聚乙烯亚胺原位改性多孔灯芯草高效吸附废水中的Cr（Ⅵ）

doi:10.11949/0438-1157.20201653

摘要/Abstract

摘要：

为了制备具有胺基利用率高、结构稳定、使用方便的Cr（Ⅵ）吸附材料，以聚乙烯亚胺（PEI）为胺基改性剂，具有类海绵多孔结构的灯芯草（JC）为支撑基材，将吸入JC的PEI通过环氧氯丙烷原位接枝于其纤维表面，获得可整块使用的多孔吸附材料（PEI-JC）。采用元素分析、SEM、FT-IR、XPS表征PEI-JC的组成与结构，分析PEI-JC对Cr（Ⅵ）的吸附机理。考察PEI浓度、溶液的pH、Cr（Ⅵ）浓度与共存化合物等因素对吸附的影响。结果表明，质量分数为10.0%的PEI所制备的PEI_10.0-JC，在30℃与pH为2.0的条件下，其Langmuir模型的最大吸附量为474.6 mg·g^-1；PEI_10.0-JC可将含各种共存化合物溶液中的Cr（Ⅵ）从10 mg·L^-1降至排放标准（0.5 mg·L^-1）以下；PEI_10.0-JC可重复使用，其结构在吸附过程中未发生明显变化；吸附与还原作用是PEI-JC去除水溶液中Cr（Ⅵ）的主要机制。

关键词: 灯芯草, 聚乙烯亚胺, 原位改性, 废水, Cr（Ⅵ）, 吸附作用

Abstract:

An adsorbent with the advantages such as high utilization of amino group, stable structure and easy-to-handle operation was prepared to efficiently capture aquatic Cr(Ⅵ) by using the polyethyleneimine (PEI) as the modification reagent and the juncus (JC), a natural biomass with sponge-like structure, as the structure support. The PEI solution containing epichlorohydrin was firstly introduced into the JC and then the PEI was in-situ attached to JC fibers by the grafting reaction, resulting in a porous adsorbent (PEI-JC). The elemental analysis, SEM, FT-IR and XPS were employed to characterize the composition and structure of PEI-JC, as well as the adsorption mechanism of Cr(Ⅵ). The effects of PEI concentration, solution pH, initial concentration of Cr(Ⅵ) and coexisting compounds on the adsorption were studied. The results show that the maximum adsorption capacity of the Langmuir model of PEI_10.0-JC prepared from PEI with concentration of 10.0%(mass) is 474.6 mg·g^-1 at 30℃ and a pH of 2.0; PEI_10.0-JC could decrease the Cr(Ⅵ) in the solutions with different coexisting compounds from 10.0 mg·L^-1 to the value that is less than the emission standard of industrial wastewater of China (0.5 mg·L^-1); PEI_10.0-JC can be reused, and its structure has not changed significantly during the adsorption process; adsorption and reduction are the main mechanisms for PEI-JC to remove Cr (Ⅵ) from aqueous solutions.

Key words: juncus, polyethyleneimine, in-situ modification, waste water, hexavalent chromium, adsorption

中图分类号:

TQ 085

梁兴唐, 李凤枝, 钟书明, 张瑞瑞, 焦淑菲, 汪双双, 尹艳镇. 聚乙烯亚胺原位改性多孔灯芯草高效吸附废水中的Cr（Ⅵ）[J]. 化工学报, 2021, 72(6): 3380-3389.

LIANG Xingtang, LI Fengzhi, ZHONG Shuming, ZHANG Ruirui, JIAO Shufei, WANG Shuangshuang, YIN Yanzhen. In-situ modification of porous juncus with polyethyleneimine for efficient capture of Cr(Ⅵ) from wastewater[J]. CIESC Journal, 2021, 72(6): 3380-3389.

