生物油—甲醇在镍基催化剂上的催化转化制氢研究
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摘要
氢气不仅是一种重要的化工原料,而且还是一种能源的载体。氢能被认为是21世纪最具有发展潜力的清洁能源之一。目前,氢气的生产主要依赖于石化原料的转化,不仅对环境造成了很大污染,而且也加速了化石燃料的枯竭。在环境污染和能源危机双重压力下,人们渴望寻求可循环、无污染的制氢技术。
生物质能源作为一种清洁的可再生能源,将在未来世界能源结构中占据越来越重要的位置,对于发展低碳技术也具有十分重要的现实意义。在生物质能源利用的多种途径之中,生物质热解液体产物的催化转化制氢已成为生物质能源研究中的热点与重点。
本文首先利用实验室自行研发的生物质快速热解系统制备生物油,研究了生物油的含水量、热值、粘度、pH值等理化特性,通过GC-MS分析了生物油的化学组成。分析结果表明,通过分级冷凝系统得到的一级生物油成分复杂,水分含量为24.21%,较适合提取高附加值化学品或提质改性为高品位燃料；二三、四级混合生物油成分简单,水分含量为55.54%,较适合催化重整制氢。
本文主要研究了生物油-甲醇混合样品在镍基催化剂上催化转化制氢方面的内容。首先选择了商业催化剂ICI46-1对生物油进行催化转化,再利用正交试验的方法考查了生物油与甲醇混合样品催化转化制氢各反应参数的影响,包括生物油-甲醇混合比例、水碳比、反应温度和进样流速,优化了催化重整制氢的实验条件,建立了催化剂性能评价的一般方法。然后,实验选择镁橄榄石为载体,CeO2 MgO为助剂,依据前一阶段的研究成果制备了一种镍基催化剂,并对其催化性能进行考察。
研究结果表明,采用生物油-甲醇混合样品催化重整制氢,不仅提高了氢气产率与碳转化率,而且可以明显减少催化剂积炭,提高了催化剂的活性与稳定性。通过正交试验得知,甲醇与生物油质量混合比为50%：50%的结果最佳,应用ICI46-1催化剂时氢气产率和碳转化率分别为34.66%及63.02%。合成催化剂6%Ni-3%Ce-1%Mg/olivine催化重整的效果相对于ICI46-1催化剂有所改善,同等实验条件下,碳转化率和氢气产率相对提高,最佳实验条件下碳转化率和氢气产率分别为68.29%和38.52%。
Hydrogen is not only an important chemical raw material, but also an energy carrier. Hydrogen is considered the most development potential clean energy sources in the 21st century. Currently, hydrogen production mainly depends on the conversion of petrochemical raw materials, such a process causes great pollution to the environment, and accelerates the depletion of fossil fuels. In the dual pressures of environ-mental pollution and energy crisis, people eager to search for recycling, pollution-free hydrogen production methods.
As a clean renewable energy, biomass will play a more and more important role in the future. And it is also of great practical significance to the development of low carbon technology. Among varietal biomass energy application ways, hydrogen production by catalytic reforming of biomass pyrolysis liquid has become a hot research point and focus.
Firstly, bio-oil was produced through fast pyrolysis of biomass under laboratory-developed system, in which physical properties such as water content, calorific value, viscosity, pH value, etc., are studied. The chemical composition of bio-oil was analyzed by GC-MS. The results show that the first grade bio-oil obtained through the grading system has a complex composition with a moisture content of 24.21%, which is suitable for extraction of high value-added chemicals or a high quality high-grade fuel after modification; and the second, third, fourth hybrid bio-oil with a simple composition consisting of moisture content of 55.54%, is more suitable for catalytic reforming.
Hydrogen production by catalytic reforming of bio-oil & methanol over nickel catalysts is studied in this thesis. A commercial catalyst ICI46-1 was selected for catalytic conversion of bio-oil, an orthogonal experiment was used in the fixed micro-reactor to systematically examine the effect of various reaction parameters, such as the ratio of bio-oil and methanol mixture, reaction temperature, steam carbon ratio, and sample flow rate. Such a text can optimize conditions and hence, established a popular method for evaluating the performance of catalysts. Forsterite was chose as the catalysts'carrier, CeC2, MgO as additives according to results of previous studies, and the properties of a laboratory-made nickel-based catalyst uesd were investigated.
The results show that hydrogen production by catalytic reforming of mixed samples of bio-oil-methanol not only improves the hydrogen yield and carbon conversion, but also reduces obviously the catalyst carbon deposition, and therefore effectively improves the catalyst activity and stability. The results of orthogonal test show that the optimum mixing mass ratio of methanol and bio-oil is 50%:50%, hydrogen yield and carbon conversion rate was 34.66% and 63.02%, respectively by using ICI46-1. The effect of catalytic reforming with a synthesis catalyst of 6% Ni-3% Ce-1% Mg/olivine improved in comparison with ICI46-1, where the carbon conversion and hydrogen yield is relatively increased, respectively in the same conditions. And under optimum conditions, the carbon conversion and hydrogen production rates were 68.29% and 38.52%, respectively.
