Calcined Mg/Al hydrotalcites for CO2 removal in anaerobic digestion biogas: Performances and mechanisms

doi:10.16085/j.issn.1000-6613.2023-1272

Abstract

Abstract:

Carbon dioxide (CO₂) in the anaerobic digestion biogas can decrease the utility value of biogas, and removing CO₂ efficiently is the research hotspot in the biogas utilization area. Calcined Mg/Al hydrotalcites (CLDHs) has desirable CO₂ adsorption property. In this study, Box-Behnken model in the response surface methodology was applied to optimize the condition for CO₂ adsorption by CLDHs, and the effects of adsorbents dosage, calcination temperature and reaction temperature on adsorption performances were investigated. The CO₂ adsorption mechanisms were analyzed by adsorbents characterization and adsorption process test. Experimental results indicated that adsorbents dosage, calcination temperature and reaction temperature all showed significant effects on CO₂adsorption performance, and the optimal adsorption conditions were: CLDHs dosage of 0.016g/mL, calcination temperature of 400℃ and reaction temperature of 55℃. Under the optimal conditions, CO₂content decreased from initial 23.51% to 0, and CO₂adsorption capacity of 0.625mmol/g and CH₄ recovery rate of 94.7% were achieved. Meanwhile, adsorbent had desirable regeneration property after 6 cycles of adsorption-desorption. The adsorption process test and adsorbents characterization results, including X-ray diffractometer (XRD), Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), specific surface area, point of zero charge and pore structure, revealed that the CO₂ adsorption process was very quick, and the surface basic sites adsorption as well as layer anion intercalation promoted CO₂adsorption simultaneously.

Key words: calcined Mg/Al hydrotalcites, anaerobic digestion biogas, CO₂ adsorption, response surface methodology optimal design, adsorption mechanisms

摘要：

厌氧消化沼气中含有的CO₂会降低沼气利用价值，高效去除CO₂是沼气利用领域的研究热点。焙烧镁铝水滑石具有良好的CO₂吸附性能，本文利用响应面法的Box-Behnken模型优化CO₂吸附条件，考察吸附剂剂量、焙烧温度和反应温度对吸附效果的影响；通过吸附材料表征、吸附过程测定分析吸附作用机制。实验结果表明，吸附剂剂量、焙烧温度和反应温度均对CO₂吸附有显著影响，最适宜的吸附条件为：投加量0.016g/mL、400℃焙烧、55℃反应。在此条件下，沼气中的CO₂体积分数从23.51%降至0，CO₂吸附容量为0.625mmol/g，CH₄回收率为94.7%，经过6次循环吸附后，吸附剂仍具有良好的再生性能。吸附过程及吸附材料的X射线衍射、扫描电子显微镜、傅里叶变换红外光谱、比表面积、等电点及孔结构测试结果表明，焙烧镁铝水滑石的吸附过程十分迅速，表面碱性位点吸附及层间阴离子插层作用同时促进了CO₂吸附。

关键词: 焙烧镁铝水滑石, 厌氧消化沼气, CO₂吸附, 响应面法优化设计, 吸附机理

CLC Number:

X511

WU Yuqi, LI Jiangtao, DING Jianzhi, SONG Xiulan, SU Bingqin. Calcined Mg/Al hydrotalcites for CO₂ removal in anaerobic digestion biogas: Performances and mechanisms[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5250-5261.

吴宇琦, 李江涛, 丁建智, 宋秀兰, 苏冰琴. 焙烧镁铝水滑石脱除厌氧消化沼气中CO₂的效果及机制[J]. 化工进展, 2024, 43(9): 5250-5261.

