磺化偶联改性赤泥对垃圾渗滤液中COD和氨氮的吸附特性

黄明琴; 蔡深文; 程俊伟; 曾伯平

doi:10.12476/kczhly.202307020358

磺化偶联改性赤泥对垃圾渗滤液中COD和氨氮的吸附特性

遵义师范学院，贵州　遵义　563006

基金项目: 遵义市科技计划项目（遵市科合HZ字[2022]140）；贵州省教育厅青年科技人才成长项目（黔教合KY字[2020]104）；赤水河流域环境保护与山地农业发展人才基地

详细信息

作者简介: 黄明琴（1987-），女，硕士，讲师，研究方向为固废资源化与环境监测

通讯作者: 蔡深文（1984-），男，博士，教授，主要从事环境污染物的生态效应及机制研究

中图分类号: TD989

收稿日期: 2023-07-02

刊出日期: 2025-08-25

Adsorption of COD and Ammonia Nitrogen in Landfill Leachate on Red Mud Modified by Sulfonation Coupling

Zunyi Normal University, Zunyi, Guizhou 563006, China

More Information

Corresponding author: CAI Shenwen, caishenwen@163.com

Received Date: 02 July 2023

Publish Date: 25 August 2025

摘要

摘要:
以对氨基苯磺酸钠和硅烷偶联剂（KH560）为改性剂，对铝业赤泥进行了磺化偶联改性，并用于垃圾渗滤液的吸附处理，研究了溶液pH值、吸附剂投加量、吸附时间、反应温度等对COD和氨氮的吸附影响，采用红外光谱和扫描电镜对改性赤泥进行表征，并就吸附等温线、动力学和热力学特征进行了探讨。结果表明：磺化偶联改性赤泥（SCRM）对渗滤液中COD和氨氮的吸附效果显著提高，在溶液pH值为8，投加量60 g /L，吸附时间90 min，反应温度20 ℃条件下，对COD和氨氮的平衡吸附量可达81.51 mg /g 和19.24 mg /g，去除率分别达87.57%和72.05%。改性后赤泥颗粒孔道结构由浅隙孔转变为贯穿孔，并出现明显的磺化特征基团。SCRM对COD和氨氮的吸附分别属于单层吸附和多层吸附，吸附动力学更符合拟二级动力学模型，且均为吸热、熵增的自发反应过程。
- 赤泥 /
- 磺化偶联 /
- 吸附 /
- COD /
- 氨氮
Abstract:
Using polysodium p-styrene sulfonate and silane coupling agent (KH560) as modifiers, red mud was modified by sulfonation and coupling, and used in the adsorption treatment of landfill leachate. The effects of pH value, dosage of adsorbent, adsorption time and reaction temperature on the adsorption of COD and ammonia nitrogen were studied. The modified red mud was characterized by infrared spectroscopy and scanning electron microscope and the isotherm, kinetic and thermodynamic of adsorption were also discussed. The results showed that the adsorption effect of red mud modified by sulfonation coupling (SCRM) on COD and ammonia nitrogen in leachate was significantly improved. At the conditions of pH value 8, dosage of 60 g/L, adsorption time of 90 min and reaction temperature of 20 ℃, the equilibrium adsorption capacity of COD and ammonia nitrogen were 81.51 mg/g and 19.24 mg/g, and the removal rate reached 87.57% and 72.05%, respectively. The pore structure of red mud particles changed from shallow pores to penetrating pores, and obvious sulfonated characteristic groups appeared after modification. The adsorption of COD and ammonia nitrogen by SCRM belonged to monolayer adsorption and multilayer adsorption, respectively. The adsorption kinetics of the two adsorption processes were more consistent with the pseudo-second-order kinetic model, and both were endothermic and entropic spontaneous reaction processes.
- red mud /
- sulfonation coupling /
- adsorption /
- COD /
- ammonia nitrogen

HTML全文

图 1 RM和SCRM的FTIR

Figure 1.

下载: 全尺寸图片幻灯片

图 2 改性反应机理

Figure 2.

下载: 全尺寸图片幻灯片

图 3 RM和SCRM的SEM

Figure 3.

下载: 全尺寸图片幻灯片

图 4 吸附剂用量对COD和氨氮的吸附影响

Figure 4.

下载: 全尺寸图片幻灯片

图 5 渗滤液初始pH值对COD和氨氮的吸附影响

Figure 5.

下载: 全尺寸图片幻灯片

图 6 反应时间对COD和氨氮的吸附影响

Figure 6.

下载: 全尺寸图片幻灯片

图 7 COD和氨氮的吸附拟一级、拟二级动力学模型拟合曲线

Figure 7.

下载: 全尺寸图片幻灯片

图 8 COD和氨氮的吸附等温模型拟合曲线

Figure 8.

