FeCl3和十六烷基三甲基溴化铵改性赤泥对水中铜离子的吸附性能和机理

doi:10.16085/j.issn.1000-6613.2019-0788

摘要/Abstract

摘要：

含铜废水主要来自电镀、有色冶炼、有色金属矿山开采、染料生产等过程。因Cu(Ⅱ)具有高毒性和生物富集性，严重威胁生态环境和人类健康。利用浓盐酸、三氯化铁（FeCl₃）、十六烷基三甲基溴化铵（CTAB）依次对拜耳法赤泥（RM）进行处理、改性，制备出了一种去除率高、吸附量大、吸附效果好的重金属离子吸附剂。通过SEM、TEM、XRD、BET、元素分析、FTIR、热重分析等手段对其进行表征，并探究溶液pH、吸附剂投加量以及吸附温度等条件对水溶液中Cu(Ⅱ)吸附效果的影响。结果表明：酸浸赤泥（RM-HCl）比表面积比RM增大20倍，经过FeCl₃和CTAB改性后赤泥表面负载了大量羟基氧化铁（FeOOH）并且改善了吸附材料的表面性质，提高了吸附材料与Cu(Ⅱ)之间的亲和力和单层吸附能力。综合改性赤泥（FeCl₃/CTAB/RM）对铜的吸附时间在100min达到平衡，其最佳吸附pH为6、最佳吸附剂投加量为2g/L、饱和吸附量为221mg/g。吸附过程较好地符合准二级动力学模型和Langmuir吸附等温模型，热力学数据说明该吸附是吸热、自发的过程。吸附机理主要是FeCl₃/CTAB/RM表面的羟基（Si-OH、α-FeOOH和β-FeOOH）以及掺杂的氯原子和表面活性剂，通过物理吸附（微胶束、静电引力）和化学吸附（离子交换、氢键）有效地去除Cu(Ⅱ)离子。

关键词: 重金属, 赤泥, 吸附, 综合改性, 羟基氧化铁, 表面活性剂

Abstract:

Copper-containing wastewater mainly comes from electroplating, non-ferrous smelting, non-ferrous metal mining, dye production and other processes. Due to its high toxicity and bioaccumulation, Cu(Ⅱ) is a serious threat to the ecological environment and human health. In this paper, concentrated red hydrochloric acid, ferric chloride (FeCl₃), hexadecyl trimethyl ammonium bromide (CTAB) were used to treat and modify Bayer red mud (RM), and a high removal rate was prepared. It was characterized by SEM, TEM, XRD, BET, elemental analysis, FTIR, thermogravimetric analysis, etc., and the effects of solution pH, adsorbent dosage and adsorption temperature on the adsorption of Cu(Ⅱ) in aqueous solution were investigated. The results showed that the specific surface area ratio of acid-immersed red mud (RM-HCl) was increased by 20 times. After modification by FeCl₃ and CTAB, the surface of red mud was combined with a large amount of hydroxyl oxidize iron (FeOOH) and improved the surface properties of the adsorbent as well as affinity and single layer adsorption capacity between adsorbent material and Cu(II). The adsorption time of copper by comprehensive modified red mud (FeCl₃/CTAB/RM) reached equilibrium at 100min, the optimum adsorption pH was 6, the optimal adsorbent dosage was 2g/L, and the saturated adsorption amount was 221mg/g. The adsorption process was in good agreement with the quasi-secondary kinetic model and the Langmuir adsorption isotherm model. The thermodynamic data indicated that the adsorption is an endothermic and spontaneous process. The adsorption mechanism is mainly the grafting of hydroxyl groups (Si-OH, α-FeOOH and β-FeOOH) on FeCl₃/CTAB/RM surface and doped chlorine atoms and surfactants. It effectively removed Cu(Ⅱ) by physical adsorption (chelation, electrostatic attraction) and chemical adsorption (ion exchange, hydrogen bonding).

Key words: heavy metal, red mud, adsorption, comprehensive modification, hydroxyl oxidize iron, surfactant

中图分类号:

X703.1

刘江龙,郭焱,席艺慧. FeCl₃和十六烷基三甲基溴化铵改性赤泥对水中铜离子的吸附性能和机理[J]. 化工进展, 2020, 39(2): 776-789.

Jianglong LIU,Yan GUO,Yihui XI. Adsorption and mechanism of copper ions in water by red mud modified with FeCl₃ and hexadecyl trimethyl ammonium bromide (CTAB)[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 776-789.

图/表 30

表1 拜耳法赤泥与盐酸反应实验

液固比	盐酸浓度/mol·L^-1	反应时间/h	粒径/μm
8∶1	12	1	17.8
8∶1	6	0.5	19.5
6∶1	12	1	19.9
6∶1	6	0.5	21.7
5∶1	12	1	16.3
5∶1	6	0.5	22.6

图1 RM和RM-HCl的粒径分布

图2 FeCl3/CTAB/RM颗粒改性合成流程

图3 酸浸前后赤泥的SEM图

图4 综合改性前后赤泥的SEM图

图5 吸附前后FeCl3/CTAB/RM样品的TEM图

图6 RM、RM-HCl和FeCl3/CTAB/RM样品的XRD图

1—CaCO3；2—SiO2；3—CaTiO3；4—Ca3Al2(SiO4)(OH)8 ；5—Fe2O3；6—Ca2SiO4；7—TiO2

图7 RM、RM-HCl和FeCl3/CTAB/RM样品的N2-吸脱附曲线图

表2 RM、RM-HCl和FeCl3/CTAB/RM的表面特性参数

样品	S_BET/m²·g^-1	V/cm³·g^-1	R/nm
RM	12.97	0.16	24.86
RM-HCl	233.09	0.59	9.37
FeCl₃/CTAB/RM	201.2	0.38	10.11

