Adsorption of heavy metals by agricultural solid waste based hydrogel: A review
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摘要: 随着经济的快速发展，水中重金属离子污染对人类健康以及生态系统造成威胁。水凝胶以其良好的吸附性能、可再生性和低毒性在处理重金属离子方面具有很大的潜力。本文论述了近年来国内外以农业固体废弃物为原料制备水凝胶(纤维素基水凝胶、半纤维素基水凝胶、木质素基水凝胶等)吸附重金属的研究进展。同时，讨论了农业固废基水凝胶的合成，对重金属的吸附效果、吸附机制及分析方法，并列举了工业固废基和其他固废基水凝胶吸附重金属的效果，以期帮助研究者对农业固废基水凝胶吸附重金属的探究有更深刻的理解。Abstract: With the rapid development of economy, the pollution of heavy metal ions in water poses a threat to human health and ecosystem. Hydrogels have great potential in the treatment of heavy metal ions because of their good adsorption properties, renewability and low toxicity. This paper discusses the research progress in recent years on the preparation of hydrogels (cellulose-based hydrogels, hemicellulose-based hydrogels, lignin-based hydrogels, etc.) for the adsorption of heavy metals from agricultural solid wastes at home and abroad. The synthesis of agricultural solid waste based hydrogels, the adsorption effect, adsorption mechanism, and analytical methods for the removal of heavy metals are also discussed, and the effects of heavy metal adsorption by industrial solid waste based and other solid waste based hydrogels are enumerated. In order to help the researchers to have a deeper understanding of the investigation of heavy metal adsorption by agricultural solid waste based hydrogels.
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图 1 农业固废基水凝胶用于水体中重金属吸附的示意图
Figure 1. Schematic diagram of agricultural solid waste-based hydrogel for heavy metal adsorption in water bodies
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图 2 农业固废基水凝胶合成示意图
Figure 2. Schematic synthesis of agricultural solid waste-based hydrogel
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图 3 农业固废基水凝胶吸附重金属的示意图
Figure 3. Schematic diagram of heavy metal adsorption on agricultural solid waste based hydrogel
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图 4 3种机制的吸附过程示意图
Figure 4. Schematic diagram of the adsorption process of the three mechanisms
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图 5 固废基水凝胶用于水体中重金属吸附的示意图
Figure 5. Schematic diagram of solid waste-based hydrogel for heavy metal adsorption in water bodies
表 1 重金属对人类健康的危害
Table 1 Hazards of heavy metals to human health
Heavy metal Harm to mankind Pb Accumulates in the bones, brain, kidneys and muscles of the body, leading to brain damage, mental
retardation, anemia and cancer[21]Hg Lung, kidney and chest pain, dyspnea injury[22] Cd Cadmium ions pose a threat to many organs such as kidneys, lungs and liver[23] Cu Leading to liver damage, insomnia and Wilson disease[24] Zn Zinc not only irritates the skin, but also causes headache, dry cough, dizziness and other symptoms[25] Cr Destroy human metabolism, stimulate skin and lung cancer[26] As Skin damage and affect the nervous system of the human body[27] Ni Dermatitis, nausea, chronic asthma, cough[27] Mn Excessive manganese can cause dizziness and fatigue, mental retardation, and cause neurotransmitter disorders[28] 
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表 2 农业固废基水凝胶的制备及特点
Table 2 Synthesis and characterization of agricultural solid waste-based hydrogels
Solid waste-based raw materials and other reagents Method Characteristic Ref. Cellulose base Soybean residue cellulose,
chitosan, polyvinyl alcohol,
nano-Fe3O4Freeze-thaw method The increase of cellulose content is beneficial to improve the mechanical strength and swelling properties of the hydrogel. [44] Licorice residue cellulose,
