壳聚糖接枝聚丙烯酸/凹凸棒石复合材料对毒死蜱的吸附行为

doi:10.16085/j.issn.1000-6613.2019-0227

摘要/Abstract

摘要：

以壳聚糖（chitosan，CTS）、丙烯酸（acrylic acid，AA）和凹凸棒石（attapulgite，ATP）为原料，利用分散聚合法制备壳聚糖接枝聚丙烯酸/凹凸棒石（CTS-g-PAA/ATP）复合吸附剂，以毒死蜱（chlorpyrifos，CPF）为模型农药，研究了复合吸附剂CTS-g-PAA/ATP在不同温度、时间和不同毒死蜱浓度下对毒死蜱的吸附性能，并对实验结果进行吸附热力学与动力学拟合分析。结果表明，CTS-g-PAA/ATP和HATP（酸化凹凸棒石）在24h和30℃下对毒死蜱的吸附量分别为7.42mg/g和18.95mg/g，复合材料的吸附能力提高了180%；拟合结果分析表明，吸附过程遵循Langmuir单分子层等温吸附（R²≥0.97），在30℃、35℃、40℃下理论上最大吸附量分别为57.8mg/g、54.3mg/g、51.2mg/g；并与准二级动力学模型精准拟合（R²≥0.97），化学吸附是吸附过程的主要控制因素。

关键词: 壳聚糖, 聚丙烯酸, 凹凸棒石, 毒死蜱, 吸附

Abstract:

A composite adsorbent CTS-g-PAA/ATP was synthesized by the materials of chitosan (CTS), acrylic acid and attapulgite (ATP) with the method of dispersion polymerization. Using the chlorpyrifos (CPF) as a model pesticide to study the adsorption performance of the composite adsorbent at different temperature, time and different chlorpyrifos concentration was introduced, and the adsorption thermodynamics and kinetics analysis were carried out to fit the experimental results. The results showed that the adsorption capacities of CTS-g-PAA/ATP and HATP (acidified attapulgite) on chlorpyrifos at 24h and 30℃ were 7.42g/g and 18.95mg/g, respectively, and the adsorption capacity of the composite increased by 180%. The results of the isotherm fitting analysis showed that the adsorption process followed the Langmuir model with the monolayer isotherm adsorption (R²≥0.97), and the theoretical maximum adsorption capacities were 57.8mg/g, 54.3mg/g and 51.2mg/g at 30℃, 35℃ and 40℃, respectively. With accurate fitting with the pseudo-second order kinetic model (R²≥0.97), chemical adsorption was the main controlling factor of the adsorption process in kinetics.

Key words: chitosan, polyacrylic acid, attapulgite, chlorpyrifos, adsorption

中图分类号:

TQ314

徐华, 温洪坚, 林建达, 周红军, 陈铧耀, 周新华. 壳聚糖接枝聚丙烯酸/凹凸棒石复合材料对毒死蜱的吸附行为[J]. 化工进展, 2019, 38(07): 3332-3340.

Hua XU, Hongjian WEN, Jianda LIN, Hongjun ZHOU, Huayao CHEN, Xinhua ZHOU. Adsorption performance of CTS-g-PAA/ATP composite on chlorpyrifos[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3332-3340.

图/表 15

图1 CTS-g-PAA/ATP合成示意图

图2 CTS-g-PAA/ATP、ATP、CTS和CTS-g-PAA的红外光谱

图3 HATP、CTS-g-PAA和CTS-g-PAA/ATP的SEM图

图4 HATP、 CTS-g-PAA、CTS-g-PAA/ATP和CTS的XRD光谱 a-HATP; b-CTS-g-PAA; c-CTS-g-PAA/ATP; d-CTS

图5 4种样品的TG和DSC图a-HATP； b-CTS-g-PAA/ATP； c-CTS-g-PAA； d-CTS

图6 不同材料的吸附性能对比

图7 CTS-g-PAA/ATP在不同浓度的毒死蜱下的吸附性能

表1 吸附热力学模型方程

热力学模型	方程式
Langmuir model	$C e Q e = 1 Q m a x ? C e + 1 K L Q m a x$	(3)
Freundlich model	$l g Q e = 1 n ? l g C e + l g K F$	(4)
Tempkin model	$Q e = B l n C e + B l n K T$	(5)

表1 吸附热力学模型方程

热力学模型	方程式
Langmuir model	$C e Q e = 1 Q m a x ? C e + 1 K L Q m a x$	(3)
Freundlich model	$l g Q e = 1 n ? l g C e + l g K F$	(4)
Tempkin model	$Q e = B l n C e + B l n K T$	(5)

表2 Langmuir、Freundlich和Tempkin等温吸附方程拟合参数

温度/℃	Langmuir等温吸附方程			Freundlich等温吸附方程			Tempkin等温吸附方程
温度/℃	Q_max/mg·g^-1	K_L/mg·g^-1	R²	n	K_F/mg·g^-1·(L·mg^-1)^1/ⁿ	R²	K_T/L·mg^-1	B	b_T/kJ·mol^-1	R²
30	57.8	2.86×10^-4	0.9724	1.21	4.15×10^-2	0.9721	0.833	9.52	0.264	0.9539
35	54.3	3.38×10^-4	0.9908	1.34	7.75×10^-2	0.9777	0.829	9.28	0.276	0.9493
40	51.2	3.97×10^-4	0.9863	1.37	8.99×10^-2	0.9844	0.828	9.56	0.272	0.9532

