改性蓝藻基活性炭的制备及常压下对CO2的捕集性能

doi:10.7503/cjcu20170480

摘要/Abstract

摘要：

以蓝藻为前驱体, 采用KOH活化法制备了一系列蓝藻基活性炭; 探讨了活化时间、活化温度以及碱炭比等活化参数对其孔结构的影响; 进一步分别用HNO₃, HPO₄和NH₃·H₂O进行二次改性, 制备了N或P原子掺杂的改性蓝藻基活性炭, 研究了不同改性活性炭在25 ℃和1.01×10⁵ Pa条件下对CO₂的吸附捕集性能. 结果表明, KOH活化的最佳活化时间为2 h, 活化温度800 ℃, 碱炭比为2. 样品ACK-2-8在该条件下对CO₂的吸附量达到3.85 mmol/g. 二次改性后的样品ACK-2-8-1, ACK-2-8-2和ACK-2-8-3对CO₂的吸附量分别高达4.41, 3.97和4.63 mmol/g. N的掺杂有利于CO₂的吸附捕集. 多批次重复再生实验结果表明, 本材料对CO₂吸附再生具有较稳定的重复利用性.

关键词: 蓝藻基活性炭, KOH活化, CO2的吸附, N掺杂

Abstract:

A series of porous carbon sorbents obtained through carbonization and KOH activation of the abundant waste materials cyanobacteria or further modified by HNO₃, HP $O 4$ or NH₃·H₂O was utilized for CO₂ adsorption. During the optimal activation parameters experiments, the activation time, activation temperature and the KOH/C mass ratio were 2 h, 800 ℃ and 2, respectively. Sample ACK-2-8 was capable of uptake CO₂ capacities near 3.85 mmol/g at 25 ℃ and 1.01×10⁵ Pa. At the same time, the secondary modification samples of ACK-2-8-1, ACK-2-8-2 and ACK-2-8-3 exhibited CO₂ uptake capacities up to 4.41, 3.97 and 4.63 mmol/g in turn. It was notable that the N-doping enhanced CO₂ uptake from samples ACK-2-8-1 or ACK-2-8-3. It could be reused for five batches of continuous operation without a significant loss of CO₂ uptake capacity and thus has a great potential of real-world applications.

Key words: Cyanobacteria-derived activated carbon, KOH activation, CO2 uptake, N-Doping

中图分类号:

O647
X51

TrendMD:

高俊, 胡辉, 刘雪岩. 改性蓝藻基活性炭的制备及常压下对CO₂的捕集性能. 高等学校化学学报, 2018, 39(2): 284.

GAO Jun, HU Hui, LIU Xueyan. Preparation and Evaluation of Modified Cyanobacteria-derived Activated Carbon for CO₂ Adsorption^†. Chem. J. Chinese Universities, 2018, 39(2): 284.

图/表 12

Fig.1 TG(a) and DTG(b) curves of cyanobacteria

Table 1 Proximate and ultimate analysis of cyanobacteria

Proximate analysis^a		Ultimate analysis
Component	Mass fraction(%)	Element	Mass fraction(%)
Moisture	15.03	C	43.28
Volatile	68.04	H	6.36
Ash	5.97	O^b	35.81
Fixed carbon	10.96	N	7.70
		S	0.88

Fig.2 Effects of activation time on N2 adsorption-desorption experiment of ACK-2-7(a), ACK-2-8(b) and ACK-3-8(c)

Table 2 Structural parameters for AC and ACK-X-Y samples

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	V_micro(cm³·g^-1)	$D ?$ /nm
AC	10.7	0.011		4.02
ACK-1-6	705	0.429	0.344	4.62
ACK-1-7	932	0.514	0.425	2.87
ACK-1-8	1247	0.646	0.491	2.65
ACK-2-6	1006	0.578	0.505	2.30
ACK-2-7	1694	0.887	0.700	2.10
ACK-2-8	1951	1.092	0.756	2.27
ACK-3-6	970	0.545	0.454	2.23
ACK-3-7	1111	0.592	0.487	2.13
ACK-3-8	1854	0.992	0.724	2.26