crosslinker epichlorohydrinSolution polymerization The adsorption capacity, chemical stability, pore size distribution and mechanical properties of the hydrogel are improved by using epichlorohydrin as cross-linking agent. [45] Bagasse cellulose, polyvinyl alcohol, crosslinker glutaraldehyde Microwave assisted irradiation Microwave assisted irradiation technology can save time and energy. [46] Wheat straw cellulose, monomer acrylic acid and acrylamide, crosslinker N, N'-methylene-bis-acrylamide, initiator ammonium persulfate Free radical graft copolymerization Hydrogel has good thermal stability at temperature below 392℃. [47] Poplar wood flour cellulose, 3-mercaptopropionic acid, L-cysteamine hydrochloride, initiator ammonium persulfate Ultraviolet photoinitiation The cellulose ester synthesized by esterification of anhydride with cellulose under homogeneous condition has higher reaction activity. [48] Banana cellulose, chitosan, crosslinker epichlorohydrin Solution polymerization There are a large number of hydrophilic groups of hydroxyl and amino groups in the synthesized hydrogel, and the surface distributes irregular pore structure. [49] Lignin based Wheat straw lignin, montmorillonite, monomer acrylic acid, crosslinker N, N'-methylene-bis-acrylamide, initiator
K2S2O8-Na2SO3Solution polymerization Montmorillonite is introduced into lignin nanocomposites to improve the adsorption and mechanical properties of lignin nanocomposites. [50] Mulberry lignin, monomer acrylic acid, intercalation agent citric acid modified montmorillonite, crosslinker N, N'-methylene-bis-acrylamide, initiator (NH4)S2O8 Graft intercalation method When the amount of lignin is too high, the excess lignin produces too many cross-linking points, which affects the gel strength and hinders the cross-linking reaction. [51] Rice husk lignin, chitosan, polyacrylamide Free radical polymerization Lignin and chitosan are mixed as the first network to provide active functional groups for the removal of heavy metals.
As a malleable second network, polyacrylamide forms a stable structural hydrogel adsorbent.[52] Hemicellulose group Corn kernel hemicellulose, monomers acrylic acid and N-isopropyl acrylamide, crosslinker N, N'-methylene-bis-acrylamide, photoinitiator benzoin dimethyl ether Ultraviolet photoinitiation Pb2+ solution pH in the range of 3.5-4.5 and elevated temperature favored the adsorption of hydrogels. [53] Reed hemicellulose, monomer acrylic acid, crosslinker N, N, N', N'-tetramethylethylenediamine Free radical polymerization After 8 cycles of adsorption-desorption, the hydrogel still has high adsorption efficiency for metal ions. [39] Xylan hemicellulose, carrageenan, initiator ammonium persulfate, polyvinylpyrrolidone Microwave assisted irradiation Compared with cellulose, xylan hemicellulose is amorphous and consists of branched chains of various sugars, which is easier to dissolve in common solvents. [54] Other types of agriculture Citrus peel pectin, crosslinker calcium chloride, metal organic frame (MOF) In-situ method MOFs can interact with other components or adjust the properties of hydrogel matrix. [55] Pomelo peel pectin, monomers acrylic acid and acrylamide, initiator ammonium persulfate, crosslinker N, N'-methylene-bis-acrylamide Graft copolymerization Microwave extraction-alcohol precipitation method for pectin extraction has the advantages of strong selectivity, short operation time, low solvent consumption and excellent quality of extracted pectin. [56] Livestock bone powder, sodium alginate Solution polymerization Adsorption kinetics and adsorption isotherms indicate that adsorption is chemically and physically interactive. [57]
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表 3 农业固废基水凝胶吸附重金属的优缺点
Table 3 Advantages and disadvantages of heavy metal adsorption on agricultural solid waste-based hydrogels
Common type Common ground Advantage Disadvantage Cellulose based hydrogel
Advantages: The raw materials are non-toxic, biodegradable and low cost; Make the hydrogel biocompatible, biodegradable and improve its adsorption performance.
