生物炭-壳聚糖磁性复合吸附剂的制备及去除地下水中铅和铜

杨梦楠; 孙晗; 曹海龙; 贾增华; 冯政远; 郑丽君; 陈男

doi:10.15898/j.ykcs.202208230155

生物炭-壳聚糖磁性复合吸附剂的制备及去除地下水中铅和铜

1.
国土环境整治中心，中国地质工程集团有限公司，北京 100093
2.
中国地质大学（北京）水资源与环境学院，地下水循环与环境演化教育部重点实验室，北京 100083

基金项目: 企事业单位委托项目“长江流域典型金属矿山酸性土壤及地下水污染协同修复技术研发”（342021399）

详细信息

作者简介:
杨梦楠，硕士研究生，主要从事生态环境系统修复研究工作。E-mail：yangyangwd@hotmail.com

通讯作者:
陈男，教授，博士生导师，地下水科学与工程专业，主要从事地下水污染控制与修复技术研究。E-mail：chennan@cugb.edu.cn

中图分类号: X523；G264.3
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出版历程
- 收稿日期: 2022-08-22
- 修回日期: 2022-11-19
- 录用日期: 2023-01-17
- 网络出版日期: 2023-05-29
- 刊出日期: 2023-06-29

Preparation and Application of Biochar-Chitosan Magnetic Composite Adsorbent for Removal of Lead and Copper from Groundwater

1.
Land and Environment Rehabilitation Center, China GEO-Engineering Corporation, Beijing 100093, China
2.
School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083, China

