滴定-凝胶法制备球形水凝胶吸附材料及其在废水处理中的应用

doi:10.11949/0438-1157.20191064

摘要/Abstract

摘要：

滴定-凝胶法制备球形水凝胶吸附材料具有3D倒漏斗状微观形貌结构，孔径分布宽泛，对水体中重金属、染料等污染物具有快速响应机制，已被广泛用于水处理过程研究。综述了滴制法制备球形水凝胶吸附材料的主要过程机理、水凝胶具有的特殊形貌结构及其在水处理过程中的应用，分析了球形水凝胶吸附材料在水处理应用过程中存在的问题和局限，并指出了其在水处理领域的应用前景及发展方向。

关键词: 凝胶, 滴定-凝胶法, 制备, 吸附剂, 废水

Abstract:

The spherical hydrogel adsorbent prepared by titration-gel method has a 3D inverted funnel-like micro-morphological structure, a wide pore size distribution, and a fast response mechanism to heavy metals, dyes and other pollutants in water. It has been widely used in water treatment process research. The one-step titration-gel method is really a facile way to fabricate the hydrogel adsorbents with observably spherical structure. Herein, the formation mechanism of the hydrogel beads which were developed by the one-step titration-gel method was discussed. And, the authors of this manuscript review the researches which published in recently that used the hydrogel beads to remove the different pollutants from waste water. The main difficulties and limitations, or the prospects of the spherical hydrogel beads used in waste water treatment, also, were stated. The authors of this manuscript hoped this work would provide a corresponding guideline for the researchers who are aiming at preparing the spherical hydrogel adsorbents for waste water treatments.

Key words: gel, one-step titration gel method, preparation, adsorbents, waste water

中图分类号:

TQ 316

林帝出, 杨佳薇, 邓玉莹, 戴敏, 郑西来, 彭昌盛. 滴定-凝胶法制备球形水凝胶吸附材料及其在废水处理中的应用[J]. 化工学报, 2020, 71(3): 914-922.

Dichu LIN, Jiawei YANG, Yuying DENG, Min DAI, Xilai ZHENG, Changsheng PENG. Fabrication of spherical hydrogel adsorbents via one-step titration-gel method for waste water treatment—a review[J]. CIESC Journal, 2020, 71(3): 914-922.

