In-situ hydrogen supplementation of biomass chemical looping gasification to produce syngas with controllable H2/CO

doi:10.11949/0438-1157.20241392

Abstract

Abstract:

This study proposes a novel technology for preparing syngas with controllable H₂/CO by in-situ hydrogenation of biomass chemical looping gasification (BCLG-CLRHP) through coupling biomass chemical looping gasification (BCLG) with steam chemical looping reforming hydrogen production (CLRHP). The maximum syngas yield, 0.61 L/g (biomass), was obtained at a reaction temperature of 900℃ and an optimal lattice oxygen to biomass (OC/B, mass) of 0.5, utilizing NiFe₂O₄(ZrO₂) as the oxygen carriers (OC). In the BCLG process, a steam/biomass (S/B, mass) of 0.24 yielded a biomass carbon conversion rate of 92%. This also resulted in a high degree of oxygen carrier reduction and a H₂/CO of 1.0 in the syngas produced. These findings suggest that the introduction of steam significantly enhances both the biomass carbon conversion and the H₂/CO in the syngas. The modulation of H₂O content within the CLRHP process facilitates the production of a high concentration of H₂. Concurrently, the integration of gases generated by both the BCLG and CLRHP processes yields a clean syngas characterized by an H₂/CO of 2.2 and a CO₂/CO of 0.67. Following 15 experimental cycles, the syngas generated via the BCLG-CLRHP process exhibited a H₂/CO of approximately 1.8 and a CO₂/CO of roughly 0.71. The proposed methodology holds potential for application in generating clean syngas with an H₂/CO ranging from 1.0 to 2.2. This could be beneficial for a variety of synthesis processes, including Fischer-Tropsch synthesis, acetic acid synthesis, and carbonyl synthesis.

Key words: biomass, syngas, chemical looping gasification, in-situ hydrogen replenishment, controllable H₂/CO, hydrogen production

摘要：

提出一种通过生物质化学链气化（biomass chemical looping gasification，BCLG）耦合水蒸气化学链重整制氢（chemical looping reforming hydrogen production，CLRHP）制备H₂/CO可控合成气的生物质化学链气化原位补氢（BCLG-CLRHP）的新型技术。以NiFe₂O₄（ZrO₂）为载氧体，在反应温度为900℃，晶格氧（OC）和生物质（B）的质量比为0.5时，合成气产率最高，为0.61 L/g（生物质）。在BCLG过程中，蒸汽（S）和生物质（B）的质量比为0.24时，生物质碳转化率为92%，载氧体还原程度较高且BCLG过程产生的合成气中H₂/CO达1.0，表明水蒸气的添加显著提高了生物质碳转化率和合成气中的H₂/CO。在CLRHP过程中调控水蒸气含量，可以制备高浓度H₂，同时整合BCLG与CLRHP过程产生的气体，可获得H₂/CO达2.2，CO₂/CO为0.67的清洁合成气。在15次循环实验后，BCLG-CLRHP过程制备的合成气中H₂/CO为1.8，CO₂/CO为0.71。所提出的方法可以潜在地应用于提供具有H₂/CO为1.0~2.2的清洁合成气，用于各种合成过程，例如费托合成、乙酸和羰基合成。

关键词: 生物质, 合成气, 化学链气化, 原位补氢, H₂/CO可控, 制氢

CLC Number:

TQ 032.4

Tianhao WU, Tingwei YE, Yan LIN, Zhen HUANG. In-situ hydrogen supplementation of biomass chemical looping gasification to produce syngas with controllable H₂/CO[J]. CIESC Journal, 2025, 76(7): 3498-3508.

吴天灏, 叶霆威, 林延, 黄振. 生物质化学链气化原位补氢制H₂/CO可控合成气[J]. 化工学报, 2025, 76(7): 3498-3508.

Figures/Tables 11

Fig.1 Schematic diagram of the BCLP-CLRHP process

Table 1 Proximate analysis and ultimate analysis of pine wood （dried basis）

元素分析/%					工业分析/%
C	H	O	N	S	灰分	挥发分	固定碳
49.69	6.51	43.75	0.04	0.01	0.61	85.7	13.69

Fig.2 Fixed bed reactor unit diagram

Fig.3 (a) Effect of reaction temperature on the gas products of the BCLG process; (b) Effect of reaction temperature on the carbon conversion and gas yield of the BCLG process; (c) Effect of reaction temperature on the H2/CO and CO2/CO in the syngas produced by BCLG; (d) XRD patterns of the OCs after the reaction at different reaction temperatures

Fig.4 (a) Effect of OC/B on gas products of BCLG process; (b) Effect of OC/B on carbon conversion and gas yield of BCLG process; (c) Effect of OC/B on H2/CO and CO2/CO in syngas produced by BCLG

Fig.5 (a) Effect of S/B on the gas products of BCLG process; (b) Effect of S/B on the carbon conversion as well as the gas yield of BCLG process; (c) Effect of S/B on the H2/CO as well as the CO2/CO in the syngas produced by BCLG; (d) XRD profiles of the OCs after the reaction with different S/B

Fig.6 (a) Effect of steam concentration on the relative concentration of CLRHP gas products; (b) Effect of S/B on the H2/CO as well as the CO2/CO in the total syngas; (c) XRD patterns of the OCs after the reaction with different vapor concentrations

Fig.7 (a) Effect of the number of cycles on the gas product of the BCLG process; (b) Effect of the number of cycles on the carbon conversion rate as well as the gas yield of the BCLG process

Fig.8 (a) Effect of the number of cycles on the gas products of the CLRHP process; (b) Effect of the number of cycles on the H2/CO as well as the CO2/CO in the total synthesis gas of BCLG-CLRHP

Fig.9 XRD analysis of fresh OCs versus those after 15 cycles

Fig.10 (a) SEM analysis of fresh OCs; (b) SEM analysis of OCs after 15 cycles; (c) H2-TPR curves of fresh and cycled OCs

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In-situ hydrogen supplementation of biomass chemical looping gasification to produce syngas with controllable H₂/CO

生物质化学链气化原位补氢制H₂/CO可控合成气

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