摘要

摘要:
壳聚糖作为天然多糖有机物，具有对环境友好的特性，其含有的大量含氮官能团可吸附水中的金属离子。但壳聚糖类吸附剂在酸性条件下适应性差，实际使用过程中需要调节pH值，因此增加了运行成本。本文选用农林废弃物花生壳（CC）和玉米芯（PS）制备生物炭，与壳聚糖进行结合，并引入磁性因子Fe₃O₄，制备了花生壳生物炭-壳聚糖磁性复合吸附剂（PSC）和玉米芯生物炭-壳聚糖磁性复合吸附剂（CCC），并研究这两种吸附剂对水中Pb²⁺和Cu²⁺的吸附性能，同时利用实际含多种金属离子的地下水对所制备的材料进行实验，以评估其实际应用潜能。比表面积仪（BET）分析表征显示，CCC相比PSC的比表面积和平均孔径更大，两种吸附剂在pH 4~7范围内均表现出稳定的吸附性能。循环5个周期后，两种吸附剂仍对Pb²⁺和Cu²⁺的去除率保持在85%以上，表现出良好的循环利用性能。CCC对Pb²⁺和Cu²⁺的最大吸附容量分别为169.10mg/g和18.69mg/g，均大于PSC的最大吸附容量。同时，CCC可有效去除含重金属地下水中的多种金属离子。在处理实际含Pb²⁺和Cu²⁺的废水时可优先选择CCC材料作为吸附剂。吸附动力学实验结果表明，两种材料对Pb²⁺的吸附以物理吸附为主，对Cu²⁺的吸附以化学吸附为主。pH值影响实验和X射线光电子能谱（XPS）表征结果说明两种材料主要通过静电吸引和含氮官能团与金属离子的螯合作用去除Pb²⁺和Cu²⁺。本文使用农林废弃物制备生物炭降低了成本，引入的磁性因子方便了脱附过程，生物炭-壳聚糖磁性复合材料的制备方法有效地改善了壳聚糖类材料在酸性条件下的适应性，所制备的材料是一种去除地下水中Pb²⁺和Cu²⁺污染的有效潜在吸附剂。
- 生物炭 /
- 壳聚糖 /
- 吸附 /
- 铅 /
- 铜 /
- 含氮官能团; X射线光电子能谱
Abstract:
BACKGROUND
Wastewater containing heavy metals produced by mining, beneficiation, smelting, forging, processing, transportation, and other industries that has been improperly disposed of, leads to heavy metals entering and polluting the groundwater environment. Heavy metals can be enriched in the human body and participate in the biological cycle. Long-term accumulation of heavy metals in the human body will bring carcinogenic, teratogenic, and mutagenic risks. Adsorption has been of wide concern in the treatment of heavy metals pollution in water, due to the advantages of low operation cost, simple engineering operation and low secondary pollution. Chitosan as a natural organic polysaccharide organic matter, has the characteristics of being environmentally friendly. It contains many nitrogen-containing functional groups that can adsorb metal ions in water. However, the adaptability of chitosan adsorbents to acidic conditions is poor, so the pH value needs to be adjusted in the actual process, which increases the operating cost. Combining biochar with chitosan can not only improve the adsorption capacity of chitosan, but also improve the separation performance of biochar. However, most of the research on chitosan modified biochar concentrate on the single biochar. There are few studies on the modification of biochar from different sources by chitosan, and the interaction between chitosan and biochar is not clear.
OBJECTIVES
The aim of this study was to prepare peanut shell biochar-chitosan magnetic composite adsorbent (PSC) and corn cob biochar-chitosan magnetic composite adsorbent (CCC), and to investigate the Pb²⁺/Cu²⁺ adsorption properties and mechanisms on PSC and CCC.
METHODS
Scanning electron microscope was used to analyze the microstructure of the material, and the material samples were treated with gold spray before photographing. The specific surface area and pore volume of the material were determined using a specific surface area analyzer, and the material was adsorption-desorption tested with nitrogen at -196℃. X-ray diffraction was used to analyze the crystal structure of materials, and the Cu Kα source was used to scan in the range of 10°-80° (2θ). X-ray photoelectron spectrometer was used to analyze the changes of functional groups on the surface of the material, and the radiation (225W, 15mA, 15kV) was carried out by monochromatic Al-Kα. Metal ion content in solution was measured by inductively coupled plasma-optical emission spectrometry.　　The adsorption experiments were carried out in a 50mL conical flask and a constant temperature shaker. The oscillation frequency was 150r/min and the reaction time was 12h. After the reaction, the concentrations of Pb²⁺ and Cu²⁺ in the solution were determined. Two parallel samples were set up in each group. Different initial pH experiments were used to evaluate the adsorption performance of materials. Kinetic and isothermic models were used to evaluate the adsorption kinetic process of materials and predict the maximum adsorption capacity of materials. Recycling experiments and actual mine groundwater adsorption experiments were used to evaluate the practical application capacity of materials.
RESULTS