图/表 7

参考文献 74

1	Qi X , Wei W , Shen J , et al . Salecan polysaccharide-based hydrogels and their applications: a review[J]. Journal of Materials Chemistry B, 2019, 7(16): 2577-2587.
2	Wang B , Wan Y , Zheng Y , et al . Alginate-based composites for environmental applications: a critical review[J]. Critical Reviews in Environmental Science and Technology, 2019, 49(4): 318-356.
3	Thakur S , Govender P P , Mamo M A , et al . Progress in lignin hydrogels and nanocomposites for water purification: future perspectives[J]. Vacuum, 2017, 146: 342-355.
4	Thakur S , Govender P P , Mamo M A , et al . Recent progress in gelatin hydrogel nanocomposites for water purification and beyond[J]. Vacuum, 2017, 146: 396-408.
5	Shojaeiarani J , Bajwa D , Shirzadifar A . A review on cellulose nanocrystals as promising biocompounds for the synthesis of nanocomposite hydrogels[J]. Carbohydrate Polymers, 2019, 216: 247-259.
6	Mohammadzadeh P P , Peighambardoust S J . A review on acrylic based hydrogels and their applications in wastewater treatment[J]. Journal of Environmental Management, 2018, 217: 123-143.
7	Chen T , Shi P , Zhang J , et al . Natural polymer konjac glucomannan mediated assembly of graphene oxide as versatile sponges for water pollution control[J]. Carbohydrate Polymers, 2018, 202: 425-433.
8	Buslovich A , Horev B , Shebis Y , et al . A facile method for the deposition of volatile natural compound-based nanoparticles on biodegradable polymer surfaces[J]. Journal of Materials Chemistry B, 2018, 6(15): 2240-2249.
9	Hou D , Ding C , Li K , et al . A novel dual-layer composite membrane with underwater-superoleophobic/hydrophobic asymmetric wettability for robust oil-fouling resistance in membrane distillation desalination[J]. Desalination, 2018, 428: 240-249.
10	Pandele A M , Ionita M , Crica L , et al . Novel chitosan-poly(vinyl alcohol)/graphene oxide biocomposites 3D porous scaffolds[J]. Composites Part B: Engineering, 2017, 126: 81-87.
11	Li Y , Xue J , Zhang X , et al . Formation of macrovoid-free PMDA-MDA polyimide membranes using a gelation/non-solvent-induced phase separation method for organic solvent nanofiltration[J]. Industrial & Engineering Chemistry Research, 2019, 58(16): 6712-6720.
12	Malaekeh-Nikouei B , Ghaeni F A , Motamedshariaty V S , et al . Controlled release of prednisolone acetate from molecularly imprinted hydrogel contact lenses[J]. Journal of Applied Polymer Science, 2012, 126(1): 387-394.
13	Gao X , Yin Y , Yan J , et al . Separation, biochemical characterization and salt-tolerant mechanisms of alkaline protease from Aspergillus oryzae [J]. Journal of the Science of Food and Agriculture, 2019, 99(7): 3359-3366.
14	Zhao N , Wu F , Xing Y , et al . Flexible hydrogel electrolyte with superior mechanical properties based on poly(vinyl alcohol) and bacterial cellulose for the solid-state zinc–air batteries[J]. ACS Applied Materials & Interfaces, 2019, 11(17): 15537-15542.
15	Qi M , Zhao K , Bao Q , et al . Adsorption and electrochemical detection of bovine serum albumin imprinted calcium alginate hydrogel membrane[J]. Polymers, 2019, 11(4): 622.
16	Du H , Shi S , Liu W , et al . Hydrophobic-force-driven adsorption of bisphenol A from aqueous solution by polyethylene glycol diacrylate hydrogel microsphere[J]. Environmental Science and Pollution Research, 2019, 26(22): 22362-22371.
17	Tekay E , Aydinoglu D , Sen S . Effective adsorption of Cr(Ⅵ) by high strength chitosan/montmorillonite composite hydrogels involving spirulina biomass/microalgae[J]. Journal of Polymers and the Environment, 2019, 27(8): 1828-1842.
18	Lin D , Shi M , Zhang Y , et al . 3D crateriform and honeycomb polymer capsule with nano re-entrant and screen mesh structures for the removal of multi-component cationic dyes from water[J]. Chemical Engineering Journal, 2019, 375: 121911.
19	Mathur A M , Moorjani S K , Scranton A B . Methods for synthesis of hydrogel networks: a review[J]. Journal of Macromolecular Science, Part C, 1996, 36(2): 405-430.
20	Ahmed E M . Hydrogel: preparation, characterization, and applications: a review[J]. Journal of Advanced Research, 2015, 6(2): 105-121.
21	Arshady R . Suspension, emulsion, and dispersion polymerization — a methodological survey[J]. Colloid and Polymer Science, 1992, 270(8): 717-732.
22	Huang X , Brittain W J . Synthesis and characterization of PMMA nanocomposites by suspension and emulsion polymerization[J]. Macromolecules, 2001, 34(10): 3255-3260.
23	Lin D , Shi M , Wei X , et al . Development of an innovative capsule with three-dimension honeycomb architecture via one-step titration-gel method for the removal of methylene blue[J]. International Journal of Biological Macromolecules, 2019, 128: 911-922.
24	Lin D C , Shi M , Cao Y , et al . Fabrication of SA-SiO₂ capsules with 3D microscopic re-entrant structures via one-step titration-gel method for the removal of methylene blue from water[J]. Express Polymer Letters, 2019, 13(4): 311-326.
25	Ali I , Peng C , Lin D , et al . Encapsulated green magnetic nanoparticles for the removal of toxic Pb²⁺ and Cd²⁺ from water: development, characterization and application[J]. Journal of Environmental Management, 2019, 234: 273-289.
