), and methyl stearate (7.11%). Therefore, methyl ester from Swida wilsoniana oil should be a potential substitute for conventional fossil diesel.
4. The catalytic pyrolysis of Swida wilsoniana oil into rich-alkyl bio-oil by alkalinity catalyst was carried out in this research. The results were described as follows:CD The composite catalysts were composed of adding KF into CaO. The lamellar structure with porosity was clearly imaged by SEM. Its specific area was enhanced significantly compared with CaO. As shown by XRD analyses, neutralization of basic sites during addition of KF was inhibited, resulting in increasing catalyst's activity and stability.②The optimal condition in KF/CaO runs were catalyst1.0%, temperature494.2℃, and reaction68.6min, in which the liquid yield reached upwards of84.0%.③There are several kinds of carboxylic acids in The pyrolysis products have several kinds of carboxylic acids resulting a high acid value. Therefore, ionic liquid [Hnmp]+HSO4-was applied as fine catalyst in order to reduce acid value of product in this study. After that treatment, the rich-alkyl bio-oils with good quality were obtained. The highest esterification rate was shown as95.7%. In addition, the total esterification rate could be kept as over90%after recovering6times. The optimal condition was alcohol/oil rate30%, reaction temperature75℃, reaction time100min, and catalyst additive2.0%.
5. Based on the principle of eco-energy value and the input-output model, the energy life cycle analysis for biofuel from Swida wilsoniana fruits was carried out. The results showed that, before allocating co-product value, the net energy value (NEV) of carbomethoxy and rich hydrocarbon biofuel were31593.38MJ/ha and36924.16MJ, and the fossil energy ratio (FER) were3.94and6.71, respectively.And if conside the co-product value, the net energy value (NEV) of carbomethoxy and rich hydrocarbon biofuel were98453.66MJ/ha and99121.2MJ/ha, and the fossil energy ratio (FER) were4.52and7.17, respectively. And the results further demonstrated that both the carbomethoxy and the rich hydrocarbon biofuel from Swida Wilsoniana fruits have positive energy efficiency, and can save some of the fossil fuel. But from the standpoint of energy efficiency, the hydrocarbyl-rich biofuel is more competitive. Compared with the conventional transesterification technology, the catalytic pylolysis technology is more suitable for the conversion of biofuel. The research results provided some information for us to choose the emergy product or techonology which is more effective.
本论文以湖南省林科院选育出的光皮树良种(湘林G1)的果实为研究对象,以能源化利用为目的,运用生物技术、绿色化学工程技术以及生态经济能值理论进行光皮树果实中油脂的能源化转化研究。全面分析光皮树果实的基本成分,系统研究光皮树果实高效制油和油脂清洁转化制备液体燃料等绿色技术,并开展了光皮树果实能源化过程的能量平衡分析,构建出一套光皮树果能源化利用的绿色转化技术体系,为光皮树果实能源化利用提供了理论基础和技术支持。主要结果如下：
1.系统分析了光皮树(湘林G1)果实的基本组成和脂肪酸分布规律,初步建立了光皮树果实的近红外检测模型及数据库。①光皮树果由果皮(41.32%)、种皮(49.93%)和种仁(8.75%)组成,其含油率分别为55.00%、11.53%和62.14%；不同部位油的脂肪酸组成均以油酸和亚油酸含量为主,其中果皮中油脂的脂肪酸成分主要包括棕榈酸(24.41%)、亚油酸(32.46%)、油酸(30.07%)和硬脂酸(1.64%),种皮中油脂的脂肪酸主要包括棕榈酸(12.48%)、亚油酸(54.79%)、油酸(26.93%)和硬脂酸(2.18%),种仁中油脂的脂肪酸主要包括棕榈酸(6.61%)、亚油酸(58.80%)、油酸(22.32%)和硬脂酸(2.03%)。②光皮树果实的基本质量组成为：油脂(33.95%),纤维素(29.16%)、蛋白质(7.72%)、淀粉(10.60%)、糖(3.22%)、水分(9.36%)、磷脂(0.66%)和其他成分(5.33%)。③针对光皮树果实常用检测指标(含油率、水分和热值),以46个光皮树果实为基础,建立了相应指标的近红外光谱分析模型,其中含油率的相关系数为0.99,水分的相关系数为0.95,粗蛋白的相关系数为0.91,热值的相关系数为0.96。
