Research progress on absorption-microalgae fixation of low concentration CO2 and synchronous oil production in gas power plant

doi:10.16085/j.issn.1000-6613.2022-1320

Abstract

Abstract:

Gas power plants use stable and clean fossil energy to generate electricity. The capture and resource utilization of low concentration CO₂ produced in the production process under the background of double carbon are very important for carbon neutralization. In view of the difficulty of low concentration CO₂ capture and high desorption cost, a new way to solve the problem of low concentration CO₂capture and resource utilization is provided by using CO₂ absorbent solution to culture microalgae to produce oil. The absorbent solution with high capture capacity to CO₂ and simultaneous fast cultivation ability to microalgae is decisive factor for the design and preparation of solution. This paper summarizes the application of the existing absorbent solution, and combs out the development prospect of carbon capture of compound absorbent solution coupled with microalgae nutrition regulation. Moreover, the alkalinity and salinity of the absorbent solution are the most significant factors affecting the CO₂ assimilation by microalgae. The effects of different temperature and light conditions on the bioconversion of CO₂ by microalgae are discussed. The different effects of CO₂ gas flowing into the reactor by means of microporous bubbling and airlift diversion on CO₂ capture and microalgae growth are described. From the perspective of promoting CO₂ absorption and simultaneously producing oil by microalgae, the progress of algal species mutation, acclimatization, and genetic modification is introduced. In addition, the economic viability of absorption-microalgae method to realize carbon neutralization in gas power plant is analyzed according to case study. Compared with the traditional CO₂ absorption and microalgae fixation methods, the integrated absorption-microalgae method provide a competitive alternative for gas power plants to achieve carbon neutralization.

Key words: absorption-microalgae method, low concentration CO₂, absorbent solution, biodiesel, mutagenesis, genetic modification

摘要：

燃气电厂利用稳定、清洁的化石能源发电，在“双碳”背景下发电过程产生的低浓度CO₂的捕集和资源化利用，对于实现碳中和至关重要。针对低浓度CO₂捕集难度大、脱附费用高的问题，利用CO₂吸收液同步培养微藻产油提供了一种实现低浓度CO₂捕集与资源化利用于一体的新途径。具有高CO₂捕集能力和同时快速培养微藻能力的吸收液是溶液设计和配制的决定性因素。本文总结了现有吸收液的应用现状，梳理出复合吸收液耦合微藻营养调控的碳捕集发展前景，其中吸收液的碱度和盐度对微藻同化CO₂具有显著影响。讨论了在不同温度和光照的工艺条件对微藻生物转化CO₂的影响，阐述了CO₂气体以微孔鼓泡和气升导流的方式通入反应器对CO₂捕集和微藻生长的不同效果。从促进微藻吸收CO₂同步产油的角度，介绍了藻种诱变驯化和基因改造以提升环境适应性同时增强脂质生产的研究进展，最后通过经济分析展望了规模化应用吸收-微藻法的经济可行性。与传统的CO₂吸收和微藻固定方法相比，吸收-微藻法一体化复合工艺可以成为从燃气电厂中捕获 CO₂具有竞争力的替代方案。

关键词: 吸收-微藻法, 低浓度CO₂, 吸收液, 生物柴油, 诱变, 基因改造

CLC Number:

QIN Zhenfang, LIAO Rihong, MA Weifang. Research progress on absorption-microalgae fixation of low concentration CO₂ and synchronous oil production in gas power plant[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 94-106.

秦振芳, 廖日红, 马伟芳. 吸收-微藻法固定燃气电厂低浓度CO₂同步产油技术研究进展[J]. 化工进展, 2023, 42(1): 94-106.

Figures/Tables 10

项目	超低排放燃煤电厂	燃气电厂
CO₂体积分数/%	10~16	3~5
H₂O体积分数/%	5~9	7~9
N₂体积分数/%	73~77	73~75
O₂体积分数/%	3~7	11~13
NO _x 浓度/mg·m^-3	22~44	15~30
SO _x 浓度/mg·m^-3	8~24	0~5

项目	Heynigia riparia SX01	Dunaliella salina	Chlorella vulgaris P12	Scenedesmus obtusiusculus	Chlorella vulgaris (ISC-23)
CO₂体积分数/%	5（混合空气）	6（混合空气）	6（混合空气）	4~5（烟气成分）	6（混合空气）
CO₂固定效率/g·L^-1·d^-1	0.370	0.067	2.290	0.111	3.222
微藻生物量/g·L^-1	2.37	0.26	10	1.09	14.30

