膜反应器中生物质甘油制氢反应的热力学研究

The Thermodynamic Study on the Steam Reforming of Bio-Glycerol for Hydrogen Production with Membrane Reactor

采用吉布斯自由能最小化方法对膜反应器中生物质甘油水汽重整制氢反应进行热力学研究,考察了温度、压力、水与甘油进料比(S/G)等条件对反应性能的影响,并分析副产物CO和CH_4的生成、积炭的生成、移去CO_2、O_2的添加等对氢气产量和反应体系平衡组成的影响.结果表明:T=900 K,p=100 k Pa,S/G=12时,在膜反应器中及时移除CO_2可提高氢气产量和选择性,氢气产量高达6.86 mol H_2/摩尔甘油,选择性98.00%;在反应体系中添加少量的O_2(摩尔分数<1%)有利于抑制CO和CH_4的生成,而氢气产量几乎不受影响.

A thermodynamic analysis on hydrogen production by steam reforming of bio-glycerol in membrane reactor was carried out by employing the Gibbs free energy minimization principle. The influence of operating conditions such as temperature, pressure, ratio of steam and glycerol （ S/G）, the production of CO, CH＋ and coke, the removal of CO, and the addition of O2 on the reaction performance ,hydrogen production and selectivity were investigated in details. When T=900 K,p = 100 kPa,S/G = 12,hydrogen production of 6.86 mol H2/mol glycerol and hydrogen selectivity of 98.00% were achieved in a membrane reactor via CO2 removal,which could improve the hydrogen pro- duction and selectivity. Meanwhile, the addition of little amount of O2 （ 〈 1% ） was favorable for this catalysis process, showing no effects on hydrogen production, but was inhibitive of the reformation of CO and CH4.