生物油低温催化加氢预处理
摘要
本实验设计了一套处理能力为2kg/h的快速裂解装置,该装置由进料系统、反应系统、分离系统、冷凝系统和控制系统组成,进料系统采用两级螺旋进料,分离系统采用两级旋风分离,冷凝系统由三级冷凝：一级是管壁式冷凝,二级是蛇管式冷凝,三级除雾器。
应用快速流化床反应器考察了反应温度、停留时间、进料量和冷凝温度等因素对液体产率的影响,生物质的停留时间是通过气体流速控制。当气体流速达到2.8m3/h、反应温度500℃时液体产率最高(70wt%)。冷凝温度对生物油产品分布也有一定的影响：一级冷凝液(温度>100℃、液体产率25%)主要是一些大分子的酸、酯；二级冷凝液(温度>50℃,液体产率17%)除了含有大量的水之外,还含有一些极性很强的有机化合物如一些小分子的酸、醛、酚；三级是除雾器(液体产率20%)主要是收集气体中的气溶胶。
生物油因其高含水量、高含氧量、高粘度、低热值等不利因素限制了生物油的利用。实验应用高压釜反应器对生物油进行加氢脱氧预处理。实验主要考察了反应条件(温度、时间、催化助剂和催化剂)对加氢脱氧效果的影响,在最优条件下(Pt/γ-Al2O3催化剂、反应温度240℃,氢压6MPa,反应1h)下,生物油脱氧率为50wt%,生物油的热值增到33.45MJ/kg,生物油发生油水分离。GC-MS分析显示生物油中的醛、酮和酸大量减少,酚不变,酯和碳氢化合物的含量有所增加。为了进一步脱除生物油中的氧,提高生物油品质,实验在低温处理的基础上继续进行高温(<350℃)加氢脱氧,高温段的加氢催化剂选择传统石油加氢催化剂RN32V,实验同时考察了温度、时间和催化助剂对生物油精制的影响。结果显示当温度330℃、反应1h,生物油在1%三乙胺催化助剂的催化作用下的脱氧率达到84wt%。
A fast pyrolysis experimental unit with a treatment capacity of 2kg/h is designed firstly. The experimental device consists of a feeding system(two-stage spiral feeding), a reaction system, a separation system(two-stage cyclone), a condensate system(the wall condensation snake-shaped tube condenser and a mist eliminator) and a control system.
The fast pyrolysis experiment examined the influence of feeding quantity, residence time, particle size and reaction temperature on the liquid yield, the results show that the yield of liquid can reach up to 70wt% when the liquid residence time is less than Is, the granular particle diameter is less than lmm and the reaction temperature is 500℃. The experiment also investigated the influence of the condensation temperature on the quality of bio-oil. The condensate at the first level (above 100℃) mainly has acids and esters with large molecules; the condensate at the second level (above 50℃) mainly has aldehydes, ketones and phenol; and the condensate at the third level (below 50℃) mainly has small polar molecules such as acids, aldehydes, phenol as well as a lot of water. The acid has equal distribution in the three condensates.
The high water content, high oxygen content, high viscosity, low calorific value and other unfavorable factors limit the use of bio-oil. The deoxygenation of bio-oil is investigated in the presence of catalyst in an autoclave. The experiment studies the influence of the temperature, reaction time, The finally deoxynation of bio-oil was 50wt% on optimal condition (Pt/γ-Al2O3、240℃、1h、6MPa), which value jump to 33.4KJ/kg and water separated from bio-oil. The results of GC-MS revealed that the content of acid、aldehyde and alkone in the bio-oil decreased, phenol same, and eater increased with hydrocarbon. For the further deoxygenation to enhance the bio-oil quality, Continully, playing experiment at high temperature, the final deoxynation decreased 84% in 330℃、1h and exist of 1% triethylamine(promoter of RN32V).
应用快速流化床反应器考察了反应温度、停留时间、进料量和冷凝温度等因素对液体产率的影响,生物质的停留时间是通过气体流速控制。当气体流速达到2.8m3/h、反应温度500℃时液体产率最高(70wt%)。冷凝温度对生物油产品分布也有一定的影响：一级冷凝液(温度>100℃、液体产率25%)主要是一些大分子的酸、酯；二级冷凝液(温度>50℃,液体产率17%)除了含有大量的水之外,还含有一些极性很强的有机化合物如一些小分子的酸、醛、酚；三级是除雾器(液体产率20%)主要是收集气体中的气溶胶。
生物油因其高含水量、高含氧量、高粘度、低热值等不利因素限制了生物油的利用。实验应用高压釜反应器对生物油进行加氢脱氧预处理。实验主要考察了反应条件(温度、时间、催化助剂和催化剂)对加氢脱氧效果的影响,在最优条件下(Pt/γ-Al2O3催化剂、反应温度240℃,氢压6MPa,反应1h)下,生物油脱氧率为50wt%,生物油的热值增到33.45MJ/kg,生物油发生油水分离。GC-MS分析显示生物油中的醛、酮和酸大量减少,酚不变,酯和碳氢化合物的含量有所增加。为了进一步脱除生物油中的氧,提高生物油品质,实验在低温处理的基础上继续进行高温(<350℃)加氢脱氧,高温段的加氢催化剂选择传统石油加氢催化剂RN32V,实验同时考察了温度、时间和催化助剂对生物油精制的影响。结果显示当温度330℃、反应1h,生物油在1%三乙胺催化助剂的催化作用下的脱氧率达到84wt%。
A fast pyrolysis experimental unit with a treatment capacity of 2kg/h is designed firstly. The experimental device consists of a feeding system(two-stage spiral feeding), a reaction system, a separation system(two-stage cyclone), a condensate system(the wall condensation snake-shaped tube condenser and a mist eliminator) and a control system.
The fast pyrolysis experiment examined the influence of feeding quantity, residence time, particle size and reaction temperature on the liquid yield, the results show that the yield of liquid can reach up to 70wt% when the liquid residence time is less than Is, the granular particle diameter is less than lmm and the reaction temperature is 500℃. The experiment also investigated the influence of the condensation temperature on the quality of bio-oil. The condensate at the first level (above 100℃) mainly has acids and esters with large molecules; the condensate at the second level (above 50℃) mainly has aldehydes, ketones and phenol; and the condensate at the third level (below 50℃) mainly has small polar molecules such as acids, aldehydes, phenol as well as a lot of water. The acid has equal distribution in the three condensates.
The high water content, high oxygen content, high viscosity, low calorific value and other unfavorable factors limit the use of bio-oil. The deoxygenation of bio-oil is investigated in the presence of catalyst in an autoclave. The experiment studies the influence of the temperature, reaction time, The finally deoxynation of bio-oil was 50wt% on optimal condition (Pt/γ-Al2O3、240℃、1h、6MPa), which value jump to 33.4KJ/kg and water separated from bio-oil. The results of GC-MS revealed that the content of acid、aldehyde and alkone in the bio-oil decreased, phenol same, and eater increased with hydrocarbon. For the further deoxygenation to enhance the bio-oil quality, Continully, playing experiment at high temperature, the final deoxynation decreased 84% in 330℃、1h and exist of 1% triethylamine(promoter of RN32V).
引文
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