黄原酸改性交联面包酵母的制备及对Pb(Ⅱ)的吸附特性

doi:10.16085/j.issn.1000-6613.2021-1900

摘要/Abstract

摘要：

以面包酵母为基材，通过两步法制备得到黄原酸改性交联面包酵母（XCBY），并应用于水溶液中Pb(Ⅱ)的去除研究，原始面包酵母、XCBY和XCBY-Pb(Ⅱ)的理化特性分别采用SRA、SEM、EDS、FTIR、XRD和XPS等手段进行表征，研究了溶液pH、吸附剂用量、Pb(Ⅱ)初始浓度等因素对XCBY 吸附性能的影响，并探讨了吸附动力学、等温线、热力学和XCBY的再生性能。结果表明，原始面包酵母经交联和黄原酸改性后，其细胞形态没有明显变化，且对Pb(Ⅱ)的吸附性能得到明显提高。XCBY对Pb(Ⅱ)的吸附过程更符合伪二阶动力学和Langmuir吸附等温线模型，热力学分析表明吸附过程为自发的吸热反应。在30℃、吸附时间为40min的条件下，Langmuir吸附等温线拟合结果显示XCBY对Pb(Ⅱ)的最大吸附量达到319.91mg/g。此外，Pb(Ⅱ)在XCBY上的吸附机制主要依赖于XCBY表面—NH₂的配位作用、—OH的离子交换以及—C( $? ???????$ S)—S^-的螯合作用。指出作为一种简便经济的面包酵母化学改性方法，XCBY在含重金属离子废水的吸附处理方面具有潜在的发展应用前景。

关键词: 面包酵母, 黄原酸改性, 交联, 废水, 吸附机制

Abstract:

Xanthate-functionalized cross-linked baker's yeast (XCBY) was prepared by a two-step method and applied to remove Pb(Ⅱ) from aqueous solutions. The physicochemical characteristics of non-modified baker's yeast, XCBY and Pb(Ⅱ)-loaded XCBY were characterized by SRA, SEM, EDS, FTIR, XRD, and XPS. The impacts of operating parameters of pH, adsorbent dosage, initial concentration of Pb(Ⅱ) on the adsorption performance of XCBY were systematically investigated, and the adsorption kinetics, isotherm, thermodynamics and regeneration performance of XCBY were discussed. The results showed that the original baker's yeast had no significant change in cell morphology after crosslinking and xanthic acid modification, and its adsorption performance for Pb(Ⅱ) was significantly improved. Pseudo-second-order and Langmuir isotherm models effectively described the adsorption behavior of XCBY, and the thermodynamic analysis revealed that the adsorption process of Pb(Ⅱ) onto XCBY was spontaneous and endothermic. The adsorption process for Pb(Ⅱ) reached equilibrium at 30℃ in 40min with a maximum adsorption capacity of 319.91mg/g from the Langmuir isotherm model. Additionally, the adsorption mechanism of Pb(Ⅱ) on XCBY mainly depended on the coordination of —NH₂, ion exchange of —OH and complexation of —C( $? ???????$ S)—S^-. As a facile and economical chemical modification method of baker's yeast, the modified material was a potential and prospective adsorbent for use in the treatment of heavy metal-bearing wastewater.

Key words: baker's yeast, xanthate-functionalized, cross-linked, wastewater, adsorption mechanism

中图分类号:

X705

段正洋, 胡柠檬, 李天国. 黄原酸改性交联面包酵母的制备及对Pb(Ⅱ)的吸附特性[J]. 化工进展, 2022, 41(7): 3925-3937.

DUAN Zhengyang, HU Ningmeng, LI Tianguo. Preparation of xanthate-functionalized cross-linked baker's yeast and its adsorption characteristics for Pb(Ⅱ)[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3925-3937.