2.建立了适合光皮树果实制油的“冷榨-正丁醇浸提”绿色制油新工艺,实现了光皮树油和磷脂的同步提取。①采用冷榨制油技术制备光皮树油,控制光皮树果实含水率为9.00%左右,压榨榨轴转速30-40rpm,出饼孔径为4-8mm时,经一次压榨后光皮树饼粕残油率可降低到7.00%;②以正丁醇为溶剂提取光皮树油,在提取油脂的同时,实现油脂中伴随物(如磷脂、维生素E等)的高效浸提；正丁醇提油的最佳工艺参数：浸出次数3次,浸出时间为90min,浸出温度为60℃,液料比为1.2：1,浸提率可达88.62%；③采用“纤维素酶+中性蛋白酶”复合酶体系进行光皮树果实提油,最优组合方案为：先纤维素酶3h再加蛋白酶,加酶量2.5%,酶比例4：1,酶解时间4h,提取的油脂颜色浅、杂质少、流动性好,光皮树油提取率可达80.54%；④“冷榨-正丁醇浸提”制取光皮树油,可以实现提油率达96.73%,磷脂提取率达97.69%。该组合工艺既能降低冷榨制油的能耗,又能减轻后述正丁醇提油的负荷,实现油脂和磷脂等高附加值产物的同步提取,是一种极具开发潜力的绿色制油新工艺。
3.采用悬浮聚合法制备了用于固定化酶的含有环氧基团磁性多孔高分子微球,提高了酶促酯交换过程中酶的活性和稳定性。①采用悬浮聚合法制备了用于固定化酶的含环氧基团的磁性多孔高分子微球,粒径为4μm,粒子分布均匀,表面呈多孔结构；②以GHD(40)为载体优化了脂肪酶的固定化条件：载体/脂肪酶(m/m)=125mg/g,固定化时间为7h,酶的吸附量为118.5mg·g-1,比酶活7.56×105U/g,酶的活力回收率为0.95；③制备了三种不同的环氧值的固定化假丝酵母脂肪酶,采用单分子层吸附模型Langmiur方程拟合GHD吸附光皮树的吸附等温线,相关系数大于0.99；分析聚合物的环氧值和温度对光皮树油吸附量的影响,建立了拟合动力学二级吸附方程,相关系数大于0.999,光皮树油在固定化酶表面吸附活化能为30.44kJ/mol,和游离酶相比,固定化酶催化光皮树油酯交换的最佳反应温度从37℃提高到42℃,最适反应pH从7.2提高到7.5,重复使用12次,固定化酶的活力仍保持在92%以上；④GC-MS分析光皮树油甲酯,其主要成分是油酸甲酯(50.61%),棕榈酸甲酯(14.74%),硬脂酸甲酯(7.11%),是传统石化柴油的良好替代品。
4.建立了催化裂化和酯化降酸相结合的植物油裂解新工艺。①在CaO中加入KF,合成了适合植物油裂解的高效固体催化剂KF/CaO,该催化剂呈层片状多孔状态,比表面积较CaO有较大的提高,同时有效的避免了碱性中心被CO2等酸性气体中和,从而提高了催化剂的活性和稳定性；②以自制KF/CaO为催化剂进行光皮树油催化裂解,最佳工艺条件为：催化剂1.0%,温度494.2℃,反应时间68.6mmin,液相收率高达84.0%以上；③针对裂解产品中具有一定的羧酸化合物,导致产品酸偏高,采用离子液体[Hnmp]+HSO4为催化剂对裂解产物进行酯化降酸,获得了质量稳定的富烃基生物液体燃料,最高酯化率达95.7%,且离子液体重复使用4次后,总体转化率仍保持在90%以上,最佳酯化工艺参数：醇油比30%,反应温度75℃,反应时间100min,催化剂2.0%。
5.基于生态能值原理,结合投入产出模型进行了光皮树果实制备生物液体燃料过程的生命周期能量分析。结果表明：如果不考虑副产品的能量分配效益,甲酯基生物液体燃料和富烃基生物液体燃料的净能值(NEV)分别为31593.38MJ/ha和36924.16MJ,化石能效比(FER)分别为3.94和6.71；如果考虑副产品的能量分配效益,甲酯基生物液体燃料和富烃基生物液体燃料的净能值(NEV)分别为98453.66MJ/ha和99121.2MJ/ha,化石能效比(FER)分别为4.52和7.17。上述结果进一步证明了光皮树果实制备的甲酯基生物液体燃料和富烃基生物液体燃料均具有正能量效益,可以节约部分化石能源。但从能量效益的角度来说,富烃基生物液体燃料更具竞争性,现有的植物油催化裂解技术较现有的酯交换技术更适于生物液体燃料的制备。研究结果也为光皮树油料替代化石燃料的可行性研究以及光皮树能源化产品开发技术路线的选择提供了一定的借鉴作用。
China is a country short in supplies of petroleum and natural gases. The percentage of imported petrols and edible vegetable oil in China has gone up to60%in recent years. Along with the rapid development of national economy and fast depletion in fossil energy resources, however, the conflict between the supply and demand in biofuel and edible vegetable oil has become one of the key issues. As an alternative solution to energy shortage crisis, use of biofuel as a green energy resource has been received worldwide attention.To fulfill the further need in biofuel production it is thus of high importance to promote the cultivation of oil-rich plants and to develope new green technologies for biofuel processing with high efficiency. Swida wilsoniana is one of the typical plant species for biodiesel feedstock. The oil content in the whole fruit of Swida wilsoniana is higher than30%. Its oil can be converted into products in light industry and biodiesel production. Based on the principle of ecological energy value, the present study is focused on the establishment of a new green bio-energy transform technology system using the fruit of Swida wilsoniana as raw material. The results obtained from the present work will be useful with respect to the enhancement of oil-plant cultivation, reduction of fossil energy consumption, ensurence of national energy-safty and promotion of low carbon Economy.
