活性焦吸附TNT废水

doi:10.12382/bgxb.2025.0635

摘要/Abstract

摘要：

为寻找可低成本处理含有三硝基甲苯（2，4，6-trinitrotoluene，TNT）废水的吸附材料，采用褐煤制备的活性焦（Activited Coke，AC）吸附含有TNT的废水，分析动力学和热力学规律、吸附前后AC表面和热重差热变化，结果表明：AC吸附TNT的动力学符合拟二级动力学模型，颗粒内扩散是其限速步骤，吸附过程是一个吸热过程、以化学吸附为主；Redlich-Peterson吸附等温线模型更适合拟合AC吸附TNT的过程；当TNT浓度为98.8mg/L，AC浓度为2.5g/L，pH为中性，温度为40℃，振荡时间为360min时，TNT去除率可达99.4%；吸附TNT前后AC的表面孔隙被堵塞，热解峰温从546.5℃降低至521.5℃、热流量从178.5mW增大至209.6mW。

关键词: 三硝基甲苯, 活性焦, 吸附法

Abstract:

In order to find a low-cost absorbent material to treat the wastewater containing 2，4，6-trinitrotoluene （TNT），the activated coke （AC） prepared from lignite is used to adsorb the wastewater containing TNT，and the kinetics and thermodynamics of AC，and the differences of AC surface and DSC-TGA before and after adsorption are studied.The results show that the adsorption kinetics of AC adsorbing TNT conforms to the pseudo-second order kinetic model，and the intraparticle diffusion of TNT onto AC is identified to be the rate limiting step.The adsorption process of TNT by AC is an endothermic process，and mainly chemical adsorption process.The Redlich-Peterson isotherm model is more suitable to fit the adsorption process of TNT by AC.When the concentration of TNT is 98.8mg/L，the dose of AC is 2.5g/L，pH is neutral，the temperature is 40℃，and the oscillation period is 360min，99.4% of TNT can be removed.The surface pores of AC are blocked after adsorbing TNT.The peak temperature of DSC-TGA decreases from 546.5℃ to 521.5℃，and its heat flow increases from 178.5mW to 209.6mW.

Key words: 2，4，6-trinitrotoluene, activated coke, adsorption

张默贺, 庞思平. 活性焦吸附TNT废水[J]. 兵工学报, 2025, 46(S1): 250635-.

ZHANG Mohe, PANG Siping. Study on the Adsorption of TNT Wastewater by Activated Coke[J]. Acta Armamentarii, 2025, 46(S1): 250635-.

图/表 18

表1 AC的物理化学特性

Table 1 Physical and chemical properties of AC

物理特性	数值
比表面积/（m²·g^-1）	414.3247
总孔隙体积/（m³·g^-1）	0.266118
平均孔径/nm	2.6059
堆积密度/（g·cm^-3）	0.55
显性密度/（g·cm^-3）	0.39
在氮气实际压力和饱和蒸汽压力的比值条件下直径小于363.8383nm的孔的单点总孔径	0.99467422
化学特性	质量百分比/%
C	76.77
H	1.02
N	0.66
Ash	21.55

图1 不同粒径AC对TNT吸附效果影响

Fig.1 The effect of different particle sizes on the adsorption of TNT by AC

图2 pH对AC吸附TNT的影响

Fig.2 The effect of pH on the adsorption of TNT by AC

图3 反应时间对AC吸附TNT的影响

Fig.3 The effect of response time on the adsorption of TNT by AC

图4 接触时间对AC吸附TNT的影响

Fig.4 The effect of contact time on the adsorption of TNT by AC

图5 AC吸附TNT的拟一级动力学模型

Fig.5 The pseudo-first-order kinetic model of the adsorption of TNT by AC

图6 AC吸附TNT的拟二级动力学模型

Fig.6 The pseudo-second-order kinetic model of the adsorption of TNT by AC

表2 AC吸附TNT的吸附动力学参数

Table 2 Kinetics parameters for the adsorption of TNT by AC

T / ℃	q_e/ （mg· g^-1）	拟一级动力学			拟二级动力学
T / ℃	q_e/ （mg· g^-1）	q₁/ （mg· g^-1）	k₁/ （min^-1）	${R}_{1}^{2}$	q₂/ （mg· g^-1）	k₂/（g· mg^-1· min^-1）	h/ （mg· g^-1· min^-1）	${R}_{2}^{2}$
20	40.9	30.8	9.86×10^-3	0.991	44.2	5.76×10^-4	1.13	0.996
30	41.3	26.6	9.72×10^-3	0.967	44.1	6.16×10^-4	1.42	0.998
40	44.8	31.3	1.04×10^-2	0.990	47.9	6.72×10^-4	1.47	0.997

图7 qt随t0.5的变化的颗粒内扩散曲线（pH值：7；温度：40℃；TNT初始浓度：87.5mg/L；AC质量：1.5g/L）

Fig.7 Intraparticle diffusion plot for qt and t0.5 （pH：7； T：40℃；initial concentration of TNT：87.5mg/L； AC dosage：1.5g/L）

图8 不同温度下AC吸附TNT的等温曲线

Fig.8 Isotherm curves of TNT onto AC at various temperatures

图9 AC吸附TNT的Langmuir模型

Fig.9 The Langmuir model of the adsorption of TNT by AC

图10 AC吸附TNT的Freundlich模型

Fig.10 The Freundlich model of the adsorption of TNT by AC

表3 AC吸附TNT的等温曲线参数

Table 3 Isotherm parameters for the adsorption of TNT onto AC

T/ ℃	Langmuir 吸附模型			Freundlich 吸附模型			Redlich-Peterson 吸附模型
T/ ℃	q_m/ （mg· g^-1）	K_a/ （L· mg^-1）	${R}_{4}^{2}$	K_F	n	${R}_{5}^{2}$	A/ （L· mg^-1）^g	B/ （L· g^-1）	g	${R}_{6}^{2}$
20	59.5	6.03 ×10^-2	0.997	13.5	3.28	0.994	12.5	-0.421	0.764	0.999
30	53.3	1.27 ×10^-1	0.989	23.3	5.79	0.849	21.7	-0.324	0.880	0.994
40	69.5	5.97 ×10^-2	0.965	15.5	3.25	0.903	40.6	-0.835	0.718	0.984

图11 不同质量AC对TNT去除率的影响

Fig.11 The effect of AC dose on TNT removal efficiency

图12 吸附前后AC表面形貌

Fig.12 ESEM photographs of AC before and after adsorption

表4 吸附前后的AC表面的元素重量比

Table 4 The element weight of AC before and after adsorption %

状态	C	N	H
吸附前AC	76.77	0.66	1.02
吸附后AC	71.53	1.53	1.03

图13 吸附前后AC的热重差热变化

Fig.13 DSC-TGA of AC before and after adsorption

表5 不同吸附剂吸附TNT 的对比分析

Table 5 Comparison of different adsorbents adsorbing TNT

	吸附量/ （mg（TNT）·g^-1）	吸附剂价格/ （元·g^-1）	效费比/ （mg（TNT）·元^-1）
椰壳活性炭	161.3	0.003	5.37×10⁴
木质素活性炭	55.7	0.0015	3.71×10⁴
AC	58.3	0.0005	1.17×10⁵

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