图/表 18

参考文献 53

1	WANG N N, XU X J, LI H Y, et al. Enhanced selective adsorption of Pb(Ⅱ) from aqueous solutions by one-pot synthesis of xanthate-modified chitosan sponge: behaviors and mechanisms[J]. Industrial & Engineering Chemistry Research, 2016, 55(47): 12222-12231.
2	WANG N N, XU X J, LI H Y, et al. Preparation and application of a xanthate-modified thiourea chitosan sponge for the removal of Pb(Ⅱ) from aqueous solutions[J]. Industrial & Engineering Chemistry Research, 2016, 55(17): 4960-4968.
3	JIA Q J, ZHANG W T, LI D P, et al. Hydrazinolyzed cellulose-g-polymethyl acrylate as adsorbent for efficient removal of Cd(Ⅱ) and Pb(Ⅱ) ions from aqueous solution[J]. Water Science and Technology, 2017, 75(5): 1051-1058.
4	徐大勇, 张苗, 杨伟伟, 等. 氧化铝改性污泥生物炭粒制备及其对Pb(Ⅱ)的吸附特性[J]. 化工进展, 2020, 39(3): 1153-1166.
	XU Dayong, ZHANG Miao, YANG Weiwei, et al. Preparation of alumina modified sludge biocharcoal particles and their adsorption characteristics for Pb(‍Ⅱ)[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 1153-1166.
5	PENG X L, XU F, ZHANG W Z, et al. Magnetic Fe₃O₄@silica-xanthan gum composites for aqueous removal and recovery of Pb²⁺ [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2014, 443: 27-36.
6	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.
	LIU Jianglong, GUO Yan, XI Yihui. 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.
7	ZONG P F, CAO D L, WANG S F, et al. Synthesis of Fe₃O₄/CD magnetic nanocomposite via low temperature plasma technique with high enrichment of Ni(Ⅱ) from aqueous solution[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 70: 134-140.
8	ZHOU G Y, LUO J M, LIU C B, et al. A highly efficient polyampholyte hydrogel sorbent based fixed-bed process for heavy metal removal in actual industrial effluent[J]. Water Research, 2016, 89: 151-160.
9	YUAN M L, XIE T F, YAN G J, et al. Effective removal of Pb²⁺ from aqueous solutions by magnetically modified zeolite[J]. Powder Technology, 2018, 332: 234-241.
10	KUL A R, KOYUNCU H. Adsorption of Pb(Ⅱ) ions from aqueous solution by native and activated bentonite: Kinetic, equilibrium and thermodynamic study[J]. Journal of Hazardous Materials, 2010, 179(1/2/3): 332-339.
11	OKOLI C P, DIAGBOYA P N, ANIGBOGU I O, et al. Competitive biosorption of Pb(Ⅱ) and Cd(Ⅱ) ions from aqueous solutions using chemically modified moss biomass (Barbula lambarenensis)[J]. Environmental Earth Sciences, 2016, 76(1): 33-42.
12	TONG M, YU J X, SUN X M, et al. Polymer modified biomass of baker’s yeast for treating simulated wastewater containing nickel and lead[J]. Polymers for Advanced Technologies, 2007, 18(10): 829-834.
13	XIA Y X, MENG L Y, JIANG Y J, et al. Facile preparation of MnO₂ functionalized baker’s yeast composites and their adsorption mechanism for Cadmium[J]. Chemical Engineering Journal, 2015, 259: 927-935.
14	ZHANG W, MENG L Y, MU G Q, et al. A facile strategy for fabrication of nano-ZnO/yeast composites and their adsorption mechanism towards lead (Ⅱ) ions[J]. Applied Surface Science, 2016, 378: 196-206.
15	GÖKSUNGUR Y, ÜREN S, GÜVENÇ U. Biosorption of cadmium and lead ions by ethanol treated waste baker's yeast biomass[J]. Bioresource Technology, 2005, 96(1): 103-109.
16	LI T T, LIU Y G, PENG Q Q, et al. Removal of lead(Ⅱ) from aqueous solution with ethylenediamine-modified yeast biomass coated with magnetic chitosan microparticles: kinetic and equilibrium modeling[J]. Chemical Engineering Journal, 2013, 214: 189-197.
