Recent progress in the production of hydrogen-rich syngas via supercritical water gasification of microalgae

doi:10.16085/j.issn.1000-6613.2024-0047

Abstract

Abstract:

Microalgae has the advantages of short growth cycle and high photosynthetic carbon fixation efficiency, which is mainly comprised of three carbon-containing compounds (namely carbohydrates, proteins and lipids). Microalgae is a renewable biomass resource with great potential for energy production. Supercritical water gasification technology can directly convert wet microalgae (with high moisture content) into hydrogen-rich syngas without the drying of microalgae. It can avoid massive energy consumption in microalgae dehydration and has the advantages of high reaction rate and high conversion efficiency. In recent years, supercritical water gasification of microalgae has received extensive attention from domestic and foreign researchers. This study aims to provide a comprehensive review of the recent advances in hydrogen production from microalgae supercritical water gasification. The main influence factors during microalgae supercritical water gasification process are discussed in detail, including reaction temperature, pressure, residence time, microalgae/water blending ratio and reactors. The influence mechanism of different catalysts on the supercritical water gasification process of microalgae is elucidated, and the reaction mechanism of the main model compounds of microalgae in the supercritical water gasification process is also discussed. The kinetic and thermodynamic characteristics of the microalgae supercritical water gasification process are summarized. Finally, the future research direction of microalgae supercritical water gasification for hydrogen-rich syngas production is proposed, which is expected to provide theoretical guidance for the fundamental research and practical application of microalgae supercritical water gasification technology.

Key words: microalgae, supercritical water gasification, hydrogen production, influence factor, catalyst, reaction mechanism

摘要：

微藻具有生长周期短、光合固碳效率高等优势，并且含有丰富的糖类、蛋白质和油脂等含碳化合物，是极具能源化和资源化利用潜力的可再生生物质资源。超临界水气化技术能够在不需要干燥微藻的条件下直接将高含水微藻转化为富氢合成气，可节约大量微藻脱水能耗，并且具有反应速率高、转化效率高等优势，近年来受到了国内外研究者的广泛关注。基于此，本文综述了近年来微藻超临界水气化制氢的研究进展，重点讨论了微藻超临界水气化反应的主要影响因素，包括反应温度、压力、停留时间、物料浓度和反应器类型，阐释了不同催化剂对微藻超临界水气化过程的影响和作用机理。并探讨了微藻主要三组分模型化合物在超临界水气化过程的反应机理，总结了微藻超临界水气化过程的动力学和热力学特性。最后展望了微藻超临界水气化制取富氢合成气技术的未来研究方向，为微藻超临界水气化制氢技术的研究与应用提供理论指导。

关键词: 微藻, 超临界水气化, 制氢, 影响因素, 催化剂, 反应机理

CLC Number:

GONG Decheng, SHEN Qian, ZHU Xianqing, HUANG Yun, XIA Ao, ZHANG Jingmiao, ZHU Xun, LIAO Qiang. Recent progress in the production of hydrogen-rich syngas via supercritical water gasification of microalgae[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3709-3728.

龚德成, 沈倩, 朱贤青, 黄云, 夏奡, 张敬苗, 朱恂, 廖强. 微藻超临界水气化制取富氢合成气的研究进展[J]. 化工进展, 2024, 43(7): 3709-3728.

Figures/Tables 18

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微藻	反应器类型	温度/℃	压力/MPa	停留时间/min	原料质量分数/%	H₂产量/mol·kg^-1	参考文献
Cladophora glomerata	间歇式反应釜	380~460	23.2~26.8	20	1	3.2~5.25	[30]
Enteromorpha intestinalis	间歇式反应釜	400~440	25	5~30	1	1.84~5.25	[31]
Ulva rotundata和armoricana	金刚石砧座	550	23.7	7	7, 16.4	2.65，1.80	[33]
Chlorella	间歇式反应釜	500	36	30	6.7	4.05	[50]
Chlorella sp.	间歇式反应釜	380	28	30	1.4	10.40	[43]
Chlorella pyrenoidosa	间歇式反应釜	430	22~55	60	100	1.61	[51]
Chlorella pyrenoidosa	间歇式反应釜	380~600	22~55	60	10	0.2~3.08	[37]
Spirulina	间歇式反应釜	500	36	30	6.7	4.87	[50]
Saccharina	间歇式反应釜	500	36	30	6.7	5.17	[50]
C. vulgaris	间歇式反应釜	385	26	15	5.0	4.13	[24]
S. quadricauda	间歇式反应釜	385	26	15	5.0	2.87	[24]
Nannochloropsis sp.	间歇式反应釜	450	—	40	4.8	2.40	[52]
Nannochloropsis sp.	间歇式反应釜	500	24	2~77	4.7	1.12~8.27	[53]
Botryococcus braunii, Nannochloropsis oculate, Tetraselmis chuii	间歇式反应釜	400	25	10	4.3	0.6，0.02，1.28	[54]
Nannochloropsis oculata	间歇式反应釜	440	28	15	-	4.3^①	[55]
Chlorella Vulgaris	连续式反应器	400~700	24	2	7.3	1.9%~18.7% （摩尔分数）^②	[23]
Nannochloropsis gaditana	连续式反应器	600	24~33	2	1	10.45	[56]