SEM images of PS and CC showed that there were many pores on the surface of both types of carbon. There were more pores and bulges observed on the surface of CC than PS, indicating that CC had a larger contact area with pollutants than PS. The specific surface area (12.045m²/g) and mean pore diameter (3.614nm) of CC were larger than those of PS (specific surface area was 3.294m²/g and mean pore diameter was 3.067nm), which was consistent with the SEM results. The specific surface area (4.598m²/g) and average pore diameter (3.417nm) was 2.812nm), indicating that the primary structural properties of biochar affected the pore structure of the composites. SEM of CCC and PSC showed that chitosan and biochar were well combined. Compared with previous literature, the biochar-chitosan composite material in this study preserves the original structure of biochar to the greatest extent, and makes the chitosan evenly coated on the surface of biochar. The results BET showed that the primary structural properties of the biochar affected the physical properties of the modified materials. The XRD results showed that Fe₃O₄ was successfully embedded into the composite material. Three pH values (4, 7 and 10) were selected to evaluate the swelling properties of the materials. The results showed that the swelling ratios of the two materials were similar under the three pH conditions, and neither of them was more than 100.0%, which was due to the biochar as a carrier having a good supporting effect. Compared with chitosan/kiwifruit branch biochar adsorbent, the two adsorbents in this study showed relatively stable adsorption properties in the pH range of 4-7, indicating that the adsorbents had a wider range of pH value application.　　The effect of the initial pH on the adsorption was tested. As the initial pH value increased from 3 to 7, the adsorption capacity and removal efficiency of the material increased. The positive charge of the adsorbent surface also decreased, which reduced the electrostatic repulsion of Pb²⁺ and Cu²⁺ between the material surface and the solution, and increased the electrostatic attraction between the material surface and Pb²⁺ and Cu²⁺. The increasing electrostatic attraction was beneficial to the adsorption of Pb²⁺ and Cu²⁺. When PSC and CCC adsorbed Pb²⁺, the pseudo-first-order kinetic model could better describe the adsorption process than the pseudo-second-order kinetic model, indicating that physical adsorption played a dominant role in the adsorption of Pb²⁺ by PSC and CCC. Pseudo-second-order kinetics can better fit the Cu²⁺ adsorption by PSC and CCC than pseudo-second-order kinetic model, indicating that chemisorption dominates the adsorption process of Cu²⁺ by PSC and CCC. The Langmuir isotherm adsorption model can better describe the adsorption process of Pb²⁺ and Cu²⁺ than Freundlich isotherm adsorption model, indicating that the adsorption process is monolayer adsorption.　　The EDTA-2Na was used as the desorption agent of chitosan composite, the removal efficiencies of Pb²⁺ and Cu²⁺ were still above 85% after five cycles, which indicated that the two adsorbents in this study had excellent stability. PSC and CCC were the low-cost and effective adsorption materials. Groundwater of an acid mine was taken from a mining area in Dongshan District, Dafan Mountain, Anhui Province. The groundwater samples contained large amounts of metal ions, such as As, Ca, Cd, Cu, Fe, Mn, Na and Ni, the corresponding concentrations were 18.200g/L, 40.541mg/L, 3.800g/L, 13.300mg/L, 215.00mg/L, 510.00g/L, 81.694mg/L and 87.000g/L, respectively. 0.45μm filter membrane was used to remove particulate impurities from the water before adsorption. CCC was used to treat the heavy metal polluted groundwater, and the results showed that CCC has a good removal ability on a variety of metal ions in groundwater such as Cu²⁺, Cd²⁺, and Fe³⁺. The Cu²⁺ concentration in the treated water can reach the Grade IV water standard of the “Groundwater Quality Standard”.　　The pH results showed that the removal mechanisms of Pb²⁺ and Cu²⁺ by PSC and CCC mainly included electrostatic attraction. The functional groups of adsorbents before and after adsorption were analyzed through X-ray photoelectron spectroscopy (XPS). The results of XPS showed that complexation was another removal mechanism. The nitrogen (—NH) of pyrroles, amino of chitosan (—NH₂), and C=N were the main functional groups, which were responsible for the complexation with Pb²⁺ and Cu²⁺.
CONCLUSIONS
The preparation method of the materials in this study can effectively improve the adaptability of chitosan materials under different pH conditions. The adsorbents developed in this study can effectively remove heavy metals from groundwater and have a good application potential.
- biochar /
- chitosan /
- adsorption /
- lead /
- copper /
- N-containing functional groups; X-ray photoelectron spectroscopy