Figures/Tables 15

References 30

1	ANDRIAMANOHIARISOAMANANA Fetraj, IHARA Ikko, YOSHIDA Gen, et al. Comparative effects of ferric hydroxide and (semi) conductive iron oxides on the anaerobic digestion of oxytetracycline-contaminated dairy manure[J]. Journal of Environmental Management, 2022, 310: 114731.
2	LU Tiedong, ZHANG Junya, LI Ping, et al. Enhancement of methane production and antibiotic resistance genes reduction by ferrous chloride during anaerobic digestion of swine manure[J]. Bioresource Technology, 2020, 298: 122519.
3	WU Yuqi, SONG Kang. Anaerobic co-digestion of waste activated sludge and fish waste: Methane production performance and mechanism analysis[J]. Journal of Cleaner Production, 2021, 279: 123678.
4	FU Shanfei, CHEN Kaiqiang, SUN Wenxin, et al. Improved methane production of corn straw by the stimulation of calcium peroxide[J]. Energy Conversion and Management, 2018, 164: 36-41.
5	包海军. 我国沼气提纯技术及生物天然气产业发展情况[J]. 中国沼气, 2021, 39(1): 54-58.
	BAO Haijun. Biogas purification technology and development of biogas industry in China[J]. China Biogas, 2021, 39(1): 54-58.
6	韩文彪, 王毅琪, 徐霞, 等. 沼气提纯净化与高值利用技术研究进展[J]. 中国沼气, 2017, 35(5): 57-61.
	HAN Wenbiao, WANG Yiqi, XU Xia, et al. Progress on purification and high value application of biogas[J]. China Biogas, 2017, 39(1): 54-58.
7	何东发. 厌氧消化技术在造纸废水治理中的应用[J]. 能源研究与利用, 2021(6): 42-45.
	HE Dongfa. Application of anaerobic digestion technology in papermaking wastewater treatment[J]. Energy Research and Utilization, 2021(6): 42-45.
8	Ammarali ABD, OTHMAN Mohdroslee, SHAMSUDIN Ilikhairunnisa, et al. Biogas upgrading to natural gas pipeline quality using pressure swing adsorption for CO₂ separation over UiO-66: Experimental and dynamic modelling assessment[J]. Chemical Engineering Journal, 2023, 453: 139774.
9	TABAR Mohammadazadi, HOSSEINI Seyedsaeid, DENAYER Joerifm. A multicolumn vacuum pressure swing adsorption biogas upgrading process for simultaneous CO₂ and N₂ separation from methane: Exergy and energy analysis[J]. Energy Conversion and Management, 2022, 269: 116060.
10	曲伟国, 张磊, 张淑玲. 沼气提纯脱碳工艺探讨[J]. 燃气与热力, 2016, 36(4): 17-21.
	QU Weiguo, ZHANG Lei, ZHANG Shuling. Discussion on biogas purification and decarbonization process[J]. Gas＆Heat, 2016, 36(4): 17-21.
11	周春萍, 张夏卿, 姜哲. 氨基改性过程引入去离子水对层状双氢氧化物CO₂吸附性能的影响规律研究[J]. 功能材料, 2014, 22(45): 22021-22025.
	ZHOU Chunping, ZHANG Xiaqing, JIANG Zhe. Absorption capacity of carbon dioxide on Mg/Al layered double hydroxide with deionized water adding during amine modified process[J]. Journal of Functional Materials, 2014, 22(45): 22021-22025.
12	WU Yuqi, WU Zichuan, YANG Chunfan, et al. Layered double hydroxides for phosphorus recovery from lipid-rich waste anaerobic fermentation liquor[J]. Journal of Environmental Management, 2023, 326: 116759.
13	LUNDEHOJ L, JENSEN H C, WYBRANDT L, et al. Layered double hydroxides for phosphorus recovery from acidified and non-acidified dewatered sludge[J]. Water Research, 2019, 153: 208-216.
14	赵雨, 田念, 王家炜, 等. 复合氨基改性Mg-Al LDH的制备及其CO₂吸附性能的研究[J].高校化学工程学报, 2018, 32(3): 659-666.
	ZHAO Yu, TIAN Nian, WANG Jiawei, et al. Synthesis of amine modified Mg-Al LDH and their CO₂ adsorption characteristics[J]. Journal of Chemical Engineering of Chinese Universities, 2018, 3(32): 659-666.
15	孔婷婷. 钛锂铝类水滑石/炭复合材料的制备及CO₂吸附与光催化研究[D]. 西安: 西安科技大学, 2017.
	KONG Tingting. Preparation and CO₂ adsorption, photocatalysis performance of Ti/Li/Al-LDHs/coke composite[D]. Xi’an: Xi’an University of Science and Technology, 2017.
16	王君雅, 羊莹, 宁平. 碱金属硝酸盐对促进LDH基材料吸附CO₂性能的影响[J]. 环境工程学报, 2018, 12(12): 3379-3388.
