Adsorption of Rhodamine B and Congo Red in dyeing paper wastewater by chlorine-substituted UiO-66

doi:10.16085/j.issn.1000-6613.2018-1905

Abstract

Abstract:

To improve the adsorption capacity of metal-organic frameworks (MOFs), chlorine-substituted UiO-66 (UiO-66-Cl) was synthesized by replacing terephthalic acid with 2-chloroterephthalic acid as an organic ligand. With UiO-66, wood activated carbon (AC) and Bagasse as references, the adsorption capacity of UiO-66-Cl to Rhodamine B (Rh-B) and Congo Red (CR) in dyeing paper wastewater and its adaptability to pH of two dye solutions were studied. The adsorption process conditions of UiO-66-Cl were optimized. Based on isothermal adsorption models of Langmuir and Freundlich, the maximum adsorption capacity of this adsorbent was fitted. Finally, the performance of recovery, desorption and reuse of this adsorbent was also evaluated. The results showed that the adsorption capacity of UiO-66-Cl to Rh-B and CR and its adaptability to pH of two dye solutions were significantly higher than those of UiO-66, AC and Bagasse. The adsorption processes of UiO-66-Cl to Rh-B and CR were in accordance with the Freundlich isotherm adsorption model, indicating a multi-layer adsorption with heterogeneous multi-sites. Within the initial dye concentration range of 10—1000mg/L, the maximum adsorption capacity of UiO-66-Cl to Rh-B and CR were 94.28mg/L and 151.84mg/L, respectively. Compared with HCl (0.1mol/L), NaOH (0.1mol/L) and 95% (v/v) ethanol solutions, ethanol-HCl solution (volume ratio of 0.1mol/L HCl to 95% ethanol solution was 0.5∶99.5) was a good regeneration solvent system for UiO-66-Cl. When the initial dye concentration was 50mg/L, the removal of Rh-B and CR by regenerated UiO-66-Cl were both close to 90%. Therefore, UiO-66-Cl is a stable, efficient and regenerated adsorbent for the removal of Rh-B and CR from dyeing paper wastewater.

Key words: chlorine-substituted UiO-66, Rhodamine B, Congo Red, adsorption, regeneration

摘要：

为了进一步提高金属-有机骨架材料（metal-organic frameworks, MOFs）的吸附性能，本文将有机配体对苯二甲酸替换为2-氯对苯二甲酸，合成了金属-有机骨架化合物UiO-66的衍生物——氯代UiO-66（UiO-66-Cl）。以UiO-66、木质活性炭（AC）和蔗渣作为参照，研究了UiO-66-Cl对染色纸废水中罗丹明B（Rh-B）和刚果红（CR）的吸附性能和对染料废水pH的适应性，优化其吸附工艺条件，基于等温吸附模型（Langmuir和Freundlich）拟合其最大吸附量，最终对该吸附剂的回收、解吸附和再利用性能进行评价。研究结果表明：UiO-66-Cl对两种染料（Rh-B和CR）的吸附性能和对染料溶液pH的适应性均显著高于UiO-66、AC和蔗渣；其对Rh-B和CR的吸附过程符合Freundlich等温吸附模型，属于非均质多位点的多层吸附；在10~1000mg/L的初始染料浓度范围内，该吸附剂对Rh-B和CR的最大吸附容量分别为94.28mg/g和151.84mg/g；与HCl（0.1mol/L）、NaOH（0.1mol/L）和95%（体积分数）乙醇溶液相比，乙醇-HCl溶液（0.1mol/L HCl与95%乙醇溶液的体积比为0.5∶99.5）是UiO-66-Cl的良好再生溶剂体系，染料初始浓度为50mg/L时，再生UiO-66-Cl对Rh-B和CR的移除率均接近90%。由此可见，UiO-66-Cl可作为一种稳定、高效且易再生的吸附剂应用于去除染色纸废水中的Rh-B和CR。

关键词: 氯代UiO-66, 罗丹明B, 刚果红, 吸附, 再生

CLC Number:

X793

Guangxu YANG, Zhenggang GONG, Xiaolin LUO, Liulian HUANG, Lihui CHEN, Jing LIU. Adsorption of Rhodamine B and Congo Red in dyeing paper wastewater by chlorine-substituted UiO-66[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3434-3442.

杨光绪, 龚正刚, 罗小林, 黄六莲, 陈礼辉, 刘婧. 氯代UiO-66吸附染色纸废水中罗丹明B和刚果红[J]. 化工进展, 2019, 38(07): 3434-3442.

