球磨改性热解炭吸附磺胺甲唑

doi:10.16085/j.issn.1000-6613.2021-1819

摘要/Abstract

摘要：

针对热解炭颗粒大、表面活性弱、吸附能力差的问题，本文提出了一种机械球磨表面改性方法，探讨了不同球磨改性参数下热解炭对磺胺甲唑（SMZ）的吸附效果。以废橡胶连续热解炭为原料，采用不锈钢球磨制得具有不同表面性质的球磨炭，分析了球磨前后热解炭的结构、表面性质及表面形貌，并对比了球磨改性前后的SMZ吸附性能。结果表明，球磨改性过程可以有效改善废轮胎热解炭结构及表面性质，球磨处理2h的热解炭对SMZ的吸附效果最好，吸附量达到59.37mg/g，吸附动力学符合伪二级吸附模型。

关键词: 球磨, 活性炭, 吸附, 磺胺甲唑, 废物处理

Abstract:

Aiming at the problems of large particles of pyrolysis carbon, weak surface activity and poor adsorption capacity, a mechanical ball milling surface modification method was proposed, and the adsorption effect of pyrolysis carbon on sulfamethoxazole (SMZ) under different ball milling modification parameters was discussed. Using waste rubber continuous pyrolysis carbon as raw material, stainless steel ball milling was used to prepare ball milled carbon with different surface properties. The structure, surface properties and surface morphology of the pyrolysis carbon before and after ball milling were analyzed, and the SMZ adsorption before and after ball milling modification was compared. The results showed that the ball milling modification process can effectively improve the structure and surface properties of the pyrolysis carbon of waste tires. The pyrolysis carbon after the ball milling treatment for 2hours had the best adsorption effect on SMZ and the adsorption amount can reach 59.37mg/g. The adsorption kinetics was in line with the pseudo two-stage adsorption model.

Key words: ball-milled, activated carbon, adsorption, sulfamethoxazole, waste treatment

中图分类号:

TE992.3

黄平安, 徐俊, 杨宇轩, 潘宇涵, 王新文, 黄群星. 球磨改性热解炭吸附磺胺甲唑[J]. 化工进展, 2022, 41(7): 3784-3793.

HUANG Ping’an, XU Jun, YANG Yuxuan, PAN Yuhan, WANG Xinwen, HUANG Qunxing. Ball milled modified pyrolysis carbon adsorb sulfamethoxazole[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3784-3793.

图/表 15

表1 球磨前后热解炭的粒度参数

样品	最小粒径/μm	最大粒径/μm	平均粒径/μm	d₉₀/μm
C	0.08	541.89	120.30	278.50
BM0.5	0.08	43.67	14.07	30.24
BM1	0.34	2.92	1.31	2.15
BM2	0.31	2.92	1.19	2.11
BM5	0.28	2.92	1.12	2.11
BM10	0.28	2.92	1.09	2.08

图1 球磨前后热解炭的粒度分布曲线

图2 球磨前后热解炭的结构

表2 球磨前后热解炭的吸附能力、结构参数、平均粒度

样品	S_BET/m²?g^-1	S_micro/m²?g^-1	RS_micro/%	PS/nm	V_total/cm³?g^-1	V_micro/cm³?g^-1	RV_micro/%	DP/μm
C	88.31	8.03	9.09	28.57	0.63	0.0025	0.39	120.30
BM0.5	112.87	17.06	15.11	13.61	0.38	0.0073	1.90	14.07
BM1	113.52	20.14	17.74	11.57	0.33	0.0092	2.80	1.31
BM2	223.73	101.44	45.34	5.56	0.31	0.0433	13.91	1.19
BM5	203.03	94.75	46.67	5.54	0.28	0.0402	14.31	1.12
BM10	113.97	44.27	38.84	7.71	0.22	0.0190	8.64	1.09

图3 球磨前后热解炭的SEM图

表3 球磨前后热解炭的EDS数据(质量分数)

样品	元素/%
样品	C	O	S	Si
C	76.88	20.56	2.07	0.49
BM0.5	76.14	21.69	1.83	0.35
BM1	76.51	21.86	1.22	0.42
BM2	73.19	23.80	2.40	0.62
BM5	70.20	26.25	2.85	0.70
BM10	68.46	28.19	2.67	0.68

图4 球磨前后热解炭的FTIR曲线

图5 球磨前后热解炭的XPS图谱

图6 球磨前后热解炭的吸附等温线和吸附能力

表4 两种等温线模型的拟合参数

样品	Langmuir等温线模型			Freundlich等温线模型
样品	q_m/mg·g^-1	K_L	R²	K_F	n	R²
C	1.939	0.255	0.984	0.590	3.214	0.909
BM0.5	26.767	0.278	0.989	7.463	2.821	0.947
BM1	27.981	0.324	0.992	8.192	2.879	0.923
BM2	55.424	0.942	0.990	21.238	3.036	0.830
BM5	50.118	0.816	0.990	18.974	3.099	0.867
BM10	33.897	0.293	0.993	9.452	2.774	0.938

图7 吸附能力与结构参数之间的线性关系

图8 吸附动力学实验及拟合曲线

表5 两种动力学模型的拟合参数

样品	伪一级动力学模型			伪二级动力学模型
样品	k₁/mg $?$ g^-1 $?$ min^-1	q_e，cal/mg $?$ g^-1	R²	k₂/g $?$ mg^-1	q_e，cal/mg $?$ g^-1	R²
C	0.00099	1.31	0.946	0.0062	4.63	0.999
BM0.5	0.0012	6.42	0.965	0.0015	28.80	0.999
BM1	0.0013	9.29	0.971	0.0010	32.63	0.999
BM2	0.0012	12.82	0.944	0.0008	68.68	0.999
BM5	0.0014	16.81	0.919	0.0006	67.80	0.999
BM10	0.0015	14.77	0.976	0.0006	43.74	0.999

表5 两种动力学模型的拟合参数

样品	伪一级动力学模型			伪二级动力学模型
样品	k₁/mg $?$ g^-1 $?$ min^-1	q_e，cal/mg $?$ g^-1	R²	k₂/g $?$ mg^-1	q_e，cal/mg $?$ g^-1	R²
C	0.00099	1.31	0.946	0.0062	4.63	0.999
BM0.5	0.0012	6.42	0.965	0.0015	28.80	0.999
BM1	0.0013	9.29	0.971	0.0010	32.63	0.999
BM2	0.0012	12.82	0.944	0.0008	68.68	0.999
BM5	0.0014	16.81	0.919	0.0006	67.80	0.999
BM10	0.0015	14.77	0.976	0.0006	43.74	0.999

表6 粒子扩散模型的拟合参数

样品	k_d1/mg $?$ g^-1 $?$ min^-0.5①	k_d2/mg $?$ g^-1 $?$ min^-0.5②
C	0.05	0.02
BM0.5	0.35	0.11
BM1	0.60	0.15
BM2	1.01	0.19
BM5	1.63	0.25
BM10	0.89	0.22

表6 粒子扩散模型的拟合参数

样品	k_d1/mg $?$ g^-1 $?$ min^-0.5①	k_d2/mg $?$ g^-1 $?$ min^-0.5②
C	0.05	0.02
BM0.5	0.35	0.11
BM1	0.60	0.15
BM2	1.01	0.19
BM5	1.63	0.25
BM10	0.89	0.22

图9 球磨前后热解炭上磺胺甲唑（SMZ）的吸附机理

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