	WANG Junya, YANG Ying, NING Ping. Effect of alkali metal nitrates promoted LDH-based material for CO₂ sorption performance[J]. Chinese Journal of Environmental Engineering, 2018, 12(12): 3379-3388.
17	MAARTEN Everaert, RUBEN Warrinnier, STIJIN Baken, et al. Phosphate-exchanged Mg-Al layered double hydroxides: A new slow release phosphate fertilizer[J]. ACS Sustainable Chemistry＆Engineering, 2016, 4, 4280-4287.
18	张国臣. 十二烷基磺酸钠插层有机层状双氢氧化物制备及吸附性能研究[D]. 济南: 山东大学, 2012.
	ZHANG Guochen. Study on preparation and sorption behavior of sodium dodecylsulfonate intercalated organo layered double hydroxide[D]. Jinan: Shandong University, 2012.
19	邓林. 镁铝水滑石基复合材料吸附去除水中铬(Ⅵ)、磷酸盐的研究[D]. 长沙: 湖南大学, 2015.
	DENG Lin. Study on removal of chromium(Ⅵ) and phosphate from aqueous solution using Mg-Al hydrotalcite-based composites[D]. Changsha: Hunan University, 2015.
20	ABED Marwaf, FAISAL Ayadah. Calcium/iron-layered double hydroxides-sodium alginate for removal of tetracycline antibiotic from aqueous solution[J]. Alexandria Engineering Journal, 2023, 63: 127-142.
21	孔婷婷, 董羿蘩, 张颖萍, 等. 类水滑石Ti/Li/Al-LDHs的制备及其CO₂吸附性能[J]. 燃料化学学报, 2016, 44(8): 1017-1024.
	KONG Tingting, DONG Yifan, ZHANG Yingping, et al. Preparation of hydrotalcite-like Ti/Li/Al-LDHs and its performance in CO₂ adsorption[J]. Journal of Fuel Chemistry and Technology, 2016, 44(8): 1017-1024.
22	MA Xiao, YE Jiongjiong, JIANG Li, et al. Alkaline fermentation of waste activated sludge with calcium hydroxide to improve short-chain fatty acids production and extraction efficiency via layered double hydroxides[J]. Bioresource Technology, 2019, 279: 117-123.
23	KARIM Ansafv, HASSANI Aydin, EGHBALI Paria, et al. Nanostructured modified layered double hydroxides (LDHs)-based catalysts: A review on synthesis, characterization, and applications in water remediation by advanced oxidation processes[J]. Current Opinion in Solid State and Materials Science, 2022, 26(1): 100965.
24	SHENG Liang, LIU Jianyong, ZHANG Cheng, et al. Pretreating anaerobic fermentation liquid with calcium addition to improve short chain fatty acids extraction via in situ synthesis of layered double hydroxides[J]. Bioresource Technology, 2019, 271: 190-195.
25	WANG Jian, ZHANG Yan, SI Jiwen, et al. Structural engineering of NiFe-layered double hydroxides and halloysite composites for efficient CO₂ capture[J]. Chemical Engineering Journal, 2023, 463: 142502.
26	REDDY M K R, XU Z P, LU G Q, et al. Layered double hydroxides for CO₂ capture: Structure evolution and regeneration[J]. Industrial＆Engineering Chemistry Research, 2006, 45: 7504-7509.
27	ZHENG Dayang, WU Min, ZHENG Eryang, et al. Parallel adsorption of low concentrated ciprofloxacin by a CoFe-LDH modified sludge biochar[J]. Journal of Environmental Chemical Engineering, 2022, 10: 108381.
28	JIANG Li, LIU Jianyong, ZHANG Cheng, et al. Synthesis of layered double hydroxides with fermentation liquid of organic waste to extract short-chain fatty acids as a biodenitrification carbon source[J]. ACS Sustainable Chemistry＆Engineering, 2017, 5: 9095-9101.
29	ZHOU Tao, WU Shuya, SU Lianghu, et al. Innovative integrated technique for nutrient acquisition: Simultaneous recovery of carbon and nitrogen sources from the anaerobic fermentation liquid of food waste[J]. ACS Sustainable Chemistry＆Engineering, 2018, 6: 10944-10951.
30	ZHANG Weijun, CHENG Haowan, PENG Sainan, et al. Performance and mechanisms of wastewater sludge conditioning with slag-based hydrotalcite-like minerals (Ca/Mg/Al-LDH)[J]. Water Research, 2020, 169: 115265.