下载: 全尺寸图片幻灯片

表 1 原料赤泥的成分单位：%

Table 1. Composition content of the raw red mud

Na₂O	SiO₂	Al₂O₃	Fe₂O₃	CaO	TiO₂	MgO	P₂O₅	K₂O	SO₃	其他
9.62	19.39	25.66	26.91	9.82	3.82	1.22	0.15	1.35	1.67	0.39

下载: 导出CSV

表 2 RM和SCRM的比表面积及孔径分布

Table 2. BET and pore size distribution of RM and SCRM

样品	比表面积S_BET /(m²/g)	单位孔体积V /(cm³/g)	孔径R /nm
RM	11.83	0.113 4	22.79
SCRM	146.21	0.465 2	8.96

下载: 导出CSV

表 3 吸附动力学模型拟合结果

Table 3. Fitting results of adsorption kinetics model

吸附质	动力学模型	q_e/(mg/g)	K/(min^-1或g/(mg·min))	R²
COD	拟一级	265.19	0.064 80	0.831 7
COD	拟二级	93.98	0.000 46	0.990 7
氨氮	拟一级	15.77	0.046 40	0.656 1
氨氮	拟二级	21.75	0.002 39	0.991 4

下载: 导出CSV

表 4 Langmuir和Freundlich模型等温拟合参数

Table 4. Isothermal fitting parameters of Langmuir and Freundlich models

吸附指标	温度/℃	Langmuir 模型			Freundlich 模型
吸附指标	温度/℃	q_m /（mg/g）	k_l	R²	k_f	n	R²
COD	10	156.01	6.13x10^-4	0.976 5	2.214 2	1.941 2	0.964 3
	20	169.78	11.27x10^-4	0.989 3	2.226 5	2.183 5	0.962 0
	30	211.42	6.36x10^-4	0.971 3	5.489 3	2.546 7	0.919 3
氨氮	10	16.78	5.8x10^-4	0.976 6	1.93x10^-4	0.492 0	0.995 8
	20	40.31	7.2x10^-4	0.971 7	1.43x10^-3	0.640 1	0.987 8
	30	64.35	4.7x10^-4	0.983 4	3.99x10^-3	0.727 8	0.991 5

下载: 导出CSV

表 5 SCRM吸附COD和氨氮的热力学参数

Table 5. Thermodynamic parameters of adsorption of COD and ammonia nitrogen by SCRM

吸附指标	吸附温度/℃	K_c	ΔG/ （KJ/mol）	ΔH/ （KJ/mol）	ΔS/ （J/(mol·K)）
COD	10	2.39	-2.05	36.16	136.14
	20	5.93	-4.34
	30	6.65	-4.77
氨氮	10	1.12	-0.27	26.59	96.33
	20	2.71	-2.43
	30	2.39	-2.20

下载: 导出CSV

表 6 同类型改性颗粒对渗滤液指标COD和氨氮的吸附效率对比

Table 6. Comparison of adsorption efficiency of COD and ammonia nitrogen by similar modified particle

粒料类型	改性方法	渗滤液指标脱除效率/%
粒料类型	改性方法	COD	氨氮
赤泥	破碎粒化	23.81	27.35
活性炭	强酸酸化	86.79	-
矿化垃圾	焙烧	58.38	79.77
赤泥^*	磺化偶联	87.57	72.05
注：*代表本研究所用方法及吸附效率。

下载: 导出CSV

参考文献(18)