生物质能源作为一种清洁的可再生能源,将在未来世界能源结构中占据越来越重要的位置,对于发展低碳技术也具有十分重要的现实意义。在生物质能源利用的多种途径之中,生物质热解液体产物的催化转化制氢已成为生物质能源研究中的热点与重点。
本文首先利用实验室自行研发的生物质快速热解系统制备生物油,研究了生物油的含水量、热值、粘度、pH值等理化特性,通过GC-MS分析了生物油的化学组成。分析结果表明,通过分级冷凝系统得到的一级生物油成分复杂,水分含量为24.21%,较适合提取高附加值化学品或提质改性为高品位燃料；二三、四级混合生物油成分简单,水分含量为55.54%,较适合催化重整制氢。
本文主要研究了生物油-甲醇混合样品在镍基催化剂上催化转化制氢方面的内容。首先选择了商业催化剂ICI46-1对生物油进行催化转化,再利用正交试验的方法考查了生物油与甲醇混合样品催化转化制氢各反应参数的影响,包括生物油-甲醇混合比例、水碳比、反应温度和进样流速,优化了催化重整制氢的实验条件,建立了催化剂性能评价的一般方法。然后,实验选择镁橄榄石为载体,CeO2 MgO为助剂,依据前一阶段的研究成果制备了一种镍基催化剂,并对其催化性能进行考察。
研究结果表明,采用生物油-甲醇混合样品催化重整制氢,不仅提高了氢气产率与碳转化率,而且可以明显减少催化剂积炭,提高了催化剂的活性与稳定性。通过正交试验得知,甲醇与生物油质量混合比为50%：50%的结果最佳,应用ICI46-1催化剂时氢气产率和碳转化率分别为34.66%及63.02%。合成催化剂6%Ni-3%Ce-1%Mg/olivine催化重整的效果相对于ICI46-1催化剂有所改善,同等实验条件下,碳转化率和氢气产率相对提高,最佳实验条件下碳转化率和氢气产率分别为68.29%和38.52%。
Hydrogen is not only an important chemical raw material, but also an energy carrier. Hydrogen is considered the most development potential clean energy sources in the 21st century. Currently, hydrogen production mainly depends on the conversion of petrochemical raw materials, such a process causes great pollution to the environment, and accelerates the depletion of fossil fuels. In the dual pressures of environ-mental pollution and energy crisis, people eager to search for recycling, pollution-free hydrogen production methods.
As a clean renewable energy, biomass will play a more and more important role in the future. And it is also of great practical significance to the development of low carbon technology. Among varietal biomass energy application ways, hydrogen production by catalytic reforming of biomass pyrolysis liquid has become a hot research point and focus.
Firstly, bio-oil was produced through fast pyrolysis of biomass under laboratory-developed system, in which physical properties such as water content, calorific value, viscosity, pH value, etc., are studied. The chemical composition of bio-oil was analyzed by GC-MS. The results show that the first grade bio-oil obtained through the grading system has a complex composition with a moisture content of 24.21%, which is suitable for extraction of high value-added chemicals or a high quality high-grade fuel after modification; and the second, third, fourth hybrid bio-oil with a simple composition consisting of moisture content of 55.54%, is more suitable for catalytic reforming.
Hydrogen production by catalytic reforming of bio-oil & methanol over nickel catalysts is studied in this thesis. A commercial catalyst ICI46-1 was selected for catalytic conversion of bio-oil, an orthogonal experiment was used in the fixed micro-reactor to systematically examine the effect of various reaction parameters, such as the ratio of bio-oil and methanol mixture, reaction temperature, steam carbon ratio, and sample flow rate. Such a text can optimize conditions and hence, established a popular method for evaluating the performance of catalysts. Forsterite was chose as the catalysts'carrier, CeC2, MgO as additives according to results of previous studies, and the properties of a laboratory-made nickel-based catalyst uesd were investigated.
The results show that hydrogen production by catalytic reforming of mixed samples of bio-oil-methanol not only improves the hydrogen yield and carbon conversion, but also reduces obviously the catalyst carbon deposition, and therefore effectively improves the catalyst activity and stability. The results of orthogonal test show that the optimum mixing mass ratio of methanol and bio-oil is 50%:50%, hydrogen yield and carbon conversion rate was 34.66% and 63.02%, respectively by using ICI46-1. The effect of catalytic reforming with a synthesis catalyst of 6% Ni-3% Ce-1% Mg/olivine improved in comparison with ICI46-1, where the carbon conversion and hydrogen yield is relatively increased, respectively in the same conditions. And under optimum conditions, the carbon conversion and hydrogen production rates were 68.29% and 38.52%, respectively.
引文
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[4]丛德奇,侯金华,金花.生物质能开发与吉林省利用现状研究[J].农业与技术,1999,19(6)：1-4.
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[7]张长森.流化床生物质气化及热解实验研究[D].郑州：郑州大学化学系,2006.
[8]毛宗强.氢能及其近期应用前景[J].科技导报,2005,23(2)：34-38.
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