17	XU M, ZHANG Y S, ZHANG Z M, et al. Study on the adsorption of Ca²⁺, Cd²⁺ and Pb²⁺ by magnetic Fe₃O₄ yeast treated with EDTA dianhydride[J]. Chemical Engineering Journal, 2011, 168(2): 737-745.
18	BEDIAKO J K, WEI W, KIM S, et al. Removal of heavy metals from aqueous phases using chemically modified waste Lyocell fiber[J]. Journal of Hazardous Materials, 2015, 299: 550-561.
19	VIEIRA M G A, NETO A F A, GIMENES M L, et al. Removal of nickel on Bofe bentonite calcined clay in porous bed[J]. Journal of Hazardous Materials, 2010, 176(1/2/3): 109-118.
20	ÁLVAREZ-AYUSO E, GARCÍA-SÁNCHEZ A. Removal of heavy metals from waste waters by natural and Na-exchanged bentonites[J]. Clays and Clay Minerals, 2003, 51(5): 475-480.
21	OUARDI Y EL, LENOBLE V, BRANGER C, et al. Enhancing clay adsorption properties: a comparison between chemical and combined chemical/thermal treatments[J]. Groundwater for Sustainable Development, 2021, 12: 100544.
22	ZHU Y H, HU J, WANG J L. Competitive adsorption of Pb(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) onto xanthate-modified magnetic chitosan[J]. Journal of Hazardous Materials, 2012, 221/222: 155-161.
23	DENG S B, TING Y P. Characterization of PEI-modified biomass and biosorption of Cu(Ⅱ), Pb(Ⅱ) and Ni(Ⅱ)[J]. Water Research, 2005, 39(10): 2167-2177.
24	XIA L, HU Y X, ZHANG B H. Kinetics and equilibrium adsorption of copper(Ⅱ) and nickel(Ⅱ) ions from aqueous solution using sawdust xanthate modified with ethanediamine[J]. Transactions of Nonferrous Metals Society of China, 2014, 24(3): 868-875.
25	ZHENG L C, MENG P P. Preparation, characterization of corn stalk xanthates and its feasibility for Cd (Ⅱ) removal from aqueous solution[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 58: 391-400.
26	LIANG S, GUO X Y, FENG N C, et al. Application of orange peel xanthate for the adsorption of Pb²⁺ from aqueous solutions[J]. Journal of Hazardous Materials, 2009, 170(1): 425-429.
27	KANNAMBA B, REDDY K L, APPARAO B V. Removal of Cu(Ⅱ) from aqueous solutions using chemically modified chitosan[J]. Journal of Hazardous Materials, 2010, 175(1/2/3): 939-948.
28	LAGERGREN S. Zur theorie der sogenannten adsorption gelöster stoffe, Kungliga Svenska Vetenskapsakademiens[J]. Handlingar, 1898, 24(4): 1-39.
29	HO Y S, MCKAY G. Pseudo-second order model for sorption processes[J]. Process Biochemistry, 1999, 34(5): 451-465.
30	CHEN Y W, WANG J L. The characteristics and mechanism of Co(Ⅱ) removal from aqueous solution by a novel xanthate-modified magnetic chitosan[J]. Nuclear Engineering and Design, 2012, 242: 452-457.
31	KAMARI A, NGAH W S W. Isotherm, kinetic and thermodynamic studies of lead and copper uptake by H₂SO₄ modified chitosan[J]. Colloids and Surfaces B: Biointerfaces, 2009, 73(2): 257-266.
32	LI Z L, KONG Y, GE Y Y. Synthesis of porous lignin xanthate resin for Pb²⁺ removal from aqueous solution[J]. Chemical Engineering Journal, 2015, 270: 229-234.
33	LANGMUIR I. The adsorption of gases on plane surfaces of glass, mica and platinum[J]. Journal of the American Chemical Society, 1918, 40(9): 1361-1403.
34	FREUNDLICH H. Of the adsorption of gases. Section Ⅱ. Kinetics and energetics of gas adsorption. Introductory paper to section Ⅱ[J]. Transactions of the Faraday Society, 1932, 28: 195.
35	SIPS R. Combined form of Langmuir and freundlich equations[J]. Journal of Chemical Physics, 1948, 16: 490-495.
36	GUERRA D J L, MELLO I, RESENDE R, et al. Application as absorbents of natural and functionalized Brazilian bentonite in Pb²⁺ adsorption: equilibrium, kinetic, pH, and thermodynamic effects[J]. Water Resources and Industry, 2013, 4: 32-50.