图/表 16

图1 JC (a)、PEI5.0-JC (b)、PEI10.0-JC (c)与PEI15.0-JC (d)的SEM照片；PEI10.0-JC吸附Cr(Ⅵ)后的SEM照片(插图)及Cr面扫描能谱 (e)；吸附-脱附5次后PEI10.0-JC的SEM照片(f)

Fig.1 SEM images of JC (a), PEI5.0-JC (b), PEI10.0-JC (c) and PEI15.0-JC (d); SEM image(inset) and Cr mapping of PEI10.0-JC after adsorbing Cr(Ⅵ) (e); SEM image of PEI10.0-JC after 5 cycles of adsorption-desorption (f)

图2 JC (a)、PEI10.0-JC (b)、吸附Cr(Ⅵ)后PEI10.0-JC (c)以及吸附-洗脱5次后PEI10.0-JC (d)的FT-IR谱图

Fig.2 FT-IR spectra of JC (a), PEI10.0-JC (b), PEI10.0-JC after the adsorption of Cr(Ⅵ) (c) and the PEI10.0-JC after 5 cycles of adsorption-desorption (d)

图3 PEI浓度对PEI-JC的N含量及其吸附的影响

Fig.3 Effect of the PEI concentration on the N content of PEI-JC and its adsorption

图4 pH对吸附的影响（a）；PEI10.0-JC在不同pH溶液中的Zeta电位（b）

Fig.4 Effect of pH on the adsorption (a); Zeta potential as a function of pH for PEI10.0-JC (b)

图5 处理时间对吸附的影响(a)；吸附过程的准二级动力学模型拟合(b)

Fig.5 Effect of contact time on the adsorption (a); Fitting of the adsorption via pseudo-second-order model (b)

表1 PEI10.0-JC对Cr(Ⅵ)吸附的准二级动力学参数

Table 1 Kinetic parameters of PEI10.0-JC toward Cr(Ⅵ) removal fitted with pseudo-second-order model

C₀ /(mg·L^–1)	k /(g·mg^–1·min^–1)	Q_E/(mg·g^–1)	R²
100	3.74×10^-4	106.3	0.999
200	1.69×10^-4	196.1	0.998

图6 不同温度下初始浓度对吸附的影响

Fig.6 Effect of C0 on the adsorption of PEI10.0-JC toward Cr(Ⅵ) under different temperature

图7 不同温度下PEI10.0-JC吸附等温线模型拟合

Fig.7 Isotherm fitting for the adsorption of Cr(Ⅵ) onto PEI10.0-JC at different temperatures

表2 PEI10.0-JC在不同温度下等温吸附模型的拟合参数

Table 2 Isotherms parameters for the adsorption of PEI10.0-JC toward Cr(Ⅵ) at various temperatures

T/℃	Langmuir			Freundlich			Tempkin
T/℃	Q_m	K_L	R²	K_F	n	R²	K_T	b	R²
30	474.6	0.038	0.977	59.0	2.78	0.960	1.87	41.3	0.885
40	519.7	0.043	0.983	70.3	2.82	0.951	2.50	39.9	0.856
50	550.0	0.045	0.984	76.5	2.85	0.924	1.01	28.5	0.965

表3 基于PEI改性吸附剂的性能比较

Table 2 Comparison of the performance for the PEI modified adsorbents

Sample	pH	T/℃	Q_m/(mg·g^-1)	Ref.
PEI/氧化石墨	2.0	35	50.3	[11]
PEI/纤维素	2.0	25	119.4	[23]
PEI/甲壳素	2.0	25	330.4	[24]
PEI/boehmite	3.0	25	51.1	[8]
PEI/pineapple leaf fiber	2.0	30	222.4	[12]
PEI/PVA	4.0	23	150.0	[15]
PEI/carbon nanotube	2.0	25	40.3	[27]
PEI/chitosan	3.0	30	331.3	[28]
PEI/graphene oxide	2.0	30	436.2	[29]
PEI_10.0-JC	2.0	30	474.6	本研究

表4 PEI10.0-JC对Cr(Ⅵ)的吸附的热力学参数

Table 4 Thermodynamic parameters for the adsorption of Cr(Ⅵ) by PEI10.0-JC

T/K	ΔG/(kJ·mol^-1)	ΔS/(kJ·(mol·K)^-1)	ΔH/(kJ·mol^-1)
303	-19.11
313	-20.05	0.086	6.91
323	-20.83

图8 共存化合物对PEI10.0-JC吸附Cr(Ⅵ)的影响

Fig.8 Effect of coexisting compounds on the adsorption of PEI10.0-JC toward Cr(Ⅵ)

图9 循环吸附过程中PEI10.0-JC吸附量的变化

Fig.9 The change of adsorption capacity of PEI10.0-JC during the cycles of adsorption-desorption

图10 Cr(Ⅵ)吸附前、后PEI10.0-JC的全范围(a)、Cr 2p (b)和N 1s[(c)、(d)]的XPS谱图

Fig.10 Full range (a), Cr 2p (b) and N 1s [(c),(d)] XPS spectra of PEI10.0-JC before and after Cr(Ⅵ) adsorption