Table 2 Structural parameters for AC and ACK-X-Y samples

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	V_micro(cm³·g^-1)	$D ?$ /nm
AC	10.7	0.011		4.02
ACK-1-6	705	0.429	0.344	4.62
ACK-1-7	932	0.514	0.425	2.87
ACK-1-8	1247	0.646	0.491	2.65
ACK-2-6	1006	0.578	0.505	2.30
ACK-2-7	1694	0.887	0.700	2.10
ACK-2-8	1951	1.092	0.756	2.27
ACK-3-6	970	0.545	0.454	2.23
ACK-3-7	1111	0.592	0.487	2.13
ACK-3-8	1854	0.992	0.724	2.26

Fig.3 N2 adsorption-desorption isotherms(A) and pore diameter distributions(B) of ACK-2-Y and ACK-3-8 samples

Fig.4 N2 adsorption-desorption isotherms(A) and pore diameter distributions(B) of ACK-2-8 and ACK-2-8-X

Table 3 Structural parameters and CO2 adsorption capacity(25 ℃) for ACK-2-8 and ACK-2-8-X samples

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	V_micro/(cm³·g^-1)	$D ?$ /nm	CO₂ uptake at 1.01×10⁵ Pa/(mmol·g^-1)
ACK-2-8	1951	1.092	0.756	2.27	3.85
ACK-2-8-1	1846	1.023	0.735	2.22	4.41
ACK-2-8-2	1901	1.026	0.726	2.26	3.97
ACK-2-8-3	2125	1.238	0.834	2.33	4.63

Table 3 Structural parameters and CO2 adsorption capacity(25 ℃) for ACK-2-8 and ACK-2-8-X samples

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	V_micro/(cm³·g^-1)	$D ?$ /nm	CO₂ uptake at 1.01×10⁵ Pa/(mmol·g^-1)
ACK-2-8	1951	1.092	0.756	2.27	3.85
ACK-2-8-1	1846	1.023	0.735	2.22	4.41
ACK-2-8-2	1901	1.026	0.726	2.26	3.97
ACK-2-8-3	2125	1.238	0.834	2.33	4.63

Fig.5 SEM images of samples AC(A), ACK-2-8(B), ACK-2-8-1(C), ACK-2-8-2(D) and ACK-2-8-3(E)

Fig.6 XPS spectra of carbon materials with further modified on sample ACK-2-8 (A) ACK-2-8-1, N1s; (B) ACK-2-8-2, P2p; (C) ACK-2-8-3, N1s.

Fig.7 CO2 uptake isotherms measured at 25 ℃ for AC, AC-2-8 and AC-2-8-X samples

Table 4 Comparison of CO2 adsorption and SBET on various materials

Sample	S_BET/(m²·g^-1)	CO₂ uptake at 1.01×10⁵ Pa/(mmol·g^-1)	Ref.
ACK-2-8	1951	3.85	This work
ACK-2-8-1	1846	4.41	This work
ACK-2-8-2	1901	3.97	This work
ACK-2-8-3	2125	4.63	This work
N-doped porous carbons NC-1-600	807	4.07	[2]
NC-2-600	986	4.61	[2]
N-doped porous carbons(coconut shell) NC-650-3	1535	4.8	[3]
NC-700-3	1596	4.7	[3]
NC-700-4	1937	4.4	[3]
Porous carbon(petroleum coke) K4-700	1745	3.45	[12]
Porous carbon(rice husk char) PC1-710	1041	4.16	[13]
PC3-780	2695	3.71	[13]
Activated carbon(bamboo) bamboo-3-873	1846	4.5	[16]
N-doped active carbon(chitosan) AC800	728	4.17	[21]
Activated carbons(pine cone shell) PAC-650/2	3135	4.73	[28]
Activated carbon(petroleum coke) UC-650-2	1394	4.4	[29]
Porous carbon(popcorn) PC-0.5K	867	4.6	[30]
Porous carbon(waste polyurethane foam) PUF-400-KOH-1-700	1516	4.33	[31]

Fig.8 Relationship between the amount of CO2 adsorbed and running times for sample ACK-2-8-X

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改性蓝藻基活性炭的制备及常压下对CO₂的捕集性能

Preparation and Evaluation of Modified Cyanobacteria-derived Activated Carbon for CO₂ Adsorption^†

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