Along with the rapid development of national economy and fast depletion in fossil energy resources, however, the conflict between the supply and demand in biofuel and edible vegetable oil has become one of the key issues. The consumption of the edible vegetable oil in China has been increasing significantly and the proportion of the edible vegetable oil imported from overseas has amounted up to more than60%. China is a country short in supplies of petroleum and natural gases and the percentage of imported petrols in China has gone up to60%in recent years. As an alternative solution to energy shortage crisis, use of biofuel as a green energy resource has been received worldwide attention. To fulfill the further need in biofuel production it is thus of high importance to promote the cultivation of oil-rich plants and to develope new green technologies for biofuel processing with high efficiency. Swida wilsoniana is one of the typical plant species for biodiesel feedstock. The oil content in the whole fruit of Swida wilsoniana is higher than30%. Its oil can be converted into products in light industry and biodiesel production. Based on the principle of ecological energy value, the present study is focused on the establishment of a new green bio-energy transform technology system using the fruit of Swida wilsoniana as raw material. The results obtained from the present work will be useful with respect to the enhancement of oil-plant cultivation, reduction of fossil energy consumption, ensurence of national energy-safty and promotion of low carbon Economy.
In this work, the Swida wilsoniana fruits of the improved varieties (Xianglin Gl) cultivated by the Hunan Academy of Forestry (HAF) were selected as the raw material, to explore the bio-transformation of the Swida wilsoniana fruit on the basis of bio-techniques, green chemical engineering technology and emergy theory. Grounded on the comprehensive analysis of the composition of Swida fruits, the thesis probed into the green technologies of efficient oil extraction and clean liquid fuel bioconversion. In addition, life cycle assessment of the whole procedure was carried out. A set of green conversion technology system on Swida wilsoniana fruit was build up, which provided a theoretical ground and technology support for energy-application of Swida wilsoniana fruit. The results were summerized as follows:
1. The compounds and distribution of fatty acids in Swida wilsoniana fruit (Xianglin G1) were systematically investigated, and the near infrared NIR model and database of Swida wilsoniana fruit were built.①The whole fruit was included sarcocarp (41.32%), testa (49.93%) and kernel (8.75%). The oil content varied in the different part of fruit, which was shown as55.00%,11.53%and62.14%in sarcocarp, pit and kernel, respectively. Oleic acid and linoleic acid were the main fatty acids in fruit. The main fatty acid compounds in sarcocarp were cetylic acid (24.41%), linoleic acid (32.46%), oleic acid (30.07%) and octadecanoic acid (1.64%), respectively. The main fatty acid compounds in testa were cetylic acid (12.48%), linoleic acid (54.79%), oleic acid (26.93%) and octadecanoic acid (2.18%), respectively. The main fatty acid compounds in testa were cetylic acid (6.61%), linoleic acid (58.80%), oleic acid (22.32%) and octadecanoic acid (2.03%), respectively.②The Swida wilsoniana fruit (Xianglin G1) was composed of oil of33.95%, cellulose of29.16%, protein of7.72%, starch of10.60%, sugar of3.22%, water of9.36%, phospholipid of0.66%, and some other of5.33%.③Based on46samples of fruit, the Near Infrared Spectroscopy (NIRS) model was established with the convention properties of fruit including oil content, moisture and calorific value. The correlation coefficients of oil content, moisture, protein and calorific value were0.99,0.95,0.91and0.96, respectively.