[1]	詹静芳, 王珊珊. 中国生活垃圾填埋场甲烷源碳排放量预测评估[J]. 环境科学与技术, 2022, 45(11):147-155.ZHAN J F, WANG S S. Assessment of methane generation and relevant carbon emission from MSW landfills in China[J]. Environmental Science & Technology, 2022, 45(11):147-155. ZHAN J F, WANG S S. Assessment of methane generation and relevant carbon emission from MSW landfills in China[J]. Environmental Science & Technology, 2022, 45(11):147-155.
[2]	尹文俊, 周伟伟, 王凯, 等. 垃圾渗滤液物化与生化处理工艺技术现状[J]. 环境工程, 2018, 36(2):83-87.YIN W J, ZHOU W W, WANG K, et al. Analysis of physical-chemistry and biochemical treatmenttechnologies on landfill leachate[J]. Environmental Engineering, 2018, 36(2):83-87. YIN W J, ZHOU W W, WANG K, et al. Analysis of physical-chemistry and biochemical treatmenttechnologies on landfill leachate[J]. Environmental Engineering, 2018, 36(2):83-87.
[3]	张璇, 袁林江, 马保卫, 等. 西安某垃圾填埋场渗滤液生物净化性能改善研究[J]. 水处理技术, 2012, 38(11):69-72.ZHANG X, YUAN L J, MA B W, et al. Study on biological degradation of leachate from a landfill in xi'an[J]. Technology of Water Treatment, 2012, 38(11):69-72. doi: 10.3969/j.issn.1000-3770.2012.11.015 ZHANG X, YUAN L J, MA B W, et al. Study on biological degradation of leachate from a landfill in xi'an[J]. Technology of Water Treatment, 2012, 38(11):69-72. doi: 10.3969/j.issn.1000-3770.2012.11.015
[4]	何耀. 拜尔法赤泥利用现状及高效资源化利用新技术[J]. 矿产综合利用, 2022(4):106-110.HE Y. New technology for efficient resource utilization of red mud from Bayer process[J]. Multipurpose Utilization of Mineral Resources, 2022(4):106-110. doi: 10.3969/j.issn.1000-6532.2022.04.019 HE Y. New technology for efficient resource utilization of red mud from Bayer process[J]. Multipurpose Utilization of Mineral Resources, 2022(4):106-110. doi: 10.3969/j.issn.1000-6532.2022.04.019
[5]	CARLO E D, BOULLEMANT A, COURTNEY R. A field assessment of bauxite residue rehabilitation strategies[J]. Science of the Total Environment, 2019, 663:915-926. doi: 10.1016/j.scitotenv.2019.01.376
[6]	冉浩学,谢名淇,朱燕,等. 赤泥在水、土、气环境治理中的应用研究进展[J]. 矿产综合利用, 2022(2):167-176.RAN H X, XIE M Q, ZHU Y, et al. Research progress in the application of red mud in water, soil and air environmental treatment[J]. Multipurpose Utilization of Mineral Resources, 2022(2):167-176. doi: 10.3969/j.issn.1000-6532.2022.02.030 RAN H X, XIE M Q, ZHU Y, et al. Research progress in the application of red mud in water, soil and air environmental treatment[J]. Multipurpose Utilization of Mineral Resources, 2022(2):167-176. doi: 10.3969/j.issn.1000-6532.2022.02.030
[7]	DU X L, CUI S S, FANG X, et al. Adsorption of Cd(II), Cu(II), and Zn(II) by granules prepared using sludge from a drinking water purification plant[J]. Journal of Environmental Chemical Engineering, 2020, 8(6):104530. doi: 10.1016/j.jece.2020.104530
[8]	杨世诚, 孙琦, 谌伦建, 等. 赤泥改性及其对丁苯橡胶复合材料微观结构和力学性能的影响[J]. 化工进展, 2019, 38(7):3297-3303.YANG S C, SUN Q, CHEN L J, et al. Effect of modified red mud on microstructure and mechanical properties of butadiene-styrene rubber composites[J]. Chemical Industry and Engineering Progress, 2019, 38(7):3297-3303. YANG S C, SUN Q, CHEN L J, et al. Effect of modified red mud on microstructure and mechanical properties of butadiene-styrene rubber composites[J]. Chemical Industry and Engineering Progress, 2019, 38(7):3297-3303.
[9]	孙发孟, 白蕊, 张发爱. PolyHIPEs块体的磺化改性及其吸附研究[J]. 化学研究与应用, 2014, 26(8):1266-1271.SUN F M, BAI R, ZHANG F A. Sulfonation and adsorption of PolyHIPEs[J]. Chemical Research and Application, 2014, 26(8):1266-1271. doi: 10.3969/j.issn.1004-1656.2014.08.017 SUN F M, BAI R, ZHANG F A. Sulfonation and adsorption of PolyHIPEs[J]. Chemical Research and Application, 2014, 26(8):1266-1271. doi: 10.3969/j.issn.1004-1656.2014.08.017