37	邹雪, 龚正君. 黄原酸功能化蛋壳膜及其对Pb(Ⅱ)的吸附研究[J]. 西南大学学报(自然科学版), 2020, 42(11): 141-146.
	ZOU Xue, GONG Zhengjun. Study on adsorption removal of Pb(Ⅱ) by xanthated eggshell membrane[J]. Journal of Southwest University (Natural Science Edition), 2020, 42(11): 141-146.
38	FENG K, WEN G H. Absorbed Pb²⁺ and Cd²⁺ ions in water by cross-linked starch xanthate[J]. International Journal of Polymer Science, 2017, 2017: 1-9.
39	LV L, CHEN N, FENG C P, et al. Heavy metal ions removal from aqueous solution by xanthate-modified cross-linked magnetic chitosan/poly(vinyl alcohol) particles[J]. RSC Advances, 2017, 7(45): 27992-28000.
40	GAO T T, YU J G, ZHOU Y, et al. Performance of xanthate-modified multi-walled carbon nanotubes on adsorption of lead ions[J]. Water, Air, & Soil Pollution, 2017, 228(5): 172-183.
41	WANG C Q, WANG H, GU G H. Ultrasound-assisted xanthation of cellulose from lignocellulosic biomass optimized by response surface methodology for Pb(Ⅱ) sorption[J]. Carbohydrate Polymers, 2018, 182: 21-28.
42	CHEN M, WANG X F, ZHANG H. Comparative research on selective adsorption of Pb(Ⅱ) by biosorbents prepared by two kinds of modifying waste biomass: highly-efficient performance, application and mechanism[J]. Journal of Environmental Management, 2021, 288: 112388.
43	EVERETT D H. The thermodynamics of adsorption. Part Ⅱ.—Thermodynamics of monolayers on solids[J]. Transactions of the Faraday Society, 1950, 46: 942-957.
44	DENG J Q, LIU Y G, LIU S B, et al. Competitive adsorption of Pb(Ⅱ), Cd(Ⅱ) and Cu(Ⅱ) onto chitosan-pyromellitic dianhydride modified biochar[J]. Journal of Colloid and Interface Science, 2017, 506: 355-364.
45	GÖK Ö, ÖZCAN A, ERDEM B, et al. Prediction of the kinetics, equilibrium and thermodynamic parameters of adsorption of copper(Ⅱ) ions onto 8-hydroxy quinoline immobilized bentonite[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2008, 317(1/2/3): 174-185.
46	QIN F, BAI B, JING D W, et al. CdS nanoparticles anchored on the surface of yeast via a hydrothermal processes for environmental applications[J]. RSC Advances, 2014, 4(66): 34864-34872.
47	CHANG Y K, LEU M H, CHANG J E, et al. Combined two-stage xanthate processes for the treatment of copper-containing wastewater[J]. Engineering in Life Sciences, 2007, 7(1): 75-80.
48	HE J, LU Y C, LUO G S. Ca(Ⅱ) imprinted chitosan microspheres: an effective and green adsorbent for the removal of Cu(II), Cd(Ⅱ) and Pb(Ⅱ) from aqueous solutions[J]. Chemical Engineering Journal, 2014, 244: 202-208.
49	ZHAO F P, REPO E, SONG Y, et al. Polyethylenimine-cross-linked cellulose nanocrystals for highly efficient recovery of rare earth elements from water and a mechanism study[J]. Green Chemistry, 2017, 19(20): 4816-4828.
50	ODIO O F, LARTUNDO-ROJAS L, PALACIOS E G, et al. Synthesis of a novel poly-thiolated magnetic nano-platform for heavy metal adsorption. Role of thiol and carboxyl functions[J]. Applied Surface Science, 2016, 386: 160-177.
51	GEDAM N, NETI N R, KORMUNDA M, et al. Novel lead dioxide-graphite-polymer composite anode for electrochemical chlorine generation[J]. Electrochimica Acta, 2015, 169: 109-116.
52	ZINGG D S, HERCULES D M. ChemInform abstract: electron spectroscopy for chemical analysis studies of lead sulfide oxidation[J]. Chemischer Informationsdienst, 1978, 9(50): 1992-1995.
53	LIANG X F, XU Y M, SUN G H, et al. Preparation, characterization of thiol-functionalized silica and application for sorption of Pb²⁺ and Cd²⁺ [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2009, 349(1/2/3): 61-68.