微藻	反应器类型	温度/℃	压力/MPa	停留时间/min	原料质量分数/%	H₂产量/mol·kg^-1	参考文献
Cladophora glomerata	间歇式反应釜	380~460	23.2~26.8	20	1	3.2~5.25	[30]
Enteromorpha intestinalis	间歇式反应釜	400~440	25	5~30	1	1.84~5.25	[31]
Ulva rotundata和armoricana	金刚石砧座	550	23.7	7	7, 16.4	2.65，1.80	[33]
Chlorella	间歇式反应釜	500	36	30	6.7	4.05	[50]
Chlorella sp.	间歇式反应釜	380	28	30	1.4	10.40	[43]
Chlorella pyrenoidosa	间歇式反应釜	430	22~55	60	100	1.61	[51]
Chlorella pyrenoidosa	间歇式反应釜	380~600	22~55	60	10	0.2~3.08	[37]
Spirulina	间歇式反应釜	500	36	30	6.7	4.87	[50]
Saccharina	间歇式反应釜	500	36	30	6.7	5.17	[50]
C. vulgaris	间歇式反应釜	385	26	15	5.0	4.13	[24]
S. quadricauda	间歇式反应釜	385	26	15	5.0	2.87	[24]
Nannochloropsis sp.	间歇式反应釜	450	—	40	4.8	2.40	[52]
Nannochloropsis sp.	间歇式反应釜	500	24	2~77	4.7	1.12~8.27	[53]
Botryococcus braunii, Nannochloropsis oculate, Tetraselmis chuii	间歇式反应釜	400	25	10	4.3	0.6，0.02，1.28	[54]
Nannochloropsis oculata	间歇式反应釜	440	28	15	-	4.3^①	[55]
Chlorella Vulgaris	连续式反应器	400~700	24	2	7.3	1.9%~18.7% （摩尔分数）^②	[23]
Nannochloropsis gaditana	连续式反应器	600	24~33	2	1	10.45	[56]

微藻	反应器类型	温度 /℃	压力 /MPa	反应时间 /min	原料浓度 (质量分数)/%	催化剂	H₂产量/mol·kg^-1	参考文献
Cladophora glomerata	间歇式反应釜	460	26.9	15	0.05g	衍生生物炭	5.78~9.1	[30]
Enteromorpha intestinalis	间歇式反应釜	440	25	10	1	Ru-Ni-Fe/γ-Al₂O₃	5.05~12.02	[31]
Chlorella pyrenoidosa	间歇式反应釜	380~600	22~55	60	10	Ru/C, Rh/C	1.77~4.30	[37]
Nannochloropsis sp.	间歇式反应釜	410	—	40	1.8, 4.3, 9, 13.5	Ru/C	11.48, 6.71, 3.87, 2.79	[38]
Spirulina platensis	间歇式反应釜	500	36	30	6.7	NaOH, Ni/Al₂O₃	4.66~11.31	[50]
Saccharina latissima	间歇式反应釜	500	36	30	6.7	NaOH, Ni/Al₂O₃	4.44~15.1	[50]
Chlorella vulgaris	间歇式反应釜	500	36	30	6.7	NaOH、Ni/Al₂O₃	4.6~11.83	[50]
Chlorella sp.	间歇式反应釜	380	28	30	1.4	Ni/rGO, Cu/rGO, Co/rGO, Mn/rGO, Cr/rGO	0.29~0.69	[43]
Chlorella pyrenoidosa	间歇式反应釜	430	22~55	60	1	Ru/C, Pd/C, Pd/C, Rh/C, Ir/C	3.80~5.97	[51]
C. vulgaris	间歇式反应釜	385	26	15-90	5.0	Ni/Al₂O₃	1.70~2.93	[24]
Nannochloropsis sp.	间歇式反应釜	450	—	40	4.8	Ru/C、NaOH、KOH	5.47~16.3	[52]
Botryococcus braunii,	间歇式反应釜	400	25	10	4.3	Ni、NaCl	0.16, 0.03, 0.05	[54]
Nannochloropsis oculate	间歇式反应釜	400	25	10	4.3	Ni、NaCl	0.73, 0.49	[54]
Tetraselmis chuii	间歇式反应釜	400	25	10	4.3	Ni、NaCl	0.29, 0.45, 1.99	[54]
Nannochloropsis oculata	间歇式反应釜	400~500	28	15	—	La-Ni/γ-Al₂O₃	13.8, 14.9	[55]
Scenedesmus sp.	间歇式反应釜	320~480	—	60	—	ZnO	21.2%~38.27% （质量分数）	[61]
Chlorella vulgaris	连续式反应器	650	30	—	—	衍生生物炭	19.13~46.95	[62]
C. glomerata	间歇式反应釜	460	26.9	10	—	衍生生物炭	7.85~11.63	[63]

