固体热载体法生物质催化气化制氢新工艺研究
摘要
为改善未来的能源结构和缓解目前严重的环境污染问题，人们越来越重视清洁能源——氢能的开发和利用。生物质催化气化制氢是富有发展前景的利用可再生资源制氢技术。但是，制约目前生物质气化制氢技术发展的主要问题是产气中H_2含量低和焦油含量高。水蒸汽作为气化剂和使用催化剂是提高产气中H_2含量和降低焦油含量的有效手段。基于此，本论文提出了用循环固体热载体法的ECCMB(External CirculatingConcurrent Moving-Bed，外循环并流移动床)催化气化制氢工艺，目标是减少焦油产生和提高产气中H_2含量。ECCMB反应系统由气固并流移动床气化器和快速流化床燃烧器构成。催化剂同时作为固体热载体在两器间循环，将燃烧半焦和催化剂积炭释放的热量提供给气化反应。在气化器内，顺序发生灼热固体热载体加热条件下的生物质快速热解、热解焦油催化转化和半焦气化等过程。ECCMB气化工艺综合了生物质快速热解、焦油催化转化、热载体加热和催化剂再生无切换连续进行等特点。
围绕该工艺的构建，本论文主要展开下述工作：
作为ECCMB气化过程的初始阶段，快速热解过程对气化产品分布有重要影响。本论文用落下床反应器研究生物质快速热解和水蒸汽气化特性，考察了原料、粒度、温度、S／B比(水蒸汽与生物质进料质量比)等对产品分布的影响。研究发现，在落下床中短停留时间(＜2s)和高加热速率下，生物质热解和原位焦油水蒸汽转化、半焦水蒸汽气化、水煤气变换反应同时发生；高加热速率有利于生物质转化、提高产气中H_2含量和减少焦油含量。研究还发现，在落下床生物质水蒸汽气化过程中，高温下水煤气变换反应对产气组成有重要影响；在落下床中催化剂和焦油的接触时间短，焦油不能得到充分转化。
ECCMB气化工艺要求催化剂具有高催化活性和强抗磨损能力，并且价格低廉。本沦文通过比较石灰石、白云石和橄榄石等天然矿石的焦油转化催化活性，筛选出适合用于ECCMB气化工艺的催化剂。研究发现，煅烧预处理可以提高橄榄石的催化活性，其原因是高温煅烧使Fe从镁铁硅酸盐结构中脱出，在颗粒表面生成α-Fe_2O_3；在生物质水蒸汽气化过程中，α-Fe_2O_3被产气中的H_2原位还原为金属Fe，充当催化活性中心；随着煅烧温度升高和时间延长，可还原α-Fe_2O_3生成量增多，橄榄石催化活性提高；煅烧预处理使橄榄石颗粒表面Fe的分布比原矿均匀；MgO和Fe_2O_3含量高的橄榄石有较高催化活性；橄榄石的抗磨损能力强，因此它是一种理想的气化器内焦油转化催化剂。虽然白云石催化活性高，但是煅烧后质地软，不适合用于流化床气化反应体系。
For optimizing the energy utilizations and reducing environmental problems, more and more people paid much attention to hydrogen energy. Gasification of the renewable biomass for hydrogen production is a promising technology. However, there are still many obstacles required to resolve until the commercial breakthrough could be obtained, such as high tar content in dry gas and low hydrogen yield. The addition of steam and catalyst favor hydrogen production and tar reduction. In this thesis, a novel process of catalytic gasification of biomass with solid heat carrier is proposed, which is called ECCMB (External Circulating Concurrent Moving-Bed) gasification system. The ECCMB gasification system is composed of two reactors, a gas-solid concurrent moving-bed gasifier and a riser-type combustor. A circulation loop of bed material is achieved between the two reactors. The circulating bed material acts as not only solid heat carrier from the combustor to the gasifier, which supplies the required energy of gasification reactions of biomass, but also catalyst in tar reduction. In gasifier, fast pyrolysis of biomass, catalytic reforming of tar and gasification of char sequently occurs. A dry gas with low tar content and high hydrogen content should be obtained in the ECCMB process. In the combustor, reheating of solid heat carrier and regenerated catalyst are made by burning off the residual char and coke on catalyst.