C₀/mg·L ^-¹	q_{e， exp}/mg·g ^-¹	伪一阶动力学模型			伪二阶动力学模型
C₀/mg·L ^-¹	q_{e， exp}/mg·g ^-¹	q_e/mg·g ^-¹	k₁/min ^-¹	R²	q_e/mg·g ^-¹	k₂/g·mg ^-¹·min ^-¹	R²
25	117.78	112.25	0.285	0.9788	119.21	0.00367	0.9995
50	231.77	222.28	0.320	0.9749	235.04	0.00214	0.9991
100	307.58	296.96	0.509	0.9757	309.93	0.00280	0.9988
200	317.10	308.74	0.537	0.9785	321.62	0.00289	0.9989

C₀/mg·L ^-¹	q_{e， exp}/mg·g ^-¹	伪一阶动力学模型			伪二阶动力学模型
C₀/mg·L ^-¹	q_{e， exp}/mg·g ^-¹	q_e/mg·g ^-¹	k₁/min ^-¹	R²	q_e/mg·g ^-¹	k₂/g·mg ^-¹·min ^-¹	R²
25	117.78	112.25	0.285	0.9788	119.21	0.00367	0.9995
50	231.77	222.28	0.320	0.9749	235.04	0.00214	0.9991
100	307.58	296.96	0.509	0.9757	309.93	0.00280	0.9988
200	317.10	308.74	0.537	0.9785	321.62	0.00289	0.9989

t /℃	q_{e， exp}/mg·g ^-¹	Langmuir模型			Freundlich模型			Langmuir-Freundlich模型
t /℃	q_{e， exp}/mg·g ^-¹	q_max/mg·g ^-¹	K_L /L·mg ^-¹	R²	K_F /mg·g ^-¹	n	R²	q_max /mg·g ^-¹	K_LF/L·mg ^-¹	n_LF	R²
25	306.51	308.95	0.433	0.9972	122.38	4.746	0.9217	317.79	0.392	0.868	0.9988
30	317.87	319.91	0.496	0.9927	131.23	4.906	0.9069	323.59	0.478	0.932	0.9922
35	321.90	322.39	0.871	0.9954	149.63	5.531	0.9103	331.11	0.795	0.829	0.9982

t /℃	q_{e， exp}/mg·g ^-¹	Langmuir模型			Freundlich模型			Langmuir-Freundlich模型
t /℃	q_{e， exp}/mg·g ^-¹	q_max/mg·g ^-¹	K_L /L·mg ^-¹	R²	K_F /mg·g ^-¹	n	R²	q_max /mg·g ^-¹	K_LF/L·mg ^-¹	n_LF	R²
25	306.51	308.95	0.433	0.9972	122.38	4.746	0.9217	317.79	0.392	0.868	0.9988
30	317.87	319.91	0.496	0.9927	131.23	4.906	0.9069	323.59	0.478	0.932	0.9922
35	321.90	322.39	0.871	0.9954	149.63	5.531	0.9103	331.11	0.795	0.829	0.9982

吸附剂	吸附量/mg·g ^-¹	参考文献
黄原酸改性交联面包酵母	319.91	本研究
黄原酸改性壳聚糖海绵	216.45	［1］
黄原酸改性纤维素	531.29	［18］
黄原酸改性玉米秸秆	20.58	［25］
黄原酸改性多孔木质素	64.90	［32］
黄原酸功能化蛋壳膜	33.11	［37］
黄原酸改性交联淀粉	47.11	［38］
黄原酸改性交联磁性壳聚糖/聚乙烯醇颗粒	59.86	［39］
黄原酸改性多壁纳米碳管	83.01	［40］
超声协助黄原酸改性纤维素	134.41	［41］
黄原酸改性板栗壳	124.84	［42］