图8 RM、RM-HCl和FeCl3/CTAB/RM样品的FTIR图谱

表3 RM、RM-HCl和FeCl3/CTAB/RM样品的元素分析％

成分	RM	RM-HCl	FeCl₃/CTAB/RM
C	1	0.9	1.97
N	0.45	0.17	0.24
H	0.90	0.81	1.52

图9 RM、RM-HCl和FeCl3/CTAB/RM样品的TG图

图10 RM、RM-HCl和FeCl3/CTAB/RM在不同pH下的zeta电位

图11 不同pH对Cu(Ⅱ)吸附过程的影响

图12 吸附剂投加量对Cu(Ⅱ)吸附的影响

图13 温度对FeCl3/CTAB/RM吸附去除效率的影响

图14 Cu(Ⅱ)初始浓度对FeCl3/CTAB/RM吸附去除率和平衡吸附量的影响

图15 不同初始浓度的Cu(Ⅱ)准一级、准二级和Elovich动力学模型拟合曲线

表4 不同初始Cu(Ⅱ)浓度下吸附的动力学参数

C₀/mg·L^-1	Q_e,exp/mg·g^-1	准一级动力学模型			准二级动力学模型			Simple Elovich方程
C₀/mg·L^-1	Q_e,exp/mg·g^-1	k₁/min^-1	Q_e,cal/mg·g^-1	R²	k₂/min^-1	Q_e,cal/mg·g^-1	R²	α/mg·g^-1·min^-1	β/mg·g^-1	R²
200	86	0.513	82.36	0.972	0.011	86.7	0.994	62.54	4.82	0.936
300	126.6	0.497	121.84	0.989	0.009	127.03	0.998	98.31	5.88	0.854
400	161.6	0.341	153.89	0.972	0.002	163.85	0.997	104.39	12.19	0.887

图16 不同初始温度Cu(Ⅱ)Langmuir、Freundlich和Temkin吸附等温线模型拟合曲线

表5 在不同温度下Cu(Ⅱ)吸附的等温线参数

T/K	Langmuir模型			Freundlich模型				Temkin方程
T/K	Q_m,cal/mg·g^-1	K_L/L·mg^-1	R²	Q_m,exp/mg·g^-1	K_F/(mg·g^-1)(mg·L^-1)^-ⁿ	1/n	R²	b_T/J·mol^-1	K_T/L·mg^-1	R²
288	304.9	0.01	0.998	219.8	11.59	0.58	0.996	31.34	9.97	0.982
298	313.6	0.014	0.998	221	16.5	0.52	0.985	36.43	6.89	0.986
308	315.7	0.016	0.996	224.2	18.92	0.5	0.991	37.77	6.05	0.975

表6 FeCl3/CTAB/RM吸附Cu(Ⅱ)热力学参数

T/K	ΔH⁰/kJ·mol^-1	ΔS⁰/J·mol^-1·K^-1	ΔG⁰/kJ·mol^-1
288			-0.77
298	37.82	137.8	-1.56
308			-1.92

表7 不同吸附剂材料对铜离子的吸附性能比较

吸附剂	实验方法	吸附量/mg·g^-1	参考文献
FeCl₃/CTAB/RM	12mol·L^-1 HCl+0.5mol·L^-1 FeCl₃+0.5%CTAB	221	本文
RM/HCl	2.25mol·L^-1 HCl	78.13	[25]
RM/壳聚糖	0.01g·mL^-1壳聚糖	7.2	[26]
RM/NaHSO₄	0.32mol·L^-1 NaHSO₄	200	[27]

图17 FeCl3/CTAB/RM吸附Cu(Ⅱ)前后SEM、氯元素EDS-mapping表征结果

表8 FeCl3/CTAB/RM吸附Cu(Ⅱ)前后EDS元素分析数据

样品	C	N	O	Si	Fe	Cl	Cu
RM	5.57	1.66	66.84	25.84	0.05	0.03	0
RM-HCl	7.65	1.61	45.82	44.68	0.23	0	0
FeCl₃/CTAB/RM	29.86	2.45	27.13	35.51	3.1	1.64	0
FeCl₃/CTAB/RM-Cu	25.54	2.32	30.95	36.25	2.7	0.58	1.05

图18 FeCl3/CTAB/RM吸附Cu(Ⅱ)前后XRD图

图19 FeCl3/CTAB/RM对Cu(Ⅱ)吸附前后样品FTIR图谱a—FeCl3/CTAB/RM；b—吸附铜后FeCl3/CTAB/RM

图20 吸附Cu(Ⅱ)前后FeCl3/CTAB/RM材料的XPS的O1s图谱

图21 FeCl3/CTAB/RM对Cu(Ⅱ)吸附后的Cu2p的XPS分峰

图22 Cu(Ⅱ)的吸附机理

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FeCl₃和十六烷基三甲基溴化铵改性赤泥对水中铜离子的吸附性能和机理

Adsorption and mechanism of copper ions in water by red mud modified with FeCl₃ and hexadecyl trimethyl ammonium bromide (CTAB)

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