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碲和硒是稀散元素，在高新科技领域具有重要应用，已被中国和欧美国家列为战略性关键矿产资源^［1-2］。一直以来全球碲、硒矿产资源主要采自斑岩-矽卡岩铜金矿床，如中国广东大宝山铜矿和江西城门山铜矿^［3-4］，研究斑岩矿床中碲、硒的产出情况对国家资源战略保障具有重要意义。云南普朗斑岩型铜金矿床位于三江特提斯成矿域义敦岛弧南部，属于超大型斑岩矿床，已探明铜资源储量4.31Mt，金资源量113t^［5］。矿区内出露的地层为中三叠统尼汝组和上三叠统图姆沟组，侵入岩为普朗复式岩体，由石英闪长玢岩（～216Ma）、石英二长斑岩（～215Ma）和花岗闪长斑岩（～206Ma）组成，岩体出露总面积约为11km²（图1）。前人对普朗矿床的地质特征、成岩成矿时代、成矿物质来源、成矿流体性质等作了大量工作，但对矿床中碲硒的含量和赋存状态等研究还较为薄弱。本文报道了普朗矿床中产出的碲化物和硒化物，以期为斑岩矿床中碲硒的勘查和综合利用提供资料。

图 1 普朗斑岩铜金矿床地质简图（据Leng等^［5］修改）

Figure 1. Geological map of the Pulang porphyry Cu-Au deposit (Modified from Leng, et al ^［5］ ).

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本次研究对象主要为普朗矿床中的铜精矿和钼精矿样品，测试分析均在东华理工大学核资源与环境国家重点实验室完成。样品的矿相学观察利用ZEISS Axio Scope A1光学显微镜及ZEISS Sigma 300场发射扫描电镜完成，扫描电镜的加速电压为20kV，发射电流为10μA^［6］。矿物成分利用JXA-8530F Plus型电子探针分析完成，实验设定加速电压为15kV，电流为20nA，探针直径为1μm，使用ZAF方法对X射线强度进行校正。分析标样选择砷化镓（As），黄铜矿（Cu），黄铁矿（Fe、S），自然银（Ag），碲铋矿（Te、Bi），辉钼矿（Mo），自然铅（Pb），自然锑（Sb），硒化镉（Se），自然金（Au），自然铂（Pt），自然钯（Pd）。测试主量元素的精确度和准确度均小于2%。

普朗铜金矿床中的碲和硒含量高，并形成大量碲化物、硒化物和富硒矿物。矿床精矿中的碲和硒含量分别达74.3×10⁻⁶和270×10⁻⁶。碲在钾化带中的含量为0.3×10⁻⁶～0.43×10⁻⁶，较绢英岩化带中的高（0.02×10⁻⁶～0.12×10⁻⁶），由矿体中心向外，碲品位逐渐降低^［7］。硒在钾化带和绢英岩化带的含量无明显差别，分别为1.49×10⁻⁶～2.44×10⁻⁶和1.04×10⁻⁶～3.00×10⁻⁶。矿石中的碲与金呈正相关关系，硒与银呈正相关关系。普朗铜矿床中，碲和硒主要以碲化物、硒化物和富硒矿物形式存在，形成辉碲铋矿、碲钯矿、硒银矿和富硒方铅矿等（图2）。辉碲铋矿是普朗含量最多的碲化物，反射光下为白色略带淡蓝色，矿物成分较均一，Bi含量为58.36%～61.24%，Te含量为31.03%～34.50%，S含量为3.76%～4.54%（图2e）。普朗辉碲铋矿中含有较高的Se（0.77%～3.63%）。辉碲铋矿的化学式为Bi_2.02～2.08（Te_1.74～1.93S_0.85～1.01Se_0.08～0.33）_2.90～2.98。碲钯矿属于独立铂族元素矿物，在自然界很少见，中国斑岩矿床中仅江西德兴有报道^［8］，在全球其他斑岩矿床中非常少见。普朗碲钯矿粒径为1～5μm，反射光下呈亮白色（图2a）。碲钯矿中Pd和Pt可以类质同象取代，因此含量变化较大，Pd含量为16.26%～25.69%，Pt含量为4.82%～17.66%，Te含量为61.25%～66.76%（图2f）。碲钯矿化学式为（Pd_0.64～0.98Pt_0.09～0.37）_0.98～1.03Te_1.97～1.02。硒银矿是普朗含量最多的硒化物，反射光下为白色带微蓝绿色（图2c）。硒银矿中普遍含S，含量为0.55%～2.65%，Ag含量普遍偏低，为70.22%～72.77%，Se含量为24.09%～27.31%（图2g）。硒银矿化学式为Ag_1.89～1.98（Se_0.87～1.01S_0.05～0.24）_1.02～1.11。富硒方铅矿属于PbS_1-xSe_x矿物，其中x值可在0～1之间连续变化。普朗富硒方铅矿S和Se的含量变化大，分别为4.01%～12.52%和1.85%～19.13%，Pb含量为73.91%～82.52%，大多数样品中含有Ag，最高含量达1.61%。普朗富硒方铅矿形成了较完整的PbS-PbSe固溶体系列（图2h），化学式为Pb_0.98～1.01（S_0.35～0.97Se_0.07～0.67）_0.99～1.02。