吸收液类型	成分化学式	常用吸收液	吸收反应式	优缺点	参考文献
胺基溶液	RNH₂	伯胺：MEA 仲胺：DEA 叔胺：MDEA	(1) RNH₂+CO₂+H₂O $⇌$ RNH₃+HCO₃ (2) 2RNH₂+CO₂ $⇌$ RNH₃+RNHCOO	优点：低CO₂下有高水溶性，相当大的吸收动力学速率；稳定性好缺点：吸收效率差；易被O₂降解，产生腐蚀性；CO₂负载量低	[44]
碳酸盐溶液	RCO₃	K₂CO₃、Na₂CO₃	RCO₃+CO₂+H₂O $⇌$ RHCO₃	优点：成本低；CO₂在溶剂中溶解度高；溶剂毒性低；不易降解，不易被腐蚀；缺点：反应速度慢；强腐蚀性	[45]
氨溶液	NH₃	NH₃	(1) CO₂+NH₃ $⇌$ NH₂COONH₄ (2) NH₂COONH₄+H₂O $⇌$ NH₄HCO₃+NH₃ (3) NH₄HCO₃+NH₃ $⇌$ (NH₄)₂ CO₃ (4) NH₂COONH₄+CO₂+H₂O $⇌$ 2NH₄HCO₃ (5) CO₂+NH₃+H₂O $⇌$ NH₄HCO₃	优点：在烟气环境中降解率低；腐蚀程度低；易再生，吸收能力高；可与污染性气体NO _x 反应缺点：NH₃逃逸率高	[43]
氨基酸盐溶液	RR'NH	脯氨酸钾/钠、赖氨酸钾/钠、甘氨酸钾、肌氨酸钾、氨基酸钠	(1) CO₂+RR'NH $⇌$ RR'N⁺HCOO^- (2) RR'N+HCOO^-+B $⇌$ RR'’N COO^-+BH⁺ （R代表CHCOO^-，R'代表氨基酸盐离子， B是溶液中的任何碱）	优点：低挥发性；低毒性；良好的生物降解潜力；不易被烟气中O₂降解缺点：再生能耗高；易沉淀和堵塞装置	[46]

吸收液类型	成分化学式	常用吸收液	吸收反应式	优缺点	参考文献
胺基溶液	RNH₂	伯胺：MEA 仲胺：DEA 叔胺：MDEA	(1) RNH₂+CO₂+H₂O $⇌$ RNH₃+HCO₃ (2) 2RNH₂+CO₂ $⇌$ RNH₃+RNHCOO	优点：低CO₂下有高水溶性，相当大的吸收动力学速率；稳定性好缺点：吸收效率差；易被O₂降解，产生腐蚀性；CO₂负载量低	[44]
碳酸盐溶液	RCO₃	K₂CO₃、Na₂CO₃	RCO₃+CO₂+H₂O $⇌$ RHCO₃	优点：成本低；CO₂在溶剂中溶解度高；溶剂毒性低；不易降解，不易被腐蚀；缺点：反应速度慢；强腐蚀性	[45]
氨溶液	NH₃	NH₃	(1) CO₂+NH₃ $⇌$ NH₂COONH₄ (2) NH₂COONH₄+H₂O $⇌$ NH₄HCO₃+NH₃ (3) NH₄HCO₃+NH₃ $⇌$ (NH₄)₂ CO₃ (4) NH₂COONH₄+CO₂+H₂O $⇌$ 2NH₄HCO₃ (5) CO₂+NH₃+H₂O $⇌$ NH₄HCO₃	优点：在烟气环境中降解率低；腐蚀程度低；易再生，吸收能力高；可与污染性气体NO _x 反应缺点：NH₃逃逸率高	[43]
氨基酸盐溶液	RR'NH	脯氨酸钾/钠、赖氨酸钾/钠、甘氨酸钾、肌氨酸钾、氨基酸钠	(1) CO₂+RR'NH $⇌$ RR'N⁺HCOO^- (2) RR'N+HCOO^-+B $⇌$ RR'’N COO^-+BH⁺ （R代表CHCOO^-，R'代表氨基酸盐离子， B是溶液中的任何碱）	优点：低挥发性；低毒性；良好的生物降解潜力；不易被烟气中O₂降解缺点：再生能耗高；易沉淀和堵塞装置	[46]

