Adsorption of Cu（Ⅱ） from Solution by Modified Magnetic Ethyl Cellulose

doi:10.19894/j.issn.1000-0518.210269

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (6): 969-979.DOI: 10.19894/j.issn.1000-0518.210269

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Adsorption of Cu（Ⅱ） from Solution by Modified Magnetic Ethyl Cellulose

Cong-Jun CAO(), Han-Xiao MA, Cheng-Min HOU, Xiao-Jian DING, Biao GUAN

School of Printing，Packaging Engineering and Digital Media Technology，Xi′an University of Technology，Xi′an 710048，China

Received:2021-06-02 Accepted:2021-10-29 Published:2022-06-01 Online:2022-06-27
Contact: Cong-Jun CAO
About author:caocongjun@xaut.edu.com
Supported by:
Shaanxi Province Key Scientific Research Base Project(2019HBGC?55)

Abstract

Abstract:

Heavy metal ions have caused serious harm to the ecological environment and human health. It is urgent to treat heavy metal ions in water. In this paper， a co-precipitation method was used to prepare ethyl cellulose magnetic composite material （EC/Fe₃O₄） by using ethyl cellulose as a template to compound Fe₃O₄ nanoparticles with ethyl cellulose. The influence of the adsorption dosage， pH value of the solution， adsorption time and other factors on the adsorption process of Cu（II） in the solution was explored. The results show that EC/Fe₃O₄ exhibits good adsorption rate and adsorption performance. The adsorption equilibrium can be reached within 4 min. Under the adsorption conditions of Cu（II） concentration of 20 mg/L，solution pH of 7，and adsorption time of 160 min，the unit adsorption q_e of EC/Fe₃O₄ is 76.98 mg/g， and the maximum removal rate is 94.68%. After 8 adsorption cycles， the unit adsorption capacity is 62.21 mg/g.

Key words: Heavy metal ions, Magnetic composite materials, Adsorption, Ethyl cellulose

CLC Number:

O652.6

Cong-Jun CAO, Han-Xiao MA, Cheng-Min HOU, Xiao-Jian DING, Biao GUAN. Adsorption of Cu（Ⅱ） from Solution by Modified Magnetic Ethyl Cellulose[J]. Chinese Journal of Applied Chemistry, 2022, 39(6): 969-979.

Figures/Tables 13

Table 1 Standard Cu（Ⅱ） solutions

样品 Sample	1	2	3	4	5	6	7	8	9	10
ρ（Cu（Ⅱ））/（mg·L^-1）	2	4	6	8	10	12	14	16	18	20
V（Cu（Ⅱ））/mL	0.1	0.2	0.3	0.4	0.5	0.6	0.7	0.8	0.9	1
V（H₂O）/mL	0.9	0.8	0.7	0.6	0.5	0.4	0.3	0.2	0.1	0
V（DDTC）/mL	2	2	2	2	2	2	2	2	2	2

Fig.1 Spectral curves （A） and standard copper ion curve （B） of copper ion solutions with different concentrations

Fig.2 FT-IR spectra of EC，Fe3O4 and EC/Fe3O4 before and after adsorption （A）；TG diagrams of EC，Fe3O4 and EC/Fe3O4 （B）；VSM diagrams of Fe3O4 and EC/Fe3O4 （C）；EC/Fe3O4 N2 adsorption-desorption isotherm and BJH pore size distribution map （D）

Fig.3 SEM images of Fe3O4（A，B）， EC（C，D） and EC/Fe3O4（E，F） under different magnifications

Fig.4 The influence of dosage on the unit adsorption capacity and removal rate of EC/Fe3O4

Fig.5 The effect of solution pH on the unit adsorption capacity of EC/Fe3O4

Fig.6 The influence of different adsorbents of EC， Fe3O4 and EC/Fe3O4 on the unit adsorption capacity of Cu（Ⅱ）