图 2 碲硒矿物显微照片及矿物元素含量三元图

a—碲钯矿反射光镜下照片； b—碲钯矿BSE照片； c—硒银矿反射光镜下照片； d—硒银矿BSE照片； e— Bi-Te-S体系三元图； f— Te-Pd-Pt体系三元图； g—Ag-Se-S体系三元图； h—Pb-Se-S体系三元图。Mol—辉钼矿； Mrk—碲钯矿； Nau—硒银矿； Py—黄铁矿。

Figure 2. Photomicrographs of tellurium and selenium minerals and ternary plots of element contents. a—Reflected light photomicrograph of merenskyite; b—BSE image of merenskyite; c—Reflected light photomicrograph of naumannite; d—BSE image of naumannite; e—Ternary plot of Bi-Te-S system; f—Ternary plot of Te-Pd-Pt system; g—Ternary plot of Ag-Se-S system; h—Ternary plot of Pb-Se-S system. Mol=Molybdenite, Mrk=Merenskyite, Nau=Naumannite, Py=Pyrite.

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矿床中的碲和硒可以指示物质来源和成矿过程。碲和硒具有亲硫特点，碲会部分进入硫化物晶格，但更易形成碲的独立矿物;硒属于强亲硫元素，在较高温的条件下易于进入硫化物晶格，在中低温条件下，硫含量较低时，可形成硒的独立矿物。洋壳中的铁锰结壳、页岩及浮游沉积物等是自然界中碲和硒的重要储库^［9］，因此在洋陆俯冲过程中，大陆岩石圈地幔和洋壳的部分熔融会形成富碲、硒的岩浆^［10-11］。碲和硒在硫化物熔体中的相容性很高（D_{硫化物/硅酸盐}＞600），碲倾向于存在液相硫化物（SL）中，而硒则更易进入单硫化物固熔体（MSS）（D^Te_SL/硅酸盐/D^Se _SL/硅酸盐为5～9，D^Te _{MSS/硅酸盐}/D^Se _{MSS/硅酸盐}为0.5～0.8）^［12］。当富碲、硒的岩浆到达下地壳，会结晶分异形成富Co、Ni的硅酸盐矿物，碲、硒存在硫化物熔体中继续向上运移；当岩浆到达中地壳，温度低于900℃时，硫化物熔体与Te-Se熔体发生相分离；当岩浆到达上地壳，侵位形成班岩体及Cu矿床，Ag-Pt-Pd则高度集中在富Te-Se熔体中，并最终形成贵金属矿物^［13］。普朗铜金矿床中的碲和硒可能与区内晚三叠世的俯冲造山密切相关，富碲和硒的岩浆也促进了铂族元素的富集成矿。

普朗斑岩铜金矿床中碲化物和硒化物的发现，对资源的综合利用及矿床成因研究具有重要意义。矿床中碲和硒的资源量规模大，大部分以独立矿物形式存在，且常与Au-Ag-PGE共生，具有较好的经济回收利用价值。碲化物和硒化物的产出也为成矿物质来源及岩浆演化过程提供了新的研究方向。

图 1 生物炭-壳聚糖磁性复合材料合成示意图

Figure 1. Schematic diagram of biochar-chitosan magnetic composite.