26	Ali I , Peng C , Naz I , et al . Development and application of novel bio-magnetic membrane capsules for the removal of the cationic dye malachite green in wastewater treatment[J]. RSC Advances, 2019, 9(7): 3625-3646.
27	Zhang X , Cheng C , Zhao J , et al . Polyethersulfone enwrapped graphene oxide porous particles for water treatment[J]. Chemical Engineering Journal, 2013, 215/216: 72-81.
28	Shao Z , Huang X , Yang F , et al . Engineering sodium alginate-based cross-linked beads with high removal ability of toxic metal ions and cationic dyes[J]. Carbohydrate Polymers, 2018, 187: 85-93.
29	Tong D , Fang K , Yang H , et al . Efficient removal of copper ions using a hydrogel bead triggered by the cationic hectorite clay and anionic sodium alginate[J]. Environmental Science and Pollution Research, 2019, 26(16): 16482-16492.
30	Karzar J M , Mahkam M . Magnetic nano carboxymethyl cellulose-alginate/chitosan hydrogel beads as biodegradable devices for controlled drug delivery[J]. International Journal of Biological Macromolecules, 2019, 135: 829-838.
31	Bremond N , Santanach-Carreras E , Chu L , et al . Formation of liquid-core capsules having a thin hydrogel membrane: liquid pearls[J]. Soft Matter, 2010, 6(11): 2484-2488.
32	Patil J S , Kamalapur M V , Marapur S C , et al . Ionotropic gelation and polyelectrolyte complexation: the novel techniques to design hydrogel particulate sustained, modulated drug delivery system: a review[J]. Digest Journal of Nanomaterials and Biostructures, 2010, 5(1): 241-248.
33	Rolland L , Santanach-Carreras E , Delmas T , et al . Physicochemical properties of aqueous core hydrogel capsules[J]. Soft Matter, 2014, 10(48): 9668-9674.
34	Liang W , Yang C , Wen G , et al . A facile and controllable method to encapsulate phase change materials with non-toxic and biocompatible chemicals[J]. Applied Thermal Engineering, 2014, 70(1): 817-826.
35	Nofar M , Tabatabaei A , Sojoudiasli H , et al . Mechanical and bead foaming behavior of PLA-PBAT and PLA-PBSA blends with different morphologies[J]. European Polymer Journal, 2017, 90: 231-244.
36	Aydogdu A , Sumnu G , Sahin S . A novel electrospun hydroxypropyl methylcellulose/polyethylene oxide blend nanofibers: morphology and physicochemical properties[J]. Carbohydrate Polymers, 2018, 181: 234-246.
37	Zheng B , Zhang Z , Chen F , et al . Impact of delivery system type on curcumin stability: comparison of curcumin degradation in aqueous solutions, emulsions, and hydrogel beads[J]. Food Hydrocolloids, 2017, 71: 187-197.
38	Ago M , Tardy B L , Wang L , et al . Supramolecular assemblies of lignin into nano- and microparticles[J]. MRS Bulletin, 2017, 42(5): 371-378.
39	Shang L , Cheng Y , Zhao Y . Emerging droplet microfluidics[J]. Chemical Reviews, 2017, 117(12): 7964-8040.
40	Trivedi P , Schaller J , Gustafsson J , et al . Supramolecular design of cellulose hydrogel beads[J]. Journal of Renewable Materials, 2017, 5(5): 400-409.
41	Fang W , Liu L , Li T , et al . Electrospun N-substituted polyurethane membranes with self-healing ability for self-cleaning and oil/water separation[J]. Chemistry-A European Journal, 2016, 22(3): 878-883.
42	Gulyuz U , Okay O . Self-healing poly(acrylic acid) hydrogels with shape memory behavior of high mechanical strength[J]. Macromolecules, 2014, 47(19): 6889-6899.
43	Shao Z , Huang X , Yang F , et al . Engineering sodium alginate-based cross-linked beads with high removal ability of toxic metal ions and cationic dyes[J]. Carbohydrate Polymers, 2018, 187: 85-93.
44	Li L , Xiao J , Wang Z , et al . Preparation of polyvinyl alcohol/chitosan/graphene oxide composite hydrogel and application in removal of Pb(Ⅱ) from aqueous solution[J]. New Chemical Materials, 2016, 44(4): 112-115.
45	Kong Y , Zhuang Y , Han Z , et al . Dye removal by eco-friendly physically cross-linked double network polymer hydrogel beads and their functionalized composites[J]. Journal of Environmental Sciences, 2019, 78: 81-91.
46	Oussalah A , Boukerroui A , Aichour A , et al . Cationic and anionic dyes removal by low-cost hybrid alginate/natural bentonite composite beads: adsorption and reusability studies[J]. International Journal of Biological Macromolecules, 2019, 124: 854-862.
47	Wu M , Chen W , Mao Q , et al . Facile synthesis of chitosan/gelatin filled with graphene bead adsorbent for orange Ⅱ removal[J]. Chemical Engineering Research and Design, 2019, 144: 35-46.
48	Ye X , Xu Q , Xu J . Oxidant-templating fabrication of pure polypyrrole hydrogel beads as a highly efficient dye adsorbent[J]. RSC Advances, 2019, 9(11): 5895-5900.
49	Kurczewska J , Cegłowski M , Schroeder G . Alginate/PAMAM dendrimer – halloysite beads for removal of cationic and anionic dyes[J]. International Journal of Biological Macromolecules, 2019, 123: 398-408.
50	Chatterjee S , Tran H N , Godfred O , et al . Supersorption capacity of anionic dye by newer chitosan hydrogel capsules via green surfactant exchange method[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(3): 3604-3614.
