生物质化学链气化原位补氢制H2/CO可控合成气

doi:10.11949/0438-1157.20241392

摘要/Abstract

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

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

中图分类号:

TQ 032.4

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.

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.

图/表 11

图1 BCLP-CLRHP工艺示意图

Fig.1 Schematic diagram of the BCLP-CLRHP process

表1 松木的元素分析和工业分析（干基）

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

图2 固定床反应器装置图

Fig.2 Fixed bed reactor unit diagram

图3 (a)反应温度对BCLG过程气体产物的影响；(b)反应温度对BCLG过程碳转化率以及气体产率的影响；(c)反应温度对BCLG产生合成气中H2/CO以及CO2/CO的影响；(d)不同反应温度反应后载氧体的XRD谱图

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

图4 (a)OC/B对BCLG过程气体产物的影响；(b)OC/B对BCLG过程碳转化率以及气体产率的影响；(c)OC/B对BCLG产生合成气中H2/CO以及CO2/CO的影响

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

图5 (a)S/B对BCLG过程气体产物的影响；(b)S/B对BCLG过程碳转化率以及气体产率的影响；(c)S/B对BCLG产生合成气中H2/CO以及CO2/CO的影响；(d)不同S/B反应后载氧体的XRD谱图

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

图6 (a)水蒸气浓度对CLRHP气体产物相对浓度的影响；(b)S/B对总合成气中H2/CO以及CO2/CO的影响；(c)不同蒸汽浓度反应后载氧体的XRD谱图

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

图7 (a)循环次数对BCLG过程气体产物的影响；(b)循环次数对BCLG过程碳转化率以及气体产率的影响

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

图8 (a)循环次数对CLRHP过程气体产物的影响；(b)循环次数对BCLG-CLRHP总合成气中H2/CO以及CO2/CO的影响

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

图9 新鲜载氧体与循环15次后载氧体的XRD分析

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

图10 (a)新鲜载氧体的SEM分析；(b)循环15次后载氧体的SEM分析；(c)新鲜和循环后的载氧体的H2-TPR曲线

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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生物质化学链气化原位补氢制H₂/CO可控合成气

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

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