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Cattle fat valorisation through biofuel production by hydrogenation in supercritical carbon dioxide

机译:在超临界二氧化碳中通过氢化生产生物燃料来增加牛脂肪的价值

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摘要

The use of residues or wastes in biofuel production is a potential solution to the questioned increase of the food market price. The hydrogenation (more specifically hydrodeoxygenation) of residues or wastes rich in free fatty acids seems to be an interesting option for the valorisation of this type of feedstock. The major obstacle of this process is the high temperature and high H2 pressure process requirement. The way to reduce it is the use of a co-solvent e.g. supercritical fluids. At supercritical conditions, CO2 is completely miscible with H2 and at the same time is also a great solvent for non-polar liquids allowing enhanced efficiency of the hydrogenation leading to the ability to perform reactions at milder conditions. This work deals with the heterogeneous hydrogenation of cattle fat in the presence of CO2. Total reaction pressures up to 140 bar at 340 C and the residence time from 1 to 6 hours as well as the reuse of catalyst were examined. Depending on the chosen reaction conditions a diverse end products can be obtained. The CO2 presence influences positively the concentration of hydrocarbons minimising the presence of glycerides' content in the final product mixture. At elevated CO2 pressure, a high concentration of hydrocarbons simultaneously with a low presence of free fatty acids and glycerides' content in the mixture was obtained. A similar effect was observed for reaction carried out for 6 hours, when above 90 wt% of all hydrocarbons present in the mixture were the saturated ones. Additionally, the reuse of catalyst increases the saturated hydrocarbons' content to values similar to those obtained for reactions with prolonged residence time. In the CO2-assisted reactions, the diesel-like hydrocarbons were formed with at least two fold higher content than in reactions without CO2.
机译:在生物燃料生产中使用残留物或废物是解决食品市场价格上涨的潜在解决方案。富含游离脂肪酸的残渣或废料的氢化(更具体而言是加氢脱氧)对于这类原料的增价似乎是一个有趣的选择。该过程的主要障碍是高温和高H2压力过程的要求。减少它的方法是使用助溶剂,例如超临界流体。在超临界条件下,CO2可以与H2完全混溶,同时也是非极性液体的强溶剂,可以提高氢化效率,从而可以在较温和的条件下进行反应。这项工作涉及在CO2存在下牛脂肪的异质氢化。检查了总反应压力在340°C时高达140 bar,停留时间为1到6小时以及催化剂的重复使用。根据所选择的反应条件,可以获得各种最终产物。 CO2的存在对碳氢化合物的浓度产生积极影响,从而使最终产品混合物中甘油酯含量的存在最小化。在升高的CO2压力下,获得了高浓度的烃,同时混合物中游离脂肪酸和甘油酯的含量很少。当混合物中存在的所有烃中超过90 wt%为饱和烃时,对于进行6小时的反应观察到类似的效果。另外,催化剂的再利用将饱和烃的含量增加到类似于对于具有延长停留时间的反应获得的值。在CO 2辅助反应中,形成的类柴油烃的含量至少比不含CO 2的反应高两倍。

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