51	Upadhyay A , Rao C P . Porous, pH-responsive, and reusable hydrogel beads of bovine serum albumin_Au hybrid as smart nanofactories for the removal of organic and inorganic pollutants from water: a detailed demonstration by spectroscopy and microscopy[J]. ACS Applied Materials & Interfaces, 2019, 11(8): 7965-7973.
52	Zhang H , Omer A M , Hu Z , et al . Fabrication of magnetic bentonite/carboxymethyl chitosan/sodium alginate hydrogel beads for Cu (Ⅱ) adsorption[J]. International Journal of Biological Macromolecules, 2019, 135: 490-500.
53	Hu Z , Omer A M , Ouyang X K , et al . Fabrication of carboxylated cellulose nanocrystal/sodium alginate hydrogel beads for adsorption of Pb(Ⅱ) from aqueous solution[J]. International Journal of Biological Macromolecules, 2018, 108: 149-157.
54	Arshad F , Selvaraj M , Zain J , et al . Polyethylenimine modified graphene oxide hydrogel composite as an efficient adsorbent for heavy metal ions[J]. Separation and Purification Technology, 2019, 209: 870-880.
55	Yi X , He J , Guo Y , et al . Encapsulating Fe₃O₄ into calcium alginate coated chitosan hydrochloride hydrogel beads for removal of Cu (Ⅱ) and U (Ⅵ) from aqueous solutions[J]. Ecotoxicology and Environmental Safety, 2018, 147: 699-707.
56	Wang F , Li J , Su Y , et al . Adsorption and recycling of Cd(Ⅱ) from wastewater using straw cellulose hydrogel beads[J]. Journal of Industrial and Engineering Chemistry, 2019, 80: 361-369.
57	Tao H , Li S , Zhang L , et al . Magnetic chitosan/sodium alginate gel bead as a novel composite adsorbent for Cu(Ⅱ) removal from aqueous solution[J]. Environmental Geochemistry and Health, 2019, 41(1SI): 297-308.
58	Yang X , Zhou T , Ren B , et al . Removal of Mn (Ⅱ) by sodium alginate/graphene oxide composite double-network hydrogel beads from aqueous solutions[J]. Scientific Reports, 2018, 8(1): 10717.
59	Kongarapu R J , Nayak A K , Khobragade M U , et al . Surfactant bilayer on chitosan bead surface for enhanced Ni(Ⅱ) adsorption[J]. Sustainable Materials and Technologies, 2018, 18: e00077.
60	Chen S , Hu J , Shi J , et al . Composite hydrogel particles encapsulated ammonium molybdophosphate for efficiently cesium selective removal and enrichment from wastewater[J]. Journal of Hazardous Materials, 2019, 371: 694-704.
61	Shan S , Tang H , Zhao Y , et al . Highly porous zirconium-crosslinked graphene oxide/alginate aerogel beads for enhanced phosphate removal[J]. Chemical Engineering Journal, 2019, 359: 779-789.
62	Pal P , Edathil A A , Banat F . Calcium alginate gel and hard beads for the removal of total organic acid anions and heavy metal ions from industrial lean methyldiethanolamine solvent[J]. Polymer Bulletin, 2019, 76(1): 103-118.
63	Sahraei R , Sekhavat P Z , Ghaemy M . Novel magnetic bio-sorbent hydrogel beads based on modified gum tragacanth/graphene oxide: removal of heavy metals and dyes from water[J]. Journal of Cleaner Production, 2017, 142: 2973-2984.
64	Pu S , Ma H , Zinchenko A , et al . Novel highly porous magnetic hydrogel beads composed of chitosan and sodium citrate: an effective adsorbent for the removal of heavy metals from aqueous solutions[J]. Environmental Science and Pollution Research, 2017, 24(19SI): 16520-16530.
65	Vijayalakshmi K , Devi B M , Latha S , et al . Batch adsorption and desorption studies on the removal of lead (Ⅱ) from aqueous solution using nanochitosan/sodium alginate/microcrystalline cellulose beads[J]. International Journal of Biological Macromolecules, 2017, 104: 1483-1494.
66	Li M , Wang Z , Li B . Adsorption behaviour of congo red by cellulose/chitosan hydrogel beads regenerated from ionic liquid[J]. Desalination and Water Treatment, 2016, 57(36): 16970-16980.
67	Ma J , Liu Y , Ali O , et al . Fast adsorption of heavy metal ions by waste cotton fabrics based double network hydrogel and influencing factors insight[J]. Journal of Hazardous Materials, 2018, 344: 1034-1042.
68	Lu T , Xiang T , Huang X , et al . Post-crosslinking towards stimuli-responsive sodium alginate beads for the removal of dye and heavy metals[J]. Carbohydrate Polymers, 2015, 133: 587-595.
69	Yue Y , Han J , Han G , et al . Cellulose nanofibers reinforced sodium alginate-polyvinyl alcohol hydrogels: core-shell structure formation and property characterization[J]. Carbohydrate Polymers, 2016, 147: 155-164.
70	Kong W , Yue Q , Li Q , et al . Adsorption of Cd²⁺ on GO/PAA hydrogel and preliminary recycle to GO/PAA-CdS as efficient photocatalyst[J]. Science of the Total Environment, 2019, 668: 1165-1174.
71	Xu Y , Zhu B K , Xu Y Y . A study on formation of regular honeycomb pattern in polysulfone film[J]. Polymer, 2005, 46(3): 713-717.
72	Li L , Chen C , Li J , et al . Robust and hydrophilic polymeric films with honeycomb pattern and their cell scaffold applications[J]. Journal of Materials Chemistry, 2009, 19(18): 2789-2796.
73	Wang Z , Cheng W , Ma J , et al . Condensed solute droplets templated honeycomb pattern on polymer films[J]. Journal of Colloid and Interface Science, 2014, 436: 16-18.
74	Bui V , Thuy L T , Tran Q C , et al . Ordered honeycomb biocompatible polymer films via a one-step solution-immersion phase separation used as a scaffold for cell cultures[J]. Chemical Engineering Journal, 2017, 320: 561-569.