吸收液类型	吸收液成分	微藻种类	CO₂占比	反应器	培养基	CO₂固定率	微藻生物量/ 生长速率	脂质产量	参考文献
碳酸盐溶液	K₂CO₃	Chlorella sp.	0.5和0.7的CO₂负载	锥形瓶	改良F 培养基	—	最大体积生产率：0.380g·L^-1·d^-1 生物质浓度：1.80g·L^-1	—	[47]
	Na₂CO₃	Euhalothece ZM001	—	T形瓶反应器（含剪切力）	标准M 培养基	59%	4.79g·L^-1 最大生物质产率：1.210g·L^-1·d^-1	—	[48]
	Na₂CO₃	Scenedesmus sp.	10%	玻璃瓶持续通气	BG-11 培养基	6.6%	259mg·L^-1	22.43~ 90.85mg·L^-1	[49]
	Na₂CO₃	Euhalothece sp.	35mmol·L_PBR^-1·d^-1	锥形瓶	M培养基	(0.422± 0.057)g·L^-1·d^-1	最大比生长率：1.670d^-1 生物质产率：(0.845± 0.113)g·L^-1·d^-1	—	[50]
	Na₂CO₃	T.elongatus BP-1	6.3%	静态混合-平板气升式反应器	BG-11 培养基	—	最大生物质产率：2.900g_DW·L^-1·d^-1	—	[51]
胺基溶液	MEA	Spirulina	$0.36 m L C O 2$ ·mL_medium·d^-1	半连续管式生物器	Zarrouk 培养基	16%	生物质产率：62.100mg·L^-1·d^-1	8.3%±1.4%	[52]
	TEA	Scenedesmus sp.	4%	管式玻璃鼓泡反应器	BG-11 培养基	增加了30.5%	生物质产率：664.600mg·L^-1·d^-1	—	[53]
	AMP	Scenedesmusaccuminatus	0~5%	管式玻璃鼓泡反应器	BG-11 培养基	619mg·L^-1·d^-1	细胞密度：1780mg·L^-1	—	[53]
	DEA	Coccomyxasubellipsoidea C-169	2%	管式生物器	Basal 培养基	0.97g·L^-1	生物质产率：225.980mg·L^-1·d^-1	产量：64.33%; 产率： 59.900mg·L^-1·d^-1	[54]
	DEA	Chlamydomonas sp.； Chlorella sp.； Pseudochlorococcum sp.	纯CO₂	烧瓶（螺旋管通气）	营养培养基	0.012mol·mL^-1·d^-1;0.135mol·mL^-1·d^-1; 0.012mol·mL^-1·d^-1;	比生长率： 0.365d^-1; 0.352d^-1; 0.669d^-1	—	[55]
混合吸收液	DEA+ K₂CO₃	Spirulina	0.36mL $C O 2$ ·mL_medium·d^-1	管式生物器	Zarrouk 培养基	43.7%	生物质产率：174.200mg·L^-1·d^-1	—	[56]
	NH₃+ K₂CO₃	Chlorella sp.	5%	锥形烧瓶	BG-11 培养基	>60%	生物质产率：49mg·L^-1·d^-1	59mg·L^-1·d^-1	[57]
	MDEA+ PZ	Chlorella sorokiniana BTA 9031	15%	锥形烧瓶	BG-11 培养基	72.4%~84.8%	最大生物质浓度：(1.20±0.028)g·L^-1	最高：23%±0.013%	[58]

吸收液类型	吸收液成分	微藻种类	CO₂占比	反应器	培养基	CO₂固定率	微藻生物量/ 生长速率	脂质产量	参考文献
碳酸盐溶液	K₂CO₃	Chlorella sp.	0.5和0.7的CO₂负载	锥形瓶	改良F 培养基	—	最大体积生产率：0.380g·L^-1·d^-1 生物质浓度：1.80g·L^-1	—	[47]
	Na₂CO₃	Euhalothece ZM001	—	T形瓶反应器（含剪切力）	标准M 培养基	59%	4.79g·L^-1 最大生物质产率：1.210g·L^-1·d^-1	—	[48]
	Na₂CO₃	Scenedesmus sp.	10%	玻璃瓶持续通气	BG-11 培养基	6.6%	259mg·L^-1	22.43~ 90.85mg·L^-1	[49]
	Na₂CO₃	Euhalothece sp.	35mmol·L_PBR^-1·d^-1	锥形瓶	M培养基	(0.422± 0.057)g·L^-1·d^-1	最大比生长率：1.670d^-1 生物质产率：(0.845± 0.113)g·L^-1·d^-1	—	[50]
	Na₂CO₃	T.elongatus BP-1	6.3%	静态混合-平板气升式反应器	BG-11 培养基	—	最大生物质产率：2.900g_DW·L^-1·d^-1	—	[51]
胺基溶液	MEA	Spirulina	$0.36 m L C O 2$ ·mL_medium·d^-1	半连续管式生物器	Zarrouk 培养基	16%	生物质产率：62.100mg·L^-1·d^-1	8.3%±1.4%	[52]
	TEA	Scenedesmus sp.	4%	管式玻璃鼓泡反应器	BG-11 培养基	增加了30.5%	生物质产率：664.600mg·L^-1·d^-1	—	[53]
	AMP	Scenedesmusaccuminatus	0~5%	管式玻璃鼓泡反应器	BG-11 培养基	619mg·L^-1·d^-1	细胞密度：1780mg·L^-1	—	[53]
	DEA	Coccomyxasubellipsoidea C-169	2%	管式生物器	Basal 培养基	0.97g·L^-1	生物质产率：225.980mg·L^-1·d^-1	产量：64.33%; 产率： 59.900mg·L^-1·d^-1	[54]
	DEA	Chlamydomonas sp.； Chlorella sp.； Pseudochlorococcum sp.	纯CO₂	烧瓶（螺旋管通气）	营养培养基	0.012mol·mL^-1·d^-1;0.135mol·mL^-1·d^-1; 0.012mol·mL^-1·d^-1;	比生长率： 0.365d^-1; 0.352d^-1; 0.669d^-1	—	[55]
混合吸收液	DEA+ K₂CO₃	Spirulina	0.36mL $C O 2$ ·mL_medium·d^-1	管式生物器	Zarrouk 培养基	43.7%	生物质产率：174.200mg·L^-1·d^-1	—	[56]
	NH₃+ K₂CO₃	Chlorella sp.	5%	锥形烧瓶	BG-11 培养基	>60%	生物质产率：49mg·L^-1·d^-1	59mg·L^-1·d^-1	[57]
	MDEA+ PZ	Chlorella sorokiniana BTA 9031	15%	锥形烧瓶	BG-11 培养基	72.4%~84.8%	最大生物质浓度：(1.20±0.028)g·L^-1	最高：23%±0.013%	[58]