图8 Langmuir模型的线性拟合结果图

图9 CTS-g-PAA/ATP在不同吸附时间下的吸附性能

表3 吸附动力学模型方程

动力学模型	方程式
准一级模型	$l n q e, e x p - q t = k 1 t + l n q e, c a l$	(6)
准二级模型	$1 q t = 1 k 2 q e 2 ? 1 t + 1 q e$	(7)
Elovich方程	$q t = 1 b ? l n t + 1 b ? l n a b$	(8)
内扩散模型	$q t = k i d t 12 + C$	(9)
Bangham扩散模型	$l g l g C 0 C 0 - q t m = l g k 3 m 2.303 V + α l g t$	(10)

表3 吸附动力学模型方程

动力学模型	方程式
准一级模型	$l n q e, e x p - q t = k 1 t + l n q e, c a l$	(6)
准二级模型	$1 q t = 1 k 2 q e 2 ? 1 t + 1 q e$	(7)
Elovich方程	$q t = 1 b ? l n t + 1 b ? l n a b$	(8)
内扩散模型	$q t = k i d t 12 + C$	(9)
Bangham扩散模型	$l g l g C 0 C 0 - q t m = l g k 3 m 2.303 V + α l g t$	(10)

表4 准一级动力学和准二级动力学方程拟合参数

浓度/mg·mL^-1(温度/℃)	准一级动力学				准二级动力学
浓度/mg·mL^-1(温度/℃)	q_e,cal	q_e,exp	k₁	R²	q_e	k₂	R²
0.5 (30)	5.60	6.03	-0.0141	0.9417	9.30	7.70×10^-4	0.9868
1.0 (30)	9.32	11.32	-0.0215	0.9600	23.32	2.11×10^-4	0.9983
1.5 (30)	15.95	26.48	-0.0328	0.8836	69.59	3.85×10^-5	0.9968
2.0 (30)	18.95	27.67	-0.0304	0.9282	42.28	1.56×10^-4	0.9732
0.5 (35)	6.50	6.92	-0.0129	0.9857	15.34	2.73×10^-4	0.9932
1.0 (35)	10.06	13.01	-0.0239	0.9290	15.77	6.74×10^-4	0.9763
1.5 (35)	16.43	24.05	-0.0296	0.9305	58.48	6.03×10^-5	0.9972
2.0 (35)	19.80	31.60	-0.0345	0.9085	42.37	1.79×10^-4	0.9984
0.5 (40)	6.80	9.11	-0.0229	0.8413	17.39	2.74×10^-4	0.9949
1.0 (40)	10.95	13.52	-0.0255	0.9515	16.57	8.11×10^-4	0.9948
1.5 (40)	16.70	23.89	-0.0304	0.9475	52.91	8.09×10^-5	0.9960
2.0 (40)	21.00	27.18	-0.0284	0.9513	34.61	3.48×10^-4	0.9941

表5 Elovich动力学模型、颗粒内扩散方程和Bangham动力学模型拟合参数

浓度/mg·mL^-1(温度/℃)	Elovich动力学			颗粒内扩散方程			Bangham动力学
浓度/mg·mL^-1(温度/℃)	a	b	R²	k_id	C	R²	k₃	α	R²
0.5 (30)	0.0402	0.513	0.9166	0.433	-0.407	0.9360	3.17×10^-3	0.822	0.9708
1.0 (30)	0.0224	0.272	0.9603	0.830	-0.700	0.9600	3.27×10^-3	0.800	0.9892
1.5 (30)	0.0102	0.139	0.9696	1.545	-1.605	0.9424	2.85×10^-3	0.919	0.9878
2.0 (30)	0.0099	0.122	0.9487	1.825	-1.591	0.9479	3.26×10^-3	0.824	0.9743
0.5 (35)	0.0332	0.446	0.9598	0.487	-0.494	0.9459	3.00×10^-3	0.880	0.9917
1.0 (35)	0.0224	0.256	0.9391	0.903	-0.696	0.9641	3.75×10^-3	0.750	0.9869
1.5 (35)	0.0109	0.139	0.9773	1.577	-1.444	0.9522	3.14×10^-3	0.879	0.9847
2.0 (35)	0.0110	0.122	0.9766	1.908	-1.296	0.9710	3.76×10^-3	0.767	0.9897
0.5 (40)	0.0296	0.375	0.9493	0.593	-0.550	0.9530	3.48×10^-3	0.854	0.9901
1.0 (40)	0.0278	0.251	0.9797	0.994	-0.401	0.9900	4.75×10^-3	0.663	0.9967
1.5 (40)	0.0116	0.139	0.9835	1.614	-1.277	0.9594	3.42×10^-3	0.844	0.9783
2.0 (40)	0.0138	0.126	0.9855	1.960	-0.797	0.9859	4.59×10^-3	0.678	0.9886

图10 不同温度下准二级动力学模型的线性拟合结果图

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