Disadvantages: Unhomogeneity of raw materials, structural complexity, and difficulty in obtaining pure substances, and poor mechanical strength of prepared hydrogels.Contains hydroxyl, carboxyl and hydrogen bonding to improve the adsorption and mechanical properties
of hydrogels.Refractory; After several cycles of use, the morphology and mechanical properties of the hydrogel will change considerably, resulting in an unstable adsorption capacity. Hemicellulose based hydrogel Contains functional groups such as hydroxyl, acetyl and carboxyl groups; Good water solubility. The mechanical strength of the prepared hemicellulose-based hydrogels is poor due to the small molecular weight of hemicellulose and low degree of polymerization. Lignin based hydrogel Hydroxyl and carbonyl groups can chelate with metal ions; Active site for chemical reactions. The inhomogeneity and structural complexity of lignin and the difficulty of obtaining pure lignin；And when the amount of lignin is too high, excess lignin produces too many cross-linking points, which affects the gel strength and hinders the cross-linking reaction. Other agricultural solid waste-based hydrogels Pectin contains reactive groups such as carboxyl and hydroxyl groups. Insoluble; Pectins from different sources have different gelling and adsorption capacities due to different sizes and chemical structures, and are less stable.
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表 4 农业固废基水凝胶对重金属的吸附性能总结
Table 4 Summary of adsorption properties of agricultural solid waste-based hydrogels for heavy metals
Hydrogel Target
pollutantAdsorption
conditionMaximum adsorption capacity/(mg·g−1) Adsorption kinetic/
adsorption isothermRecycling rate Ref. Cellulose base Soybean residue cellulose magnetic hydrogel Cu(II) pH=5.0 15.94 Pseudo-second-order/
Freundlich4 times
＞80%[44] Licorice residue cellulose hydrogel Pb(II)
Cr(III)
Cu(II)pH=5.0(Pb)
t=120 min,
pH=4.0(Cr)(Cu)
t=60 min591.8
458.3
121.4Pseudo-second-order/
Langmuir5 times
＞75%[45] Bagasse carboxymethyl cellulose hydrogel Cu(II) pH=5.0 2.3 — — [46] Wheat straw cellulose hydrogel Cu(II)
Mn(II)500 mg/L Co (Cu)
400 mg/L Co (Mn)238.1
176.9Pseudo-second-order — [47] Aspen cellulose methacrylate hydrogel Pb(II)
Hg(II)Hydrogel
dosage 0.2 g148.44
112.55Pseudo-second-order/
Langmuir— [48] Grapefruit peel cellulose-based hydrogel Cu(II)
Cr(VI)
Cd(II)Hydrogel dosage 10 g/L, pH=7.0, T=33℃, t=60 min, 10 mg/L Co Removal rate 96.21%, 98.02%,
95.43%— — [59] Banana fiber-chitosan hydrogel Cu(II)
Cd(II)
Pb(II)Hydrogel dosage 5 g/L, t=40 min Removal rate 98.35%, 79.22%,
77.3%Pseudo-second-order — [49] Lignin base Wheat straw lignin-montmorillonite hydrogel Cu(II) pH=6.5 74.35 Pseudo-second-order/
Freundlich5 times
＞80%[50] Mulberry lignin hydrogel Mn(II)
Zn(II)
Pb(II)320 mg/L Co (Mn),
160 mg/L Co (Zn),
1000 mg/L Co (Pb),
t =720 min77.09
73.95
383.90— — [51] Hemicellulose based Reed hemicellulose-based hydrogel Pb(II)
Cd(II)
Zn(II)200 mg/L Co,
pH=5.5(Pb),
pH=6.5(Cd)(Zn)699
521
265Pseudo-second-order/
Langmuir— [39] Yellow bamboo xylan hemicellulose-acrylic hydrogel Pb(II)
Cd(II)
Zn(II)t=60 min,
pH=5.5(Pb),
pH=6.5(Cd)(Zn)859
495
274Pseudo-second-order/
Langmuir5 times
＞90%[60] Other
categoriesMetal-organic frame composite citrus peel gum hydrogel Cr(VI)
Pb(II)pH=1(Cr),
pH=5(Pb)825.97
913.88Pseudo-second-order/
Langmuir8 times
＞85%[55] Grapefruit peel pectin-based composite hydrogel Cu(II) pH=6.0 80.6 Pseudo-second-order/
Freundlich4 times
＞90%[61] Bone hydrogel of abandoned livestock and poultry in rural area Cd(II) pH=4.0, t=720 min 1010.19 Pseudo-second-order and intra-particle diffusion models/
Langmuir and Freundlich3 times
＞90%[57] Notes: T—Temperature; t—Time.
