基于热解-重整-燃烧解耦三床气化系统的生物质催化制富氢气体

    Catalytic biomass gasification for hydrogen rich gas production in decoupled-triple-bed gasification system

    • 摘要: 生物质催化气化是将生物质转换成富氢气体的有效途径。该研究提出了一种由热解反应器、重整反应器和提升管燃烧器三部分构成的解耦三床生物质气化(decoupled triple bed gasification,DTBG)工艺。在实验室规模的DTBG气化反应装置上,以水蒸气为气化剂,以橄榄石为原位焦油裂解催化床料,进行了生物质水蒸气催化气化试验,考察了生物质种类、重整器温度、生物质进料速率对气化效果的影响规律,并且对气化副产物焦油的特性进行了分析。试验结果表明,生物质原料的挥发分对气化产物分布的影响很大,原料挥发分含量越高,气体产率越高,碳转化率越高,气体中的H2和CO体积分数越大、CO2体积分数越低。当重整器温度由750升高到850 ℃时,气体产率从0.91增加到1.08 m3/kg,焦油质量浓度从19.1降低到7.3 g/m3,同时气体品质大幅度提升。随着生物质进料速率的增加,产气中H2体积分数大幅度增加,CO2体积分数大幅度降低,但是焦油质量浓度基本不变。当重整器温度为800 ℃,白松木屑进料速率为220 g/h时,H2和CO体积分数分别达到了42.2%和14.6%,产气中焦油质量浓度为10.1 g/m3。气化焦油的主要成分为多环芳烃,其中萘含量最高。当重整器温度从700℃升高到850 ℃时,焦油中单环化合物几乎全部分解,3~4环多环芳烃化合物逐步降低,萘的相对含量从54.7%升高到75.6%。该研究结果可为大规模气化装置的设计、运行以及优化提供理论指导。

       

      Abstract: Biomass steam gasification is a promising technology for hydrogen-rich gas production. In this paper the decoupled triple bed gasification (DTBG) system has been proposed. The system is composed of 3 decoupled reactors, i.e., gas-solid countercurrent moving bed pyrolyzer, radial-flow moving bed reformer and riser-type combustor. The steam was used as gasifying agent and the calcined olivine was used as circulating heat carrier and in-situ tar destruction catalyst as well. Experiments have been conducted at a pyrolyzer temperature of 700 ℃, a combustor temperature of 850 ℃ and the ratio of steam mass to biomass mass (S/B) of 0.65. The influences of biomass type on the gasification performance were investigated with saw dust, rice husk, wheat straw and cotton stalk as biomass feedstock at the reformer temperature of 800 ℃. The effects of reformer temperature (700-850 ℃) and biomass feeding rate (120-220 g/h) on gas yield, tar content, gas composition, carbon conversion as well as gasification efficiency were investigated with saw dust as feedstock. Besides, the characteristics of gasification tar at the varied reformer temperatures were investigated using gas chromatograph. The results indicated that the volatiles of biomass have great effect on the gasification performance. The gas yield, carbon conversion, the concentration of H2 and CO increased and CO2 concentration decreased with increasing volatile matter content of biomass. In the DTBG system, the pyrolyzer and reformer are separated and the volatiles released from pyrolyzer were the main source of the product gas. Therefore, a secondary reaction of volatiles in reformer with the presence of the olivine, such as steam reforming reaction, tar creaking reaction, plays a critical role in determining product gas composition as well as gas yield. The saw dust was found to be preferable biomass type for hydrogen-rich gas production. Gas yield increased from 0.91 to 1.08 m3/kg while tar content decreased from 19.1 to 7.3 g/m3 at the reformer temperature range of 750-850 ℃. At the same time, carbon conversion and gasification efficiency were dramatically increased from 71.4% to 81.4% and from 56.4% to 65.2%, respectively, with increasing reformer temperature from 750 to 850 ℃. The H2 concentration increased and CO2 concentration decreased with the increasing biomass feeding rate, which yet had little impact on tar content. Specifically, product gas with the H2 concentration of 42.2%, CO concentration of 14.6% and the tar content of 10.1 g/m3 has been obtained at the reformer temperature of 800 ℃ and biomass feeding rate of 220 g/h. The gasification tar was basically composed of naphthalene, biphenyl, acenaphthene, dibenzofuran, fluorene, phenanthrene, fluoranthene, and pyrene, in which naphthalene was found to be the dominate component. Single ring hydrocarbons were totally destructed and 3-4 ring PAHs (polycyclic aromatic hydrocarbons) decreased, while the concentration of naphthalene was dramatically increased from 54.7% to 75.6% at the reformer temperature range of 750-850 ℃. It can be demonstrated that the novel design of reformer in the DTBG system with olivine not only is favorable to increase tar reforming/cracking reactions which favors tar removal, but also appears as a feasible technology for hydrogen-rich gas production. This work is expected to be helpful for the design, operation and optimization of large-scale gasification plant.

       

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