Fig.7 （A） The linear fitting curve of the quasi-first-order kinetic model；（B） The linear fitting curve of the quasi-second-order kinetic model

Table 2 Kinetic model equations and related parameters

动力学模型

Kinetic model

方程

Formula

q_e

R²

准一阶动力学

Quasi?first?order dynamics model

l n ? q e - q t = - k 1 t + l n ? q e

准二阶动力学

Quasi?second?order dynamics model

$t q t = 1 k 2 q e 2 + 1 q e t$

$h = k 2 × q e 2$

Table 2 Kinetic model equations and related parameters

动力学模型

Kinetic model

方程

Formula

q_e

R²

准一阶动力学

Quasi?first?order dynamics model

l n ? q e - q t = - k 1 t + l n ? q e

0.0303

7.6118

0.8575

—

准二阶动力学

Quasi?second?order dynamics model

$t q t = 1 k 2 q e 2 + 1 q e t$

$h = k 2 × q e 2$

0.0297

65.350

0.9999

125.00

Fig.8 （A） Langmuir model fitting curve；（B） Freundlich model fitting curve；（C） Temkin model fitting curve；（D） Dubinin-Radushkevich model fitting curve

Table 3 Isotherm model equations and related parameters

等温线模型 Isotherm model	方程 Formula	参数 Parameter	数值 Value
Langmuir	$ρ e q e = 1 q m a x × ρ e + 1 K L × q m a x$ $R L = 1 1 + K L × ρ 0$	q_max	108.70
		K_L	0.355 2
		R_L	0.123 4
		R²	0.994 3
Freundlich	$l n ? q e = 1 n × l n ? ρ e + l n ? K F$	n	2.925 7
		K_F	1.406 5
		R²	0.762 2
Temkin	$q e = R T b T l n ? k T + R T b T l n ? ρ e$	b_T	129.19
		k_T	6.050
		R²	0.831 7
Dubinin?Radushkevich	$l n ? q e = l n ? q m a x - β ε 2$ $ε = R T l n ? 1 + 1 ρ e$ $E = 1 2 β$	q_max	97.553
		E	912.87
		R²	0.923 2

Table 3 Isotherm model equations and related parameters

等温线模型 Isotherm model	方程 Formula	参数 Parameter	数值 Value
Langmuir	$ρ e q e = 1 q m a x × ρ e + 1 K L × q m a x$ $R L = 1 1 + K L × ρ 0$	q_max	108.70
		K_L	0.355 2
		R_L	0.123 4
		R²	0.994 3
Freundlich	$l n ? q e = 1 n × l n ? ρ e + l n ? K F$	n	2.925 7
		K_F	1.406 5
		R²	0.762 2
Temkin	$q e = R T b T l n ? k T + R T b T l n ? ρ e$	b_T	129.19
		k_T	6.050
		R²	0.831 7
Dubinin?Radushkevich	$l n ? q e = l n ? q m a x - β ε 2$ $ε = R T l n ? 1 + 1 ρ e$ $E = 1 2 β$	q_max	97.553
		E	912.87
		R²	0.923 2

Fig.9 The influence of cycle times on the unit adsorption capacity of EC/Fe3O4

Table 4 Comparison of the renewable performance of similar adsorbents

序号 No.	吸附剂 Adsorbents	吸附条件 Condition	可再生性能 Reusable performance	参考文献 Ref.
1	DTPA?壳聚糖 DTPA?Chitosan	pH=3，25 ℃	经过6个循环后，去除率从42.38%降低至24.23% After 6 cycles，the removal rate decreased from 42.38% to 24.23%	［21］
2	Fe₃O₄@SO₃Na	pH=5，25 ℃	经过2个循环后，吸附量从16.13降低至14.54 mg/g After 2 cycles，the adsorption capacity decreased from 16.13 to 14.54 mg/g	［22］
3	磁性氧化石墨烯 Magnetic graphene oxide	pH=6，20 ℃	经过5个循环后，吸附容量减少16.25% After 5 cycles，the adsorption capacity is reduced by 16.25%	［23］
4	PEI改性磁性膨润土 PEI/KH560/MBent	pH=5，20 ℃	经过5个循环后，吸附量为首次吸附量的60% After 5 cycles，the adsorption capacity is 60% of the first adsorption capacity	［24］