For developing the ECCMB process, investigations were conducted in this thesis as follows:
As a part of the ECCMB process, fast pyrolysis of biomass influences greatly the product distribution. As a preliminary work, fast pyrolysis and steam gasification of biomass were studied in a free fall reactor. Effects of reactor temperature, particle size, fuel type and S/B ratio (steam to biomass mass ratio) on product distribution were investigated. It has been shown that the occurrence of the in-situ steam reforming of tar, the steam gasification of char and the water-gas shift reaction after the primary fast pyrolysis of the biomass took place even in a short gas residence time in the free fall reactor. Fast pyrolysis favors biomass conversion for tar reduction and hydrogen production. In addition, during steam gasification of biomass, water-gas shift reaction influences greatly the gas composition at higher temperature. In the free fall reactor, only a limited conversion of tar was achieved because of the short contact time between the catalyst and volatiles.
围绕该工艺的构建，本论文主要展开下述工作：
作为ECCMB气化过程的初始阶段，快速热解过程对气化产品分布有重要影响。本论文用落下床反应器研究生物质快速热解和水蒸汽气化特性，考察了原料、粒度、温度、S／B比(水蒸汽与生物质进料质量比)等对产品分布的影响。研究发现，在落下床中短停留时间(＜2s)和高加热速率下，生物质热解和原位焦油水蒸汽转化、半焦水蒸汽气化、水煤气变换反应同时发生；高加热速率有利于生物质转化、提高产气中H_2含量和减少焦油含量。研究还发现，在落下床生物质水蒸汽气化过程中，高温下水煤气变换反应对产气组成有重要影响；在落下床中催化剂和焦油的接触时间短，焦油不能得到充分转化。
ECCMB气化工艺要求催化剂具有高催化活性和强抗磨损能力，并且价格低廉。本沦文通过比较石灰石、白云石和橄榄石等天然矿石的焦油转化催化活性，筛选出适合用于ECCMB气化工艺的催化剂。研究发现，煅烧预处理可以提高橄榄石的催化活性，其原因是高温煅烧使Fe从镁铁硅酸盐结构中脱出，在颗粒表面生成α-Fe_2O_3；在生物质水蒸汽气化过程中，α-Fe_2O_3被产气中的H_2原位还原为金属Fe，充当催化活性中心；随着煅烧温度升高和时间延长，可还原α-Fe_2O_3生成量增多，橄榄石催化活性提高；煅烧预处理使橄榄石颗粒表面Fe的分布比原矿均匀；MgO和Fe_2O_3含量高的橄榄石有较高催化活性；橄榄石的抗磨损能力强，因此它是一种理想的气化器内焦油转化催化剂。虽然白云石催化活性高，但是煅烧后质地软，不适合用于流化床气化反应体系。
For optimizing the energy utilizations and reducing environmental problems, more and more people paid much attention to hydrogen energy. Gasification of the renewable biomass for hydrogen production is a promising technology. However, there are still many obstacles required to resolve until the commercial breakthrough could be obtained, such as high tar content in dry gas and low hydrogen yield. The addition of steam and catalyst favor hydrogen production and tar reduction. In this thesis, a novel process of catalytic gasification of biomass with solid heat carrier is proposed, which is called ECCMB (External Circulating Concurrent Moving-Bed) gasification system. The ECCMB gasification system is composed of two reactors, a gas-solid concurrent moving-bed gasifier and a riser-type combustor. A circulation loop of bed material is achieved between the two reactors. The circulating bed material acts as not only solid heat carrier from the combustor to the gasifier, which supplies the required energy of gasification reactions of biomass, but also catalyst in tar reduction. In gasifier, fast pyrolysis of biomass, catalytic reforming of tar and gasification of char sequently occurs. A dry gas with low tar content and high hydrogen content should be obtained in the ECCMB process. In the combustor, reheating of solid heat carrier and regenerated catalyst are made by burning off the residual char and coke on catalyst.
For developing the ECCMB process, investigations were conducted in this thesis as follows:
As a part of the ECCMB process, fast pyrolysis of biomass influences greatly the product distribution. As a preliminary work, fast pyrolysis and steam gasification of biomass were studied in a free fall reactor. Effects of reactor temperature, particle size, fuel type and S/B ratio (steam to biomass mass ratio) on product distribution were investigated. It has been shown that the occurrence of the in-situ steam reforming of tar, the steam gasification of char and the water-gas shift reaction after the primary fast pyrolysis of the biomass took place even in a short gas residence time in the free fall reactor. Fast pyrolysis favors biomass conversion for tar reduction and hydrogen production. In addition, during steam gasification of biomass, water-gas shift reaction influences greatly the gas composition at higher temperature. In the free fall reactor, only a limited conversion of tar was achieved because of the short contact time between the catalyst and volatiles.
引文
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