Figures/Tables 13

References 33

1	金玉红. 试论中国最早的染色纸[J]. 中国造纸, 2016, 35(8): 71-74.
	JINY H．Discussion on earliest dyed paper in China[J]. China Pulp & Paper, 2016, 35(8): 71-74.
2	黎珊, 任庆功, 纪俊玲. 纤维素纤维的新型染色技术研究进展[J]. 染整技术, 2010, 32(11): 6-12.
	LIS, RENQ G, JIJ L. Research progress on new dyeing technology of cellulose fiber[J]. Textile Dying and Finishing Journal, 2010, 32(11): 6-12.
3	YAGUBM T, SEN T K, AFROZES, et al. Dye and its removal from aqueous solution by adsorption: a review[J]. Advances in Colloid & Interface Science, 2014, 209(07): 172-184.
4	陈梅兰. 罗丹明B的危害及其在食品中快速检测方法的建立[D]. 福州: 福州大学, 2014.
	CHENM L. The toxicity of Rhodamine B and establishment of its rapid detection method in food products[D]. Fuzhou：Fuzhou University, 2014.
5	TIANJ, ZHAOJ, OLAJUYINA M, et al. Effective degradation of Rhodamine B by electro-Fenton process, using ferromagnetic nanoparticles loaded on modified graphite felt electrode as reusable catalyst: in neutral pH condition and without external aeration[J]. Environmental Science & Pollution Research, 2016, 23(15): 15471-15482.
6	TIANJ, OLAJUYINA M, MUT, et al. Efficient degradation of Rhodamine B using modified graphite felt gas diffusion electrode by electro-Fenton process[J]. Environmental Science & Pollution Research International, 2016, 23(12): 11574-11583.
7	YANGZ Y, SHENG Y, HEY P, et al. Preparation of TiO₂/SiO₂, composite oxide and its photocatalytic degradation of Rhodamine B[J]. Journal of Porous Materials, 2016, 23(3): 589-599.
8	LIUY, GUOH, ZHANGY, et al. Activation of peroxymonosulfate by BiVO₄, under visible light for degradation of Rhodamine B[J]. Chemical Physics Letters, 2016, 653: 101-107.
9	YUJ X, LIB H, SUNX M, et al. Adsorption of methylene blue and Rhodamine B on baker's yeast and photocatalytic regeneration of the biosorbent[J]. Biochemical Engineering Journal, 2009, 45(2): 145-151.
10	张亚丹, 万永军, 陈丽燕, 等. 米根霉磁性生物吸附剂的制备及其对刚果红的吸附[J]. 过程工程学报, 2012, 12(6): 1014-1019.
	ZHANGY D, WANY J, CHENL Y, et al. Preparation and adsorption properties of magnetic rhizopus oryzae biosorbent for Congo Red[J]. The Chinese Journal of Process Engineering, 2012, 12(6): 1014-1019.
11	JIANGX, HUANGJ. Adsorption of Rhodamine B on two novel polar-modified post-cross-linked resins: equilibrium and kinetics[J]. Journal of Colloid & Interface Science, 2016, 467: 230-238.
12	SCHAPIRER, FREUNDY. An investigation into the effect of porosities on the adsorption of Rhodamine B using titania-silica mixed oxide xerogels[J]. Journal of Environmental Management, 2013, 128(20): 530-539.
13	ZOUZ, ZHANGY, ZHANGH, et al. A combined H₃PO₄ activation and boron templating process for easy synthesis of highly porous, spherical activated carbons as a superior adsorbent for Rhodamine B[J]. RSC Advances, 2016, 6(18): 15226-15233.
14	NATARAJANS, BAJAJH C, TAYADR J. Recent advances based on the synergetic effect of adsorption for removal of dyes from waste water using photocatalytic process[J]. Journal of Environmental Sciences, 2018, 65: 201-222.
15	FORGACSE, CSERHATIT, OROSG. Removal of synthetic dyes from wastewaters: a review[J]. Environment International, 2004, 30(7): 953-971.
16	XUANW, ZHUC, LIUY, et al. Mesoporous metal–organic framework materials [J]. Chemical Society Reviews, 2012, 41(5): 1677-1695.
17	白杨, 张尔攀, 赵红挺. 缺陷UiO-66对水中塑化剂的吸附[J]. 化工进展, 2018, 37(3): 1062-1069.
	BAIY, ZHANGE P, ZHAOH T. Defected UiO-66 for adsorption of plasticizer in aqueous phase[J]. Chemical Industry and Engineering Progress, 2018, 37(3): 1062-1069.