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表 5 工业固废基水凝胶对重金属的吸附性能总结
Table 5 Summary of adsorption properties of industrial solid waste-based hydrogels for heavy metals
Hydrogel adsorption
materialTarget pollutant Adsorption condition Maximum adsorption
capacity/(mg·g−1)Ref. Red mud-sodium alginate hydrogel Pb(II) pH=6.0, T=25℃, t=900 min, 900 mg/L Co 454.54 [80] Fly ash-hydroxyethyl cellulose-chitosan hydrogel Cu(II) 100 mg/L Co 130.7 [81] Modified fly ash-sodium alginate crosslinked
acrylic hydrogelCu(II) 300 mg/L Co 131.09 [82] Magnetic attapulgite/fly ash/polyacrylic
acid hydrogelPb(II) pH=5.0, 100 mg/L Co, t=24 h 38 [83] Tobe mullite-starch hydrogel Cd(II) t=12 h, pH=5.21, T=25℃, hydrogel
dosage 0.05 g591.36 [84]
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目的
水凝胶是一种具有三维立体网状结构的多孔亲水聚合物，在处理重金属离子方面具有很大的潜力。随着经济化的发展，我国固体废弃物的产生量急剧增加。利用固废制备水凝胶作为一种新型绿色材料，在去除环境中的重金属方面具有广阔的应用前景。本文主要论述了农业固废基(纤维素、半纤维素、木质素、果胶等)用于水凝胶的制备，以及对重金属离子的吸附情况，以期为更深入地了解水凝胶在处理重金属的应用提供参考。
方法查阅国内外文献，论述了现阶段利用农业固废材料制备水凝胶的情况，主要包括农业固废基水凝胶的合成，吸附重金属的效果、分析方法以及吸附机理。
结果秸秆、甘蔗渣、稻壳等农业废弃生物质，含有大量的纤维素、半纤维素和木质素。木质素、半纤维素、纤维素分子含有羟基和羧基，具有螯合能力，可以与重金属离子发生静电相互作用。将其加入到水凝胶的制备当中，可以提高水凝胶的生物可降解性以及对重金属的吸附能力。农业固废基水凝胶对重金属离子的吸附机理主要通过络合作用、静电相互作用和离子交换作用。吸附等温线与Langmuir和Freundlich模型较为复合，表明吸附是通过重金属与水凝胶发生化学和物理作用进行的。吸附动力学模型与准二级动更为拟合。
结论(1)农业废弃生物质中含有丰富的纤维素、半纤维素、木质素，这些物质不仅具有无毒性、可生物降解等特点，还含有大量的羟基、羧基和氢键等官能团，能与重金属发生螯合作用。将其加入到水凝胶的制备中，可以使水凝胶具有生物相容性、生物可降解性，并增强对重金属的吸附效果。(2)但是这些物质的不均一性、结构复杂性、纯品物质难以获得，以及分子量较小，聚合度较低，制备的水凝胶的力学强度较差等问题还需要进一步探索。(3)目前大多的研究还停留在实验室阶段，未应用到实际工程中。除了以上的不足，还需考虑以下问题。首先，多数实验所用的重金属离子溶液为实验室模拟配置的废水，为了以后更好的实际工程应用，应选用实际废水进行研究。其次，关于将农业固废经过改性或许与其他物质复合形成水凝胶等手段，以及水凝胶的制备过程都涉及较多的化学试剂，并且工艺流程复杂性、成本问题都制约其发展。
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