水凝胶	染料	最佳吸附量/(mg/g)	吸附机制	吸附等温模型	文献来源
SPSC	MB,CV,MG	394.08,1756.20,1034.04	离子交换及化学键合	Langmuir,Hill, two-step Langmuir	[18]
SASC	MB	350.80	静电结合	Langmuir	[24]
SAP	MB	1255.75	静电结合及化学键合	Langmuir	[46]
A-B 1/1	MB,CR	1171,95.55	静电结合	Langmuir,Langmuir	[47]
PHG	MO	236.9	化学键合	Langmuir	[48]
Alg/Hal_PAMAM	MB,SY	75.3,22.5	化学键合	Freundlich,Freundlich	[49]
SN5	CR	2592	静电结合	Langmuir	[50]
BSA_Au NCs	EY	245	静电结合	Langmuir	[51]

水凝胶	染料	最佳吸附量/(mg/g)	吸附机制	吸附等温模型	文献来源
SPSC	MB,CV,MG	394.08,1756.20,1034.04	离子交换及化学键合	Langmuir,Hill, two-step Langmuir	[18]
SASC	MB	350.80	静电结合	Langmuir	[24]
SAP	MB	1255.75	静电结合及化学键合	Langmuir	[46]
A-B 1/1	MB,CR	1171,95.55	静电结合	Langmuir,Langmuir	[47]
PHG	MO	236.9	化学键合	Langmuir	[48]
Alg/Hal_PAMAM	MB,SY	75.3,22.5	化学键合	Freundlich,Freundlich	[49]
SN5	CR	2592	静电结合	Langmuir	[50]
BSA_Au NCs	EY	245	静电结合	Langmuir	[51]