[10]	李宸, 鲁镜镜, 蒙梅, 等. 醇胺钛酸酯改性磁化赤泥对Pb(II)的吸附性能研究[J]. 硅酸盐通报, 2022, 41(2):625-633.LI C, LU J J, MENG M, et al. Adsorption property of Pb(II) to magnetic red mud modified by alcohol-amine titanate[J]. Bulletin of the Chinese Ceramic Society, 2022, 41(2):625-633. doi: 10.3969/j.issn.1001-1625.2022.2.gsytb202202030 LI C, LU J J, MENG M, et al. Adsorption property of Pb(II) to magnetic red mud modified by alcohol-amine titanate[J]. Bulletin of the Chinese Ceramic Society, 2022, 41(2):625-633. doi: 10.3969/j.issn.1001-1625.2022.2.gsytb202202030
[11]	张勃宇, 卢定泽. 改性矿渣处理活性艳蓝KN-R染料废水的能力[J]. 矿产综合利用, 2022, 43(3):42-46,94.ZHANG B Y, LU D Z. Ability of modified slag to treat reactive brilliant blue KN-R dye wastewater[J]. Multipurpose Utilization of Mineral Resources, 2022, 43(3):42-46,94. doi: 10.3969/j.issn.1000-6532.2022.03.008 ZHANG B Y, LU D Z. Ability of modified slag to treat reactive brilliant blue KN-R dye wastewater[J]. Multipurpose Utilization of Mineral Resources, 2022, 43(3):42-46,94. doi: 10.3969/j.issn.1000-6532.2022.03.008
[12]	段金明, 林锦美, 方宏达, 等. 改性钢渣吸附氨氮和磷的特性研究[J]. 环境工程学报, 2012, 6(1):201-205. DUAN J M, LIN J M, FANG H D, et al. Adsorption characteristic of modified steel-making slag for simultaneous removal of phosphorus and ammonium nitrogen from aqueous solution[J]. Chinese Journal of Environmental Engineering, 2012, 6(1):201-205. DUAN J M, LIN J M, FANG H D, et al. Adsorption characteristic of modified steel-making slag for simultaneous removal of phosphorus and ammonium nitrogen from aqueous solution[J]. Chinese Journal of Environmental Engineering, 2012, 6(1):201-205.
[13]	刘海伟, 刘云, 王海云, 等. 爬山虎茎粉对水体中氨氮的吸附特性[J]. 中国环境科学, 2010, 30(5):683-688LIU H W, LIU Y, WANG H Y, et al. Adsorption of ammonia nitrogen from aqueous solution by Boston ivy stem powder[J]. China Environmental Science, 2010, 30(5):683-688. LIU H W, LIU Y, WANG H Y, et al. Adsorption of ammonia nitrogen from aqueous solution by Boston ivy stem powder[J]. China Environmental Science, 2010, 30(5):683-688.
[14]	高雯雯, 苏婷, 弓莹, 等. 载铜活性炭对焦化废水的吸附性能研究[J]. 非金属矿, 2016, 39(1):40-43.GAO W W, SU T, GONG Y, et al. Study of adsorption property of coking wastewater on activated carbon loaded copper[J]. Non-Metallic Mines, 2016, 39(1):40-43. doi: 10.3969/j.issn.1000-8098.2016.01.013 GAO W W, SU T, GONG Y, et al. Study of adsorption property of coking wastewater on activated carbon loaded copper[J]. Non-Metallic Mines, 2016, 39(1):40-43. doi: 10.3969/j.issn.1000-8098.2016.01.013
[15]	骆欣,刘瑞森,徐东耀,等. 热改性粉煤灰对水中铜的动态吸附研究[J]. 矿产综合利用, 2022(3):137-142.LUO X, LIU R S, XU D Y, et al. Study on dynamic adsorption of copper in water by thermally modified fly ash[J]. Multipurpose Utilization of Mineral Resources, 2022(3):137-142. doi: 10.3969/j.issn.1000-6532.2022.03.024 LUO X, LIU R S, XU D Y, et al. Study on dynamic adsorption of copper in water by thermally modified fly ash[J]. Multipurpose Utilization of Mineral Resources, 2022(3):137-142. doi: 10.3969/j.issn.1000-6532.2022.03.024
[16]	XU H, HU X J, CHEN Y H, et al. Cd (II) and Pb (II) absorbed on humic acid-iron-pillared bentonite: kinetics, thermodynamics and mechanism of adsorption[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 612:126005. doi: 10.1016/j.colsurfa.2020.126005
[17]	姜浩, 廖立兵, 郑红, 等. 赤泥吸附垃圾渗滤液中COD和氨氮的实验研究[J]. 安全与环境工程, 2007, 14(3):69-73.JIANG H, LIAO L B, ZHENG H, et al. Adsorption of COD and ammonia-nitrogen from landfill leachate by red mud[J]. Safety and Environmental Engineering, 2007, 14(3):69-73. doi: 10.3969/j.issn.1671-1556.2007.03.019 JIANG H, LIAO L B, ZHENG H, et al. Adsorption of COD and ammonia-nitrogen from landfill leachate by red mud[J]. Safety and Environmental Engineering, 2007, 14(3):69-73. doi: 10.3969/j.issn.1671-1556.2007.03.019
[18]	蒋绪, 兰新哲, 宋永辉, 等. 酸改性兰炭基活性炭吸附焦化废水中COD研究[J]. 非金属矿, 2019, 42(3):96-99.JIANG X, LAN X Z, SONG Y H, et al. Adsorption of COD in coking wastewater on acid modified blue coke-based activated carbon[J]. Non-Metallic Mines, 2019, 42(3):96-99. doi: 10.3969/j.issn.1000-8098.2019.03.026 JIANG X, LAN X Z, SONG Y H, et al. Adsorption of COD in coking wastewater on acid modified blue coke-based activated carbon[J]. Non-Metallic Mines, 2019, 42(3):96-99. doi: 10.3969/j.issn.1000-8098.2019.03.026