生物质与煤共气化制取富氢燃气的试验及模拟研究
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摘要
能源与环境问题,已成为21世纪制约人类社会进步和发展的关键问题,开发清洁、高效的新能源已成为世界各国研究的重点项目。生物质能源由于储量丰富、利用无污染、价格低廉等优点,成为研究的重中之重。而氢能是非常重要的二次能源,是航空、化工的领域不可缺少的能源及原料。利用生物质能制取氢气,势必成为对社会、经济和技术非常有价值的研究工作。
本文是在江苏大学提出的“单一流化床两步气化法”工艺系统的基础上,对生物质与煤共气化反应过程进行了一系列的试验和模拟研究。在完成了试验台系统搭建的基础上,着重研究了生物质与煤共热解过程,及生物质与煤共流化床水蒸气气化过程,并对气化过程进行了过程模拟研究。得到如下主要结论:首先,进行了煤与生物质共热解热重试验,结果表明:共热解过程中,煤热解的失重峰有所提前,并且两者表观活化能都低于单独热解时的数值,表明两者有热解中存在一定协同性;其次,在自行设计的试验台上,利用煤与生物质为原料,完成了气化试验,并得到了反应温度,S/B,生物质与煤比例等气化制约因素对制氢的影响,结果表明生物质与煤在流化床中共同流化特性良好;气化过程中,反应温度和水蒸汽用量是提高氢气产量以及潜在产氢量的重要参数,且得到的气化燃气中焦油含量小于1.0 mg/m~3。当反应温度的区间在1050～1000℃、S/B为2.07、生物质与煤的混合比值为4/1时,每千克无灰干基生物质和煤的产氢量为60.3g,而潜在产氢量最大值达116g;最后,针对本工艺系统,利用ASPEN PLUS软件,进行了化学过程模拟,通过与试验结果的对比,证明了模型的准确性,并利用软件中灵敏度分析的功能,对反应温度,S/B,CaO催化剂等制约生物质气化制氢的因素进行了研究,模拟结果与试验结果吻合,表明高温下,增加水蒸气用量可以有效提高燃气中氢气的纯度和产量;CaO催化剂存在的情况下,可以调整气体成分。同时通过灵敏度分析得出,水蒸气与生物质的质量比(S/B)值对非可燃性气体H_2的产量和在产气中的体积百分比浓度有直接的影响,其次为气化反应温度的影响,最后是CaO催化剂的影响作用这个结论。并且在有CaO催化剂的条件下,生物质气化制氢的最适宜温度和S/B值都有所下降,表明CaO催化剂对生物质气化制氢过程有很好的定向催化的作用,能产生更多更纯的氢气。本文的研究工作对今后生物质与煤共气化技术大规模应用和产业化提供了一定的依据和有重要参考价值。
The problem of energy and enviorment,has become the key question to restrict the development of the society.To develop the efficiential and enviormental technology of the new-energy had interested all countrys over the world.For the abundant reserves,in-pollute and inexpensive characters of biomass,it become the most important research in all.Besides,Hydrogen is a much important wealth,which can be used in the chemical and navigate field.It must be able to promote the development of the total society,economy and technology in using biomass product Hydrogen project.
The article is based on the system of "One fluidied bed two-phase gasification". We do a series study on the biomass and coal' s co-gasification which include both the experimentation study and the simulation study.With the accomplishment of the test-bed project,we spent a lot of time and vigorness on the co-pyrolysisi study,the co-gasification examination and the simulation of itself.And the result is as follows:First,we do the study on the co-pyrolysis reactions of the biomass and coal blends.It turn up that during the course of the co-pyrolysis,the weightlessness peak value is declined to the lower temperature aera.The apparent activative energy of the blends is lower than that in each pyrolysis reaction themselves,which indicate that the coal and biomass have some mutual cooperative effect in the co-pyrolysis reactions.Second,we do the co-gasification test by the test bed which was designed by ourselves and was operated on biomass and coal at various Bed temperature,Biomass to steam ratio(S/B) and Biomass to coal ratio.And it turn out that the biomass and coal can have a good behavior in the fluidied state in the bed; The temperature and biomass to steam ratio is the most important factors in promoting the purity and the production of hydrogen,as well as the tar is under 10mg/m~3.When the temperature is about 1050～1000℃、S/B is to 2.07 and the biomass to steam ratio is to 4,one kilogram biomass can bring hydrogen 60.3g,and the hydrogen productive capability of the biomass is 116g.Finally,the developed two-phase air-steam gasification model was validated using the experimental results obtained from the test-bed by ASPEN PLUS software.A good agreement between the model predictions and experimental data was obtained under all operating conditions studied.Through the model sensitivity,it turn up that the higher temperature,the lower pressure,the bigger S/B value can do a favor to induce the production of the hydrogen.And the CaO can adjust the content of the gas.On a percentage increase basis(1%increase) of each of the operating variables,the Biomass to Steam ratio has the most effect on the hydrogen production followed by the temperature and then the CaO catalyzer and the pressure.Besides,on the condition of the CaO catalyzer,the rightest gasification temperature and S/B is declined.The CaO catalyzer can do a good job in the gasification reactions to bring much more pure hydrogen-rich gas.The study can be able to help the application the co-gasification of the biomass and coal blends in the near future.