图11 吸附过程溶液中铬离子种类的变化（C0 = 50 mg·L-1）

Fig.11 The change of the Cr species during the adsorption (C0 = 50 mg·L-1)

图12 PEI-JC对Cr(Ⅵ)的可能吸附机理

Fig.12 The proposed adsorption mechanism of PEI-JC toward Cr(Ⅵ)

参考文献 32

1	余淦申, 郭茂新, 黄进勇. 工业废水处理及再生利用[M]. 北京: 化学工业出版社, 2012: 266-268.
	Yu G S, Guo M X, Huang J Y. Industrial Wastewater Treatment and Reuse[M]. Beijing: Chemical Industry Press, 2012: 266-268.
2	Jobby R, Jha P, Yadav A K, et al. Biosorption and biotransformation of hexavalent chromium [Cr(Ⅵ)]: a comprehensive review[J]. Chemosphere, 2018, 207: 255-266.
3	Peng H, Guo J. Removal of chromium from wastewater by membrane filtration, chemical precipitation, ion exchange, adsorption electrocoagulation, electrochemical reduction, electrodialysis, electrodeionization, photocatalysis and nanotechnology: a review[J]. Environmental Chemistry Letters, 2020, 18: 2055-2068.
4	Hosseini S M, Sohrabnejad S, Nabiyouni G, et al. Magnetic cation exchange membrane incorporated with cobalt ferrite nanoparticles for chromium ions removal via electrodialysis[J]. Journal of Membrane Science, 2019, 583: 292-300.
5	王子帅, 王耀强, 肖刚, 等. 磁性纳米Fe₃O₄@TiO₂可见光下光催化还原Cr(Ⅵ)[J]. 化工学报, 2019, 70(10): 4062-4071.
	Wang Z S, Wang Y Q, Xiao G, et al. Photocatalytic reduction of Cr(Ⅵ) by magnetic nanomaterial Fe₃O₄@TiO₂ under visible light[J]. CIESC Journal, 2019, 70(10): 4062-4071.
6	伍清新, 刘杰, 游少鸿, 等. 李氏禾湿地系统净化Cr(Ⅵ)污染水体的机理研究[J]. 环境科学学报, 2014, 34(9): 2306-2312.
	Wu Q X, Liu J, You S H, et al. Decontamination mechanism of Cr(Ⅵ)-polluted water in constructed wetland planted with Leersia hexandra Swartz[J]. Acta Scientiae Circumstantiae, 2014, 34(9): 2306-2312.
7	Zhang Y, Zhu C, Liu F, et al. Effects of ionic strength on removal of toxic pollutants from aqueous media with multifarious adsorbents: a review[J]. Science of the Total Environment, 2019, 646: 265-279.
8	Zhang H, Li P, Wang Z, et al. Sustainable disposal of Cr(Ⅵ): adsorption-reduction strategy for treating textile wastewaters with amino-functionalized boehmite hazardous solid wastes[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(5): 6811-6819.
9	Wang J, Sun T, Saleem A, et al. Enhanced adsorptive removal of Cr(Ⅵ) in aqueous solution by polyethyleneimine modified palygorskite[J]. Chinese Journal of Chemical Engineering, 2020, 28(10): 2650-2657.
10	Yan Y, An Q, Xiao Z, et al. Flexible core-shell/bead-like alginate@PEI with exceptional adsorption capacity, recycling performance toward batch and column sorption of Cr(Ⅵ)[J]. Chemical Engineering Journal, 2017, 313: 475-486.
11	王家宏, 尹小龙, 吉艳芬. 聚乙烯亚胺改性氧化石墨对水中Cr(Ⅵ)的吸附[J]. 无机化学学报, 2015, 31(6): 1185-1193.
	Wang J H, Yin X L, Ji Y F. Cr(Ⅵ) adsorption on polyethyleneimine modified graphite oxide[J]. Chinese Journal of Inorganic Chemistry, 2015, 31(6): 1185-1193.
12	Tangtubtim S, Saikrasun S. Adsorption behavior of polyethyleneimine-carbamate linked pineapple leaf fiber for Cr(Ⅵ) removal[J]. Applied Surface Science, 2019, 467: 596-607.
13	Fayazi M, Ghanbarian M. One-pot hydrothermal synthesis of polyethylenimine functionalized magnetic clay for efficient removal of noxious Cr(Ⅵ) from aqueous solutions[J]. Silicon, 2020, 12: 125-134.
14	Setyono D, Valiyaveettil S. Functionalized paper—a readily accessible adsorbent for removal of dissolved heavy metal salts and nanoparticles from water[J]. Journal of Hazardous Materials, 2016, 302: 120-128.
15	Zhang S, Shi Q, Korfiatis G, et al. Chromate removal by electrospun PVA/PEI nanofibers: adsorption, reduction, and effects of co-existing ions[J]. Chemical Engineering Journal, 2020, 387: 124179.