References 24

1	LIU R P， XU Y N， ZHANG J H， et al. Effects of heavy metal pollution on farmland soils and crops： a case study of the Xiaoqinling Gold Belt， China［J］. China Geol， 2020， 3（3）： 402-410.
2	SHARMA R， JASROYIA T， KUMAR R， et al. Multi-biological combined system： a mechanistic approach for removal of multiple heavy metals［J］. Chemosphere， 2021， 276： 130018-130030.
3	CASTRO M R， GONZALEZ M L L， GARCIA D O. Ongoing progress on novel nanocomposite membranes for the separation of heavy metals from contaminated water［J］. Chemosphere， 2021， 270： 129421-129437.
4	ZENG W Z， GUO W X， LI B， et al. Kinetics and mechanistic aspects of removal of heavy metal through gas-liquid sulfide precipitation： a computational and experimental study［J］. J Hazard Mater， 2021， 408： 124868-124875.
5	YAZAN I， VINCENZO N， FAWZI B， et al. Preparation of novel polyvinylidene fluoride （PVDF）-Tin（IV） oxide （SnO₂） ion exchange mixed matrix membranes for the removal of heavy metals from aqueous solutions［J］. Sep Purif Technol， 2020， 250： 117250-117264.
6	EBRAHIMIAN J， MOHSENNIA M， KHAYATKASHANI M. Photocatalytic-degradation of organic dye and removal of heavy metal ions using synthesized SnO₂ nanoparticles by Vitex agnus⁃castus fruit via a green route［J］. Mater Lett， 2020， 263（263）： 127255-127258.
7	VESNA K， TAMARA U， BRANKA P. A review on adsorbents for treatment of water and wastewaters containing copper ions［J］. Chem Eng Sci， 2018， 192： 273-287.
8	王重庆，王晖，江小燕，等. 生物炭吸附重金属离子的研究进展［J］. 化工进展， 2019， 38（1）： 692-706.
	WANG C Q， WANG H， JIANG X Y， et al. Research advances on adsorption of heavy metals by biochar［J］. Chem Ind Eng Prog， 2019， 38（1）： 692-706.
9	ISMAILA O S， WEN D O， FAIZ B M S. Chitosan modifications for adsorption of pollutants⁃a review［J］. J Hazard Mater， 2021， 408（1）： 124889-124904.
10	张波波，张文娟，杜雪岩，等. 铁基磁性纳米材料吸附废水中重金属离子研究进展［J］. 材料工程， 2020， 48（7）： 93-102.
	ZHANG B B， ZHANG W J， DU X Y， et al. Research progress in adsorption of heavy metal ions in wastewater by iron-based magnetic nanomaterial［J］. J Mater Eng， 2020， 48（7）： 93-102.
11	王希越，明明，连丽丽，等. 磁性氧化石墨烯纳米粒子的制备及其对大红染料的去除［J］. 应用化工， 2019， 48（10）： 2324-2327.
	WANG X Y， MING M， LIAN L L， et al. Preparation of magnetic graphene oxide nanoparticles and its application for red dye removal［J］. Appl Chem Ind， 2019， 48（10）： 2324-2327.
12	HE X N， CHE R X， WANG Y L， et al. Core-nanoshell magnetic composite material for adsorption of Pb（II） in wastewater［J］. J Environ Chem Eng， 2015， 3（3）： 1720-1724.
13	PUJA R， PREETI， SUMAN， et al. Sequestration of cadmium ions from aqueous phase using magnetic chitosan composite［J］. Mater Today Proc， 2022， 49（8）： 3375-3383.