本文是在江苏大学提出的“单一流化床两步气化法”工艺系统的基础上,对生物质与煤共气化反应过程进行了一系列的试验和模拟研究。在完成了试验台系统搭建的基础上,着重研究了生物质与煤共热解过程,及生物质与煤共流化床水蒸气气化过程,并对气化过程进行了过程模拟研究。得到如下主要结论:首先,进行了煤与生物质共热解热重试验,结果表明:共热解过程中,煤热解的失重峰有所提前,并且两者表观活化能都低于单独热解时的数值,表明两者有热解中存在一定协同性;其次,在自行设计的试验台上,利用煤与生物质为原料,完成了气化试验,并得到了反应温度,S/B,生物质与煤比例等气化制约因素对制氢的影响,结果表明生物质与煤在流化床中共同流化特性良好;气化过程中,反应温度和水蒸汽用量是提高氢气产量以及潜在产氢量的重要参数,且得到的气化燃气中焦油含量小于1.0 mg/m~3。当反应温度的区间在1050～1000℃、S/B为2.07、生物质与煤的混合比值为4/1时,每千克无灰干基生物质和煤的产氢量为60.3g,而潜在产氢量最大值达116g;最后,针对本工艺系统,利用ASPEN PLUS软件,进行了化学过程模拟,通过与试验结果的对比,证明了模型的准确性,并利用软件中灵敏度分析的功能,对反应温度,S/B,CaO催化剂等制约生物质气化制氢的因素进行了研究,模拟结果与试验结果吻合,表明高温下,增加水蒸气用量可以有效提高燃气中氢气的纯度和产量;CaO催化剂存在的情况下,可以调整气体成分。同时通过灵敏度分析得出,水蒸气与生物质的质量比(S/B)值对非可燃性气体H_2的产量和在产气中的体积百分比浓度有直接的影响,其次为气化反应温度的影响,最后是CaO催化剂的影响作用这个结论。并且在有CaO催化剂的条件下,生物质气化制氢的最适宜温度和S/B值都有所下降,表明CaO催化剂对生物质气化制氢过程有很好的定向催化的作用,能产生更多更纯的氢气。本文的研究工作对今后生物质与煤共气化技术大规模应用和产业化提供了一定的依据和有重要参考价值。
The problem of energy and enviorment,has become the key question to restrict the development of the society.To develop the efficiential and enviormental technology of the new-energy had interested all countrys over the world.For the abundant reserves,in-pollute and inexpensive characters of biomass,it become the most important research in all.Besides,Hydrogen is a much important wealth,which can be used in the chemical and navigate field.It must be able to promote the development of the total society,economy and technology in using biomass product Hydrogen project.
The article is based on the system of "One fluidied bed two-phase gasification". We do a series study on the biomass and coal' s co-gasification which include both the experimentation study and the simulation study.With the accomplishment of the test-bed project,we spent a lot of time and vigorness on the co-pyrolysisi study,the co-gasification examination and the simulation of itself.And the result is as follows:First,we do the study on the co-pyrolysis reactions of the biomass and coal blends.It turn up that during the course of the co-pyrolysis,the weightlessness peak value is declined to the lower temperature aera.The apparent activative energy of the blends is lower than that in each pyrolysis reaction themselves,which indicate that the coal and biomass have some mutual cooperative effect in the co-pyrolysis reactions.Second,we do the co-gasification test by the test bed which was designed by ourselves and was operated on biomass and coal at various Bed temperature,Biomass to steam ratio(S/B) and Biomass to coal ratio.And it turn out that the biomass and coal can have a good behavior in the fluidied state in the bed; The temperature and biomass to steam ratio is the most important factors in promoting the purity and the production of hydrogen,as well as the tar is under 10mg/m~3.When the temperature is about 1050～1000℃、S/B is to 2.07 and the biomass to steam ratio is to 4,one kilogram biomass can bring hydrogen 60.3g,and the hydrogen productive capability of the biomass is 116g.Finally,the developed two-phase air-steam gasification model was validated using the experimental results obtained from the test-bed by ASPEN PLUS software.A good agreement between the model predictions and experimental data was obtained under all operating conditions studied.Through the model sensitivity,it turn up that the higher temperature,the lower pressure,the bigger S/B value can do a favor to induce the production of the hydrogen.And the CaO can adjust the content of the gas.On a percentage increase basis(1%increase) of each of the operating variables,the Biomass to Steam ratio has the most effect on the hydrogen production followed by the temperature and then the CaO catalyzer and the pressure.Besides,on the condition of the CaO catalyzer,the rightest gasification temperature and S/B is declined.The CaO catalyzer can do a good job in the gasification reactions to bring much more pure hydrogen-rich gas.The study can be able to help the application the co-gasification of the biomass and coal blends in the near future.
引文
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