微藻	反应器类型	温度 /℃	压力 /MPa	反应时间 /min	原料浓度 (质量分数)/%	催化剂	H₂产量/mol·kg^-1	参考文献
Cladophora glomerata	间歇式反应釜	460	26.9	15	0.05g	衍生生物炭	5.78~9.1	[30]
Enteromorpha intestinalis	间歇式反应釜	440	25	10	1	Ru-Ni-Fe/γ-Al₂O₃	5.05~12.02	[31]
Chlorella pyrenoidosa	间歇式反应釜	380~600	22~55	60	10	Ru/C, Rh/C	1.77~4.30	[37]
Nannochloropsis sp.	间歇式反应釜	410	—	40	1.8, 4.3, 9, 13.5	Ru/C	11.48, 6.71, 3.87, 2.79	[38]
Spirulina platensis	间歇式反应釜	500	36	30	6.7	NaOH, Ni/Al₂O₃	4.66~11.31	[50]
Saccharina latissima	间歇式反应釜	500	36	30	6.7	NaOH, Ni/Al₂O₃	4.44~15.1	[50]
Chlorella vulgaris	间歇式反应釜	500	36	30	6.7	NaOH、Ni/Al₂O₃	4.6~11.83	[50]
Chlorella sp.	间歇式反应釜	380	28	30	1.4	Ni/rGO, Cu/rGO, Co/rGO, Mn/rGO, Cr/rGO	0.29~0.69	[43]
Chlorella pyrenoidosa	间歇式反应釜	430	22~55	60	1	Ru/C, Pd/C, Pd/C, Rh/C, Ir/C	3.80~5.97	[51]
C. vulgaris	间歇式反应釜	385	26	15-90	5.0	Ni/Al₂O₃	1.70~2.93	[24]
Nannochloropsis sp.	间歇式反应釜	450	—	40	4.8	Ru/C、NaOH、KOH	5.47~16.3	[52]
Botryococcus braunii,	间歇式反应釜	400	25	10	4.3	Ni、NaCl	0.16, 0.03, 0.05	[54]
Nannochloropsis oculate	间歇式反应釜	400	25	10	4.3	Ni、NaCl	0.73, 0.49	[54]
Tetraselmis chuii	间歇式反应釜	400	25	10	4.3	Ni、NaCl	0.29, 0.45, 1.99	[54]
Nannochloropsis oculata	间歇式反应釜	400~500	28	15	—	La-Ni/γ-Al₂O₃	13.8, 14.9	[55]
Scenedesmus sp.	间歇式反应釜	320~480	—	60	—	ZnO	21.2%~38.27% （质量分数）	[61]
Chlorella vulgaris	连续式反应器	650	30	—	—	衍生生物炭	19.13~46.95	[62]
C. glomerata	间歇式反应釜	460	26.9	10	—	衍生生物炭	7.85~11.63	[63]

物性参数	热力学状态
物性参数	常态水	亚临界水	超临界水
温度/℃	0~100	100~374	>374
压力/MPa	0.025	0.1~22.1（100~374℃)	>22.1
聚合形态	液相	液相	无相分离
密度ρ/g·cm^-3	0.997（25℃）	0.80（250℃）	0.166（400℃, 25MPa）
介电常数ε	78.4（25℃）	27.1（250℃）	5.9（400℃, 25MPa）
比热容c_p /kJ·kg^-1·K^-1	4.18（25℃）	4.86（250℃）	13（400℃, 25MPa）
黏度μ/mPa·s	0.89（25℃）	0.11（250℃）	0.03（400℃, 25MPa）
热导率λ/W·m²·K^-1	607（25℃）	620（250℃）	160（400℃, 25MPa）
水的离子积K_w/mol²·L^-2	10^-14~10^-12（0~100℃）	10^-12~10^-11（100~300℃）	10^-20~10^-23（400~550℃）