14	高红芳，杨辉. 改性二氧化硅/乙基纤维素复合膜的制备及性能［J］. 精细化工， 2020， 37（5）： 1018-1023.
	GAO H F， YANG H. Preparation and properties of modified silica/ethyl cellulose composite film［J］. Fine Chem， 2020， 37（5）： 1018-1023.
15	WANG J， LIU M， DUAN C， et al. Preparation and characterization of cellulose-based adsorbent and its application in heavy metal ions removal［J］. Carbohydr Polym， 2019， 206： 837-843.
16	章子恒，胡然，马艺瑾，等. 紫外-可见分光光度法测定含铜废水中的铜离子［J］. 大学化学， 2021， 9： 157-163.
	ZHANG Z H， HU R， MA Y Y， et al. An experiment for determining copper（II） ions in copper-containing sewage by UV-Vis spectrophotometry［J］. Univ Chem， 2021， 9： 157-163.
17	LARISSA F C， LUIS A M R， LUCAS S R， et al. Low-cost magnetic activated carbon with excellent capacity for organic adsorption obtained by a novel synthesis route［J］. J Environ Chem Eng， 2021， 9（2）： 105061-105069.
18	张铁军，李博，韩剑宏，等. 磁性改性玉米秸秆材料吸附铬的性能及机理研究［J］. 工业水处理， 2020， 40（12）： 100-105.
	ZHANG T J， LI B， HAN J H， et al. Study on adsorption performance and mechanism of chromium on magnetic modified corn stalk［J］. Ind Water Treat， 2020， 40（12）： 100-105.
19	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 J L， GUO Y， XI Y H. Adsorption and mechanism of copper ions in water by red mud modified with FeCl₃and hexadecyl trimethyl ammonium bromide （CTAB）［J］. Chem Ind Eng Prog， 2020， 39（2）： 776-789.
20	ZHENG L W， GAO Y C， DU J H， et al. A novel， recyclable magnetic biochar modified by chitosan-EDTA for the effective removal of Pb（II） from aqueous solution［J］. RSC Adv， 2020， 10： 40196-40205.
21	SALEEM A， WANG J， SUN T， et al. Enhanced and selective adsorption of copper ions from acidic conditions by diethylenetriaminepentaacetic acid-chitosan sewage sludge composite［J］. J Environ Chem Eng， 2020， 8（6）： 104430-104439.
22	王家宏，雷思莉. 磺酸基改性磁性吸附剂去除水中的Cu（Ⅱ）［J］. 环境化学， 2019， 38（8）： 1785-1792.
	WANG J J， LEI S L. Removal of Cu（Ⅱ） by sulfonic acid modified magnetic adsorbent［J］. Environ Chem， 2019， 38（8）： 1785-1792.
23	肖海梅，蔡蕾，张朝晖，等. 磁性氧化石墨烯/MIL-101（Cr）表面金属离子印迹聚合物制备及其对Cu（Ⅱ）和Pb（Ⅱ）选择性吸附［J］. 应用化学， 2020， 37（9）： 1076-1086.
	XIAO H M， CAI L， ZHANG C H， et al. Preparation of ion-imprinted polymers based on magnetic graphene oxide/MIL-101（Cr） and selective adsorption of Cu（II） and Pb（II）［J］. Chinese J Appl Chem， 2020， 37（9）： 1076-1086.
24	孙志勇，王智懿，张娇，等. 聚乙烯亚胺改性磁性膨润土对Pb²⁺和Cu²⁺的吸附性能［J］. 精细化工， 2021， 38（1）： 169-175.
	SUN Z Y， WANG Z Y， ZHANG J， et al. Adsorption properties of polyethyleneimine modified magnetic bentonite for Pb²⁺ and Cu²⁺［J］. Fine Chem， 2021， 38（1）： 169-175.

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Adsorption of Cu（Ⅱ） from Solution by Modified Magnetic Ethyl Cellulose

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