焙烧镁铝水滑石脱除厌氧消化沼气中CO2的效果及机制

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

摘要/Abstract

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

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

中图分类号:

X511

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.

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.

图/表 15

参考文献 30

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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

焙烧镁铝水滑石脱除厌氧消化沼气中CO₂的效果及机制

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

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参考文献 30

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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

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