18	李玉洁, 苗晋朋, 孙雪娇, 等.机械化学法合成金属有机骨架材料HKUST-1及其吸附苯性能[J]. 化工学报, 2015, 66(2): 793-799.
	LIY J, MIAOJ P, SUNX J, et al. Mechano-chemical synthesis of HKUST-1 with high capacity of benzene adsorption[J]. CIESC Journal, 2015, 66(2): 793-799.
19	KANDIAHM, NILSENM H, USSEGLIOS, et al. Synthesis and stability of tagged UiO-66 Zr-MOFs [J]. Chemistry of Materials, 2010, 22(24): 6632-6640.
20	KATZM J, BROWNZ J, COLONY J, et al. A facile synthesis of UiO-66, UiO-67 and their derivatives[J]. Chemical Communications, 2013, 49(82): 9449-9451.
21	SHUAIL, PANX. Hydrolysis of cellulose by cellulase-mimetic solid catalyst[J]. Energy & Environmental Science, 2012, 5(5): 6889–6894.
22	BROMBERGL, SUX, HATTONT A. Functional networks of organic and coordination polymers: catalysis of fructose conversion[J]. Chemistry of Materials, 2014, 26(21):6257-6264.
23	JUNGB K, HASANZ, JHUNGS H. Adsorptive removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from water with a metal–organic framework[J]. Chemical Engineering Journal, 2013, 234(12): 99-105.
24	Al-DEGSY S, El-BARGHOUTHIM I, El-SHEIKHA H, et al. Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon[J]. Dyes & Pigments, 2008, 77(1): 16-23.
25	DINGL, ZOUB, GAOW, et al. Adsorption of Rhodamine-B from aqueous solution using treated rice husk-based activated carbon[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2014, 446: 1-7.
26	GUOY, ZHAOJ, ZHANGH, et al. Use of rice husk-based porous carbon for adsorption of Rhodamine B from aqueous solutions[J]. Dyes & Pigments, 2005, 66(2): 123-128.
27	GUPTAV K, MOHAND, SHARMAS, et al. Removal of basic dyes (Rhodamine B and Methylene Blue) from aqueous solutions using bagasse fly ash[J]. Separation Science and Technology, 2000, 35(13): 2097-2113.
28	TOPTASA, DEMIEREGES, AYANE M, et al. Spent mushroom compost as biosorbent for dye biosorption[J]. Clean—Soil, Air, Water, 2014, 42(12): 1721-1728.
29	LIUJ, SHIJ H, QIANC X, et al. Decolorization of Rhodamine-B from aqueous solutions by spent mushroom substrate[J]. Bioresources, 2017, 12(4): 8612-8628.
30	HUOS H, YANX P. Metal–organic framework MIL-100(Fe) for the adsorption of malachite green from aqueous solution[J]. Journal of Materials Chemistry, 2012, 22(15): 7449-7455.
31	YANT, WANGL. Adsorptive removal of Methylene Blue from aqueous solution by spent mushroom substrate: equilibrium, kinetics, and thermodynamics[J]. Bioresources, 2013, 8(3): 4722-4734.
32	KHANT A, SHARMAS, ALI I. Adsorption of Rhodamine B dye from aqueous solution onto acid activated mango (Magnifera indica) leaf powder: equilibrium, kinetic and thermodynamic studies[J]. Journal of Toxicology & Environmental Health Sciences, 2011, 3(10): 286-297.
33	SUTEUD, MALUTANT, BILBAD. Removal of reactive dye Brilliant Red HE-3B from aqueous solutions by industrial lignin: equilibrium and kinetics modeling[J]. Desalination, 2010, 255(1/2/3): 84-90.

染料	λ_max/nm	标准曲线参数		R²
染料	λ_max/nm	α	β	R²
Rh-B	554	5.568	0.045	0.992
CR	497	36.879	-0.278	0.996

染料	λ_max/nm	标准曲线参数		R²
染料	λ_max/nm	α	β	R²
Rh-B	554	5.568	0.045	0.992
CR	497	36.879	-0.278	0.996

样品	BET比表面积/m²·g^-1	孔容/cm³·g^-1
UiO-66	1182.3	0.56
UiO-66-Cl	874.6	0.49
AC	638.7	0.37
蔗渣	3.4	0.01

样品	BET比表面积/m²·g^-1	孔容/cm³·g^-1
UiO-66	1182.3	0.56
UiO-66-Cl	874.6	0.49
AC	638.7	0.37
蔗渣	3.4	0.01

模型	参数	Rh-B	CR
Freundlich	K_F/(mg·g^-1)·(L·mg^-1)^1/ⁿ	4.101	9.235
	n	2.061	2.342
	R²	0.995	0.982
Langmuir	q_max/mg·L^-1	39.526	68.027
	K_L/L·mg^-1	0.112	0.165
	R²	0.910	0.834