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图 2 （a）PS、（b）CC、（c）PSC和（d）CCC的SEM图像

Figure 2. SEM images of (a) PS, (b) CC, (c) PSC and (d) CCC

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图 3 （A）Fe₃O₄（a线）、壳聚糖（b线）、CCC（c线）、PSC（d线）的XRD谱图；（B）材料在不同pH条件下（4、7、10）的溶胀性

Figure 3. (A) XRD patterns of Fe₃O₄ (line a), chitosan (line b), CCC (c line) and PSC (d line); (B) Swelling properties of materials under different pH conditions (pH=4, 7, 10).

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图 4 pH对PSC和CCC吸附Cu²⁺和Pb²⁺效果的影响

Figure 4. Effect of pH on adsorption of Cu²⁺ and Pb²⁺ by PSC and CCC (Dosage=4g/L, initial concentration of Cu²⁺ and Pb²⁺ are both 50mg/L).

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图 5 PSC和CCC对（a）Pb²⁺和（b）Cu²⁺的循环利用性

Figure 5. The recycling of （a）Pb²⁺ and （b）Cu²⁺ by PSC and CCC.

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图 6 PSC（a）、吸附Pb²⁺后PSC（b）、吸附Cu²⁺后PSC（c）、CCC（d）、吸附Pb²⁺后CCC（e）、吸附Cu²⁺后CCC（f）的XPS谱图

Figure 6. XPS spectra of PSC (a), PSC after Pb²⁺ adsorption (b), PSC after Cu²⁺ adsorption (c), CCC (d), CCC after Pb²⁺ adsorption (e), CCC after Cu²⁺ adsorption (f).

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表 1 PSC和CCC吸附Pb²⁺、Cu²⁺动力学模型拟合参数以及PSC和CCC吸附Pb²⁺、Cu²⁺等温线模型拟合参数

Table 1 Fitting parameters of kinetic models for Pb²⁺ and Cu²⁺ adsorption by PSC and CCC, and the fitting parameters of PSC and CCC adsorption of Pb²⁺ and Cu²⁺ isotherm models.

金属离子	制备材料	伪一级动力学模型					伪二级动力学模型
金属离子	制备材料	K₁		R²		χ²	k₂		R²		χ²
Pb²⁺	PSC	0.0375		0.998		0.042	0.0062		0.936		0.114
Pb²⁺	CCC	0.0045		0.999		0.044	0.0004		0.986		0.121
Cu²⁺	PSC	0.0072		0.996		0.049	0.0009		0.997		0.135
Cu²⁺	CCC	0.0037		0.988		0.082	0.0021		0.997		0.056

金属离子	制备材料	Langmuir模型					Freundlich模型
金属离子	制备材料	q_m	K_L		R²	χ²	K_F	1/n		R²	χ²
Pb²⁺	PSC	189.09	0.0017		0.999	0.702	0.766	0.749		0.992	8.460
Pb²⁺	CCC	86.72	0.0036		0.998	1.420	1.220	0.622		0.984	9.706
Cu²⁺	PSC	18.69	0.0123		0.981	0.973	1.277	0.419		0.952	2.372
Cu²⁺	CCC	14.34	0.0197		0.979	0.667	2.72	0.368		0.928	0.375

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表 2 PSC和CCC吸附Pb和Cu的性能与其他材料对比

Table 2 Comparison of the adsorption capacities of PSC and CCC with other materials.

吸附剂	最大吸附容量（mg/g）		参考文献
吸附剂	Pb	Cu	参考文献
二甘酸功能化磁性壳聚糖	70.57	-	[36]
EDTA-改性壳聚糖/SiO₂/Fe₃O₄	123.5	44.4	[37]
磁性花生壳	28.3	-	[38]
磁性壳聚糖/纤维素微球	45.8	88.2	[39]
介孔CoFe₂O₄纳米颗粒	32.1	-	[40]
CCC	169.10	18.69	本研究
PSC	86.72	14.34	本研究
注：“-”表示文献中未提供数据。

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