2. The new "cold pression-n-butyl alcohol extraction" procedure was built up in the present work.①That procedure can be carried out without preheating, which simplifying process with lower energy requirement. In addition, protein inside would be applied as an industrially feedstock. The residual oil content of once-pressing was lower than7%, when the operation condition was fruit moisture9%, pressing axle rotation speed30-40rpm, and exit diameter4-8mm.②The by-products can be extracted by n-butyl alcohol with higher efficiency during cold compressing. The optimal condition was shown as:extraction3times, extraction time90min, extraction temperature60℃and liquid/solid ratio1.2:1, in which the oil extraction rate achieved around88.62%.③The compound enzyme of "cellulose enzyme+neutral protease" was adopted to realize oil extraction from Swida wilsoniana fruit in this study. The optimal operation process was described as following:adding2.5%of protease into system after the treatment of cellulose enzyme3h with the mixing ratio of enzyme of4:1and enzymolysis time of4h. The color of extracted oil was lighter. That process is better than the other processes with less impurity and better fluidity. However, the oil extraction rate reached80.54%.④The energy consumptions of cold-pressing were decreased by "cold pression-rc-butyl alcohol extraction" with96.73%of oil extraction rate and97.69%phospholipid extraction rate, while the load of n-butyl alcohol extraction was also reduced with simultaneous extraction of oil and phospholipid. Therefore, the "cold pression-n-butyl alcohol extraction" is a promising green processing technology.
3. The mechanism of methoxycarbonyl bio-diesel catalytically produced from Swida wilsoniana oil by CRL was studied in this work.①Porous magnetic polymer particles with epoxy group were produced for immobilized enzyme with particle diameter4μm. The surface of particles was porous with uniform distribution.②The immobilization condition of lipase was optimized with GHD(40) as carrier:lipase125mg/g, immobilization time7h, enzyme absorption118.5mg·-1, specific enzyme acitivity7.56×105U/g, and activity recovery0.95.③Three kinds of immobilized CRL with different epoxide number were made. The adsorption isotherm line was fitted by Langmiur equation of monomolecular layer, which correlation coefficient was higher than0.99. The effects of epoxide number and temperature on adsorption of Swida wilsoniana oil were researched. The fitting pseudo-second-order kinetic equation was built up with correlation coefficient higher than0.99. And for the oil of Swida wilsoniana, the surface of the immobile lipase has30.44kJ/mol activation energy of adsorption.④Compared with isolated enzyme, the optimal reaction temperature of interesterification catalyzed by immobilized enzyme was enhanced from37℃to42℃, while optimal pH was increased from7.2to7.5. After recovering12times, the acitivity of immobilized enzyme was kept over92%. However, the similar catalyzing trends were found between immobilized and isolated enzymes. That trend was shown as increasing in the initial process and then decreasing with moisture increasing.⑤As depicted by GC-MS, The main compounds in Swida wilsoniana oil methyl ester were methyloleate (50.61%), methyl hexadecanoate (14.74%), and methyl stearate (7.11%). Therefore, methyl ester from Swida wilsoniana oil should be a potential substitute for conventional fossil diesel.
4. The catalytic pyrolysis of Swida wilsoniana oil into rich-alkyl bio-oil by alkalinity catalyst was carried out in this research. The results were described as follows:CD The composite catalysts were composed of adding KF into CaO. The lamellar structure with porosity was clearly imaged by SEM. Its specific area was enhanced significantly compared with CaO. As shown by XRD analyses, neutralization of basic sites during addition of KF was inhibited, resulting in increasing catalyst's activity and stability.②The optimal condition in KF/CaO runs were catalyst1.0%, temperature494.2℃, and reaction68.6min, in which the liquid yield reached upwards of84.0%.③There are several kinds of carboxylic acids in The pyrolysis products have several kinds of carboxylic acids resulting a high acid value. Therefore, ionic liquid [Hnmp]+HSO4-was applied as fine catalyst in order to reduce acid value of product in this study. After that treatment, the rich-alkyl bio-oils with good quality were obtained. The highest esterification rate was shown as95.7%. In addition, the total esterification rate could be kept as over90%after recovering6times. The optimal condition was alcohol/oil rate30%, reaction temperature75℃, reaction time100min, and catalyst additive2.0%.
5. Based on the principle of eco-energy value and the input-output model, the energy life cycle analysis for biofuel from Swida wilsoniana fruits was carried out. The results showed that, before allocating co-product value, the net energy value (NEV) of carbomethoxy and rich hydrocarbon biofuel were31593.38MJ/ha and36924.16MJ, and the fossil energy ratio (FER) were3.94and6.71, respectively.And if conside the co-product value, the net energy value (NEV) of carbomethoxy and rich hydrocarbon biofuel were98453.66MJ/ha and99121.2MJ/ha, and the fossil energy ratio (FER) were4.52and7.17, respectively. And the results further demonstrated that both the carbomethoxy and the rich hydrocarbon biofuel from Swida Wilsoniana fruits have positive energy efficiency, and can save some of the fossil fuel. But from the standpoint of energy efficiency, the hydrocarbyl-rich biofuel is more competitive. Compared with the conventional transesterification technology, the catalytic pylolysis technology is more suitable for the conversion of biofuel. The research results provided some information for us to choose the emergy product or techonology which is more effective.
引文
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