16	Qiu B, Guo J, Zhang X, et al. Polyethylenimine facilitated ethyl cellulose for hexavalent chromium removal with a wide pH range[J]. ACS Applied Materials & Interfaces, 2014, 6: 19816-19824.
17	Song L, Liu F, Zhu C, et al. Facile one-step fabrication of carboxymethyl cellulose based hydrogel for highly efficient removal of Cr(Ⅵ) under mild acidic condition[J]. Chemical Engineering Journal, 2019, 369: 641-651.
18	Liang X, Liang B, Wei J, et al. A cellulose-based adsorbent with pendant groups of quaternary ammonium and amino for enhanced capture of aqueous Cr(Ⅵ)[J]. International Journal of Biological Macromolecules, 2020, 148: 802-810.
19	Rizzo C, Andrews J L, Steed J W, et al. Carbohydrate-supramolecular gels: adsorbents for chromium (Ⅵ) removal from wastewater[J]. Journal of Colloid and Interface Science, 2019, 548: 184-196.
20	Luo T, Tian X, Yang C, et al. Polyethylenimine-functionalized corn bract, an agricultural waste material, for efficient removal and recovery of Cr(Ⅵ) from aqueous solution[J]. Journal of Agricultural and Food Chemistry, 2017, 65: 7153-7158.
21	韩业钜, 张耿崚, 王小琴, 等. 表面活性剂强化超声波-离子液体预处理对水葫芦酶解的影响[J]. 环境科学学报, 2017, 37(7) : 2699-2706
	Han Y J, Chang K L, Wang X Q, et al. Surfactant assisted ultrasound-ionic liquid pretreatment process for enzymatic hydrolysis of water hyacinth[J]. Acta Scientiae Circumstantiae, 2017, 37(7): 2699-2706.
22	Liang X, Fan X, Li R, et al. Efficient removal of Cr(Ⅵ) from water by quaternized chitin/branched polyethylenimine biosorbent with hierarchical pore structure[J]. Bioresource Technology, 2018, 250: 178-184.
23	陈豪宇, 张胜利, 凯橙橙, 等. 聚乙烯亚胺改性纤维素纤维对Cr(Ⅵ)的吸附研究[J]. 环境科学学报, 2018, 38(8): 3090-3098.
	Chen H Y, Zhang S L, Kai C C, et al. Polyethyleneimine modified cellulose fiber for Cr(Ⅵ) removal from aqueous solution[J]. Acta Scientiae Circumstantiae, 2018, 38(8): 3090-3098.
24	梁兴唐, 钟书明, 刘子杰, 等. 甲壳素/聚乙烯亚胺复合物对水溶液中Cr(Ⅵ)的吸附[J]. 化工学报, 2018, 69(5): 2255-2262.
	Liang X T, Zhong S M, Liu Z J, et al. Chitin/polyethyleneimine composite as an adsorbent of aqueous Cr(Ⅵ)[J]. CIESC Journal, 2018, 69(5): 2255-2262.
25	Polowczyk I, Urbano B, Rivas B L, et al. Equilibrium and kinetic study of chromium sorption on resins with quaternary ammonium and N-methyl-D-glucamine groups[J]. Chemical Engineering Journal, 2016, 284: 395-404.
26	Al-Ghouti M A, Da'ana D A. Guidelines for the use and interpretation of adsorption isotherm models: a review[J]. Journal of Hazardous Materials, 2020, 393: 122383.
27	Sambaza S, Masheane M L, Malinga S, et al. Polyethyleneimine-carbon nanotube polymeric nanocomposite adsorbents for the removal of Cr⁶⁺ from water[J]. Physics and Chemistry of the Earth, 2017, 100: 236-246.
28	Zhu W J, Dang Q F, Liu C S, et al. Cr(Ⅵ) and Pb(Ⅱ) capture on pH-responsive polyethyleneimine and chloroacetic acid functionalized chitosan microspheres[J]. Carbohydrate Polymers, 2019, 219: 353-367.
29	Geng J, Yin Y, Liang Q, et al. Polyethyleneimine cross-linked graphene oxide for removing hazardous hexavalent chromium: adsorption performance and mechanism[J]. Chemical Engineering Journal, 2019, 361: 1497-1510.
30	Niazi L, Lashanizadegan A, Sharififard H. Chestnut oak shells activated carbon: preparation, characterization and application for Cr(Ⅵ) removal from dilute aqueous solutions[J]. Journal of Cleaner Production, 2018, 185: 554-561.
31	Iftime M M, Marin L. Chiral betulin-imino-chitosan hydrogels by dynamic covalent sonochemistry[J]. Ultrasonics Sonochemistry, 2018, 45: 238-247.
32	Kwak H W, Lee K H. Polyethylenimine-functionalized silk sericin beads for high-performance remediation of hexavalent chromium from aqueous solution[J]. Chemosphere, 2018, 207: 507-516.