水凝胶	重金属	最佳吸附量/（mg/g）	吸附机制	吸附等温模型	文献来源
Mag-Ben/CCS/Alg	Cu(Ⅱ)	56.79	化学键合	Langmuir	[52]
CCN-Alg	Pb(Ⅱ)	338.98	化学键合	Langmuir	[53]
FGOCA	Pb(Ⅱ),Hg(Ⅱ)	602,374	化学键合	Langmuir,Langmuir	[54]
CCM	Cu(Ⅱ),U(Ⅵ)	143.276,392.692	化学键合	Langmuir,Langmuir	[55]
SCHBs	Cd(Ⅱ)	95.62	化学键合	Langmuir	[56]
MCSB	Cu(Ⅱ)	124.53	化学键合	Langmuir	[57]
GAD	Mn(Ⅱ)	56.49	化学键合	Freundlich	[58]
POSTSC	Ni(Ⅱ)	76.92	氢键结合及化学键合	Langmuir	[59]

水凝胶	重金属	最佳吸附量/（mg/g）	吸附机制	吸附等温模型	文献来源
Mag-Ben/CCS/Alg	Cu(Ⅱ)	56.79	化学键合	Langmuir	[52]
CCN-Alg	Pb(Ⅱ)	338.98	化学键合	Langmuir	[53]
FGOCA	Pb(Ⅱ),Hg(Ⅱ)	602,374	化学键合	Langmuir,Langmuir	[54]
CCM	Cu(Ⅱ),U(Ⅵ)	143.276,392.692	化学键合	Langmuir,Langmuir	[55]
SCHBs	Cd(Ⅱ)	95.62	化学键合	Langmuir	[56]
MCSB	Cu(Ⅱ)	124.53	化学键合	Langmuir	[57]
GAD	Mn(Ⅱ)	56.49	化学键合	Freundlich	[58]
POSTSC	Ni(Ⅱ)	76.92	氢键结合及化学键合	Langmuir	[59]

Abbreviation	Meaning	Abbreviation	Meaning
A-B 1/1	SA/halloysite polyamidoamine	MCSB	magnetic chitosan/SA bead
Alg/Hal_PAMAM	chitosan	MG	malachite green
APS	one-step titration gel method	MO	methyl orange
Au NCs	liquid-liquid phase separation technique	ORII	orange Ⅱ
BSA	bovine serum albumin	OSTGM	one-step titration gel method
CAG CCM	calcium alginate gel calcium alginate coated chitosan	PAMPS	post-cross-linked 2-acrylamido-2-methylpropa-1-propanesulfonic acid
CCN-Alg	carboxylated cellulose nanocrystal-SA	PHG	polypyrrole hydrogel
CR	Congo red	POSTSC	post-micellar-chitosan beads
CS	chitosan	PS-I	PVA-SA droplets after first cross-linking
CS/Gel-GN	CS/gelatin- graphite	PVA	polyvinyl alcohol
CV	crystal violet	SA	sodium alginate
EY	Eosin yellow	SAP	single network SA/PVA bead
FC-IPNs	full cross-linking inter-penetrating polymer networks	SASC	SA-SiO₂ capsule
FGOCA	functionalization GO embedded calcium alginate	SCHBs	straw cellulose hydrogel beads
GA	glutaraldehyde	SC-IPNs	semi cross-linking interpenetrating polymer networks
GAD	GO/SA double network	SN5	CS-SDS-5%(mass) NaOH
GO	graphene oxide	SPSC	SA-PVA-SiO₂ capsule
LLPST	liquid-liquid phase separation technique	SY	sun set yellow
Mag-Ben/CCS/Alg	magnetic bentonite/carboxy-methyl chitosan/SA	Zr-GO/Alg	zirconium-crosslinked GO/SA
MB	methylene blue	ZVI	zero-valent iron