因素	编码变量		各水平编码取值
因素	编码值	非编码值	-1	0	1
焙烧温度/℃	x₁	X₁	200	400	600
反应温度/℃	x₂	X₂	25	40	55
剂量/g·mL^-1	x₃	X₃	0.008	0.012	0.016

因素	编码变量		各水平编码取值
因素	编码值	非编码值	-1	0	1
焙烧温度/℃	x₁	X₁	200	400	600
反应温度/℃	x₂	X₂	25	40	55
剂量/g·mL^-1	x₃	X₃	0.008	0.012	0.016

编号	x₁	x₂	x₃	吸附后沼气体积分数/%		CO₂占比降低率/%		CO₂吸附容量 /mmol·g^-1
编号	x₁	x₂	x₃	CH₄	CO₂	实测值	预测值	CO₂吸附容量 /mmol·g^-1
1	0	0	0	59.35	2.80	88.09	84.14	0.723
2	-1	1	0	55.85	9.72	58.67	58.60	0.537
3	0	0	0	58.68	3.81	83.79	84.14	0.760
4	-1	-1	0	54.56	13.19	43.89	43.20	0.480
5	1	-1	0	56.42	8.70	63.01	63.08	0.600
6	1	1	0	56.78	7.37	68.67	69.36	0.637
7	0	0	0	58.83	3.84	83.67	84.14	0.730
8	-1	0	1	58.47	6.32	73.12	71.61	0.495
9	0	0	0	57.79	4.03	82.86	84.14	0.730
10	-1	0	-1	53.49	15.07	35.92	38.19	0.645
11	0	-1	1	60.66	0.72	96.94	99.14	0.610
12	1	0	1	59.46	0.82	96.51	94.24	0.608
13	0	1	-1	59.63	6.71	71.46	69.26	0.980
14	1	0	-1	53.99	13.00	44.70	46.21	0.730
15	0	0	0	58.37	4.16	82.30	84.14	0.727
16	0	1	1	62.44	0	100.00	100.00	0.625
17	0	-1	-1	55.16	11.38	51.61	50.03	0.790

编号	x₁	x₂	x₃	吸附后沼气体积分数/%		CO₂占比降低率/%		CO₂吸附容量 /mmol·g^-1
编号	x₁	x₂	x₃	CH₄	CO₂	实测值	预测值	CO₂吸附容量 /mmol·g^-1
1	0	0	0	59.35	2.80	88.09	84.14	0.723
2	-1	1	0	55.85	9.72	58.67	58.60	0.537
3	0	0	0	58.68	3.81	83.79	84.14	0.760
4	-1	-1	0	54.56	13.19	43.89	43.20	0.480
5	1	-1	0	56.42	8.70	63.01	63.08	0.600
6	1	1	0	56.78	7.37	68.67	69.36	0.637
7	0	0	0	58.83	3.84	83.67	84.14	0.730
8	-1	0	1	58.47	6.32	73.12	71.61	0.495
9	0	0	0	57.79	4.03	82.86	84.14	0.730
10	-1	0	-1	53.49	15.07	35.92	38.19	0.645
11	0	-1	1	60.66	0.72	96.94	99.14	0.610
12	1	0	1	59.46	0.82	96.51	94.24	0.608
13	0	1	-1	59.63	6.71	71.46	69.26	0.980
14	1	0	-1	53.99	13.00	44.70	46.21	0.730
15	0	0	0	58.37	4.16	82.30	84.14	0.727
16	0	1	1	62.44	0	100.00	100.00	0.625
17	0	-1	-1	55.16	11.38	51.61	50.03	0.790

方差来源	平方和	自由度	均方	F	P	显著性
模型	6237.35	9	693.04	94.11	<0.0001	**
X₁	469.56	1	469.56	63.76	<0.0001	**
X₂	234.90	1	234.90	31.90	0.0008	**
X₃	3316.24	1	3316.24	450.33	<0.0001	**
X₁X₂	20.79	1	20.79	2.82	0.1368
X₁X₃	53.36	1	53.36	7.25	0.0310	*
X₂X₃	70.48	1	70.48	9.57	0.0175	*
X₁²	1948.31	1	1948.31	264.57	<0.0001	**
X₂²	69.78	1	69.78	9.48	0.0179	*
X₃²	0.02	1	0.02	0.0027	0.9601
残差	51.55	7	7.36
失拟项	30.58	3	10.19	1.94	0.2643	不显著
净误差	20.97	4	5.24
总离差	6288.89	16
R²	0.9918
R²_校正	0.9813
R²_预测	0.9170
精密度	30.457

Calcined Mg/Al hydrotalcites for CO₂ removal in anaerobic digestion biogas: Performances and mechanisms

焙烧镁铝水滑石脱除厌氧消化沼气中CO₂的效果及机制

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 15

References 30

Related Articles 2

Recommended Articles

Metrics

Comments

样品	比表面积/m²·g^-1	总孔容/cm³·g^-1	平均孔径/nm
初始LDHs	130.32	0.380	11.66
CLDHs₂₀₀	130.92	0.382	11.66
CLDHs₄₀₀	153.24	0.483	12.61
CLDHs₆₀₀	184.98	0.873	18.87

[1]	BAI Yadi, DENG Shuai, ZHAO Ruikai, ZHAO Li, YANG Yingxia. Exploration on standardized test scheme and experimental performance of temperature swing adsorption carbon capture unit [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3834-3846.
[2]	Hongxia GUO, Yan NAN, Xiaochen KOU, Shengping WANG, Yujun ZHAO, Xinbin MA. Research on doping modification and morphology control of calcium-based CO₂ sorbents [J]. Chemical Industry and Engineering Progress, 2019, 38(01): 457-466.