[1]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[2]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[3]	张艳梅, 袁涛, 李江, 刘亚洁, 孙占学. 高效SRB混合菌群构建及其在酸胁迫条件下的性能研究[J]. 化工学报, 2023, 74(6): 2599-2610.
[4]	张兰河, 赖青燚, 王铁铮, 关潇卓, 张明爽, 程欣, 徐小惠, 贾艳萍. H₂O₂对SBR脱氮效率和污泥性能的影响[J]. 化工学报, 2023, 74(5): 2186-2196.
[5]	闫新龙, 黄志刚, 胡清勋, 张新, 胡晓燕. Cu/Co掺杂多孔炭活化过硫酸盐降解水中硝基酚研究[J]. 化工学报, 2023, 74(3): 1102-1112.
[6]	李承威, 骆华勇, 张铭轩, 廖鹏, 方茜, 荣宏伟, 王竞茵. 氢氧化镧交联壳聚糖微球的微流控制备及其除磷性能[J]. 化工学报, 2022, 73(9): 3929-3939.
[7]	赵希强, 张健, 孙爽, 王文龙, 毛岩鹏, 孙静, 刘景龙, 宋占龙. 生物质炭改性微球去除化工废水中无机磷的性能研究[J]. 化工学报, 2022, 73(5): 2158-2173.
[8]	贾艳萍, 丁雪, 刚健, 佟泽为, 张海丰, 张兰河. Mn强化Fe/C微电解工艺条件优化及降解油墨废水机理[J]. 化工学报, 2022, 73(5): 2183-2193.
[9]	王祺, 房阔, 贺聪慧, 王凯军. 流动电极电容去离子技术综述：研究进展与未来挑战[J]. 化工学报, 2022, 73(3): 975-989.
[10]	毛恒, 王月, 王森, 刘伟民, 吕静, 陈甫雪, 赵之平. APTES改性ZIF-L/PEBA混合基质膜强化渗透汽化分离苯酚研究[J]. 化工学报, 2022, 73(3): 1389-1402.
[11]	王洒, 温怡静, 郭丹煜, 周欣, 李忠. 锆基MOF次级结构单元调控及轻烃吸附分离性能增强[J]. 化工学报, 2022, 73(2): 730-738.
[12]	郑喜, 王涛, 任永胜, 赵珍珍, 王雪琪, 赵之平. 聚间苯二甲酰间苯二胺平板膜的制备及其性能研究[J]. 化工学报, 2022, 73(10): 4707-4721.
[13]	张兰河, 汪露, 李梓萌, 唐宏, 郭静波, 贾艳萍, 张明爽. 电极超滤膜生物反应器处理阴离子表面活性剂废水[J]. 化工学报, 2022, 73(10): 4679-4691.
[14]	付鹏波,田金乙,吕文杰,黄渊,刘毅,卢浩,杨强,修光利,汪华林. 物理法水处理技术[J]. 化工学报, 2022, 73(1): 59-72.
[15]	黄莉婷, 韩昫身, 金艳, 马强, 于建国. 煤化工反渗透浓水的高效降解菌株筛选、鉴定及应用研究[J]. 化工学报, 2021, 72(9): 4881-4891.