性状	微藻	诱变方法	改进后性状	参考文献
高生长速率	Chlorella sp.	Se-137-伽马射线照射突变	生物质产量提高25%	[87]
高生长速率	Chlorella vulgaris	紫外线照射突变	比增长率提高29.4%	[88]
对环境的高耐受性	Chlorella sp. S30	ALE	得到耐受30g·L^-1盐的淡水菌株	[89]
脂质的高产量	Desmodesmus sp.	大气和室温等离子体的突变	脂质生产增加>100%	[90]
	Chlorella L166	低温等离子体（LTP）	油脂含量提高>12%	[91]
	Tetraselmis sp.	EMS	产脂率最高达到48%±0.9%	[92]

基因改造方法	微藻	目标基因	对基因表达的影响	改进结果	参考文献
参与脂质生物合成的酶的过度表达	Fistuliferasolaris	G6PD和PGD的过度表达	5.5倍和4.8倍增长	脂质产量增加1.5倍	[93]
参与脂质生物合成的酶的过度表达	Neochloris oleoabundans	DGAT2的过度表达	2倍增长	总脂质含量增加1.6~2.3倍，总脂质生产力增加1.6~3.2倍；而TAG含量增加1.8~3.2倍，TAG生产力增加1.6~4.3倍	[94]
阻断竞争途径	Chlamydomonasreinhardtii	ADP-葡萄糖焦磷酸化酶（AGPase）	钝化AGPase钝化	TAG含量增加10倍	[95]
阻断竞争途径	Thalassiosirapseudonana	脂肪酶/磷脂酶/脂酰基转移酶	RNAi方法	脂质含量增加3.5倍	[96]
改变脂肪酸链长度	Phaeodactylumtricornutum	Δ 5去饱和酶 PtD5b的过表达	3.2倍增长	单不饱和脂肪酸（MUFA）和多不饱和脂肪酸（PUFA）分别增加了75%和64%	[97]
改变脂肪酸链长度	Chlamydomonas reinhardtii	Cracs1/Cracs2的敲除	减少55%	分泌的FAs可以达到8.19mg·（10⁹细胞）^-1和9.66mg·（10⁹细胞）^-1	[98]

因素	假设参数
S-V比/m^-1	4
太阳辐射/MJ·m^-2·d^-1	20
光合效率/%	2~6
CO₂固定率/%	0、10、25、40
特定种植成本/CNY·m^-3	1080~2160
特定运营成本/CNY·dt^-1	720~1224
特定能耗/W·m^-3	4
(意外开支+所有者成本)/%	30
贴现现金流/%	8

财务参数	价值
总收益/CNY·a^-1	33582953
总运营成本/CNY·a^-1	29511332
EBITDA/CNY·a^-1	4071627
折旧、利息、维修费/CNY·a^-1	3572957
净收益/CNY·a^-1	498663
ROI/%	10
回报时间/a	10

项目	传统化学吸收法	吸收-微藻法
固定资本/10⁶CNY	552	357
运行费用/10⁶CNY·a^-1	44	113
预期收入/10⁶CNY·a^-1	—	100

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[15]	Zejian HUANG,Yiqing LUO,Xigang YUAN. Environmental impact assessment of water treatment integrated microalgae biodiesel life cycle system [J]. Chemical Industry and Engineering Progress, 2020, 39(1): 34-41.

Research progress on absorption-microalgae fixation of low concentration CO₂ and synchronous oil production in gas power plant

吸收-微藻法固定燃气电厂低浓度CO₂同步产油技术研究进展

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