Dynamic adsorption of phosphorus by modified nano cellulose and its regeneration

doi:10.16085/j.issn.1000-6613.2019-1757

Abstract

Abstract:

The iron-modified nanocellulose (Fe(OH)₃@CNFs) was used as an adsorbent for dynamic phosphorus removal experiments, and the effects of different column heights and different flow rates on Fe(OH)₃@CNFs phosphorus adsorption performance were investigated. The results showed that the higher the packing column (6—16cm) and the slower the flow velocity of the water (5—10mL/min), the longer the time required for the adsorption to reach equilibrium and the more favorable for Fe(OH)₃@CNFs to phosphorus dynamic adsorption. The NaOH solution was used to desorb the adsorbent for in-situ regeneration. After regeneration, the adsorption capacity of the adsorption column was 83% of the original adsorption column, indicating that the Fe(OH)₃@CNFs material had a good regeneration capacity. The Yoon-Nelson model was used to calculate the time required to adsorb 50% of the target pollutants. The average relative deviation between the fitted value and the experimental value was between 1.8% and 6.9%, which showed that the Yoon-Nelson model could well describe the dynamic adsorption behavior of phosphorus by Fe(OH)₃@CNFs materials. Using FTIR and XPS to analyze the adsorption mechanism, it was found that Fe(OH)₃@CNFs material had the ability to adsorb phosphorus, and mainly existed as FePO₄ and Fe₂(HPO₄)₃ after adsorption. The adsorption column was used to dynamically adsorb the effluent from the secondary sedimentation tank of the domestic sewage treatment plant, and at a flow rate of 10 mL/min and a packing height of 12cm, the adsorption capacity at saturation was 34.5mg/g.

Key words: iron-modified nanocellulose, dynamic adsorption, phosphorus, regeneration

摘要：

以铁改性纳米纤维素[Fe(OH)₃@CNFs]为吸附剂进行动态吸附除磷试验，探究了不同柱高和不同流速对Fe(OH)₃@CNFs吸附磷性能的影响。结果表明：吸附柱填充越高（6～16cm），进水流速越慢（5～10mL/min），吸附达到平衡所需时间越长，越有利于Fe(OH)₃@CNFs对磷的动态吸附。采用NaOH溶液对吸附剂解吸进行原位再生，再生后吸附柱对磷的吸附量为原吸附柱的83%，表明Fe(OH)₃@CNFs材料具有较好的再生能力。通过Yoon-Nelson模型计算吸附50%目标污染物所需的时间，拟合值与实验值的平均相对偏差在1.8%～6.9%之间，表明Yoon-Nelson模型能够很好地描述Fe(OH)₃@CNFs材料对磷的动态吸附行为。使用红外光谱和X射线光电子能谱对吸附机理进行分析发现Fe(OH)₃@CNFs材料对磷具有吸附能力，并且吸附后主要以FePO₄和Fe₂(HPO₄)₃的形式存在。利用吸附柱对生活污水处理厂二沉池出水进行动态吸附，在流速为10mL/min、填装高度为12cm的条件下，饱和时的吸附容量为34.5mg/g。

关键词: 铁改性纳米纤维素, 动态吸附, 磷, 再生

CLC Number:

X703.1

Lin YUAN, Ying CHEN, Min LIU, Tingting WANG. Dynamic adsorption of phosphorus by modified nano cellulose and its regeneration[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2907-2914.

袁林, 陈滢, 刘敏, 王婷庭. 改性纳米纤维素对磷的动态吸附及再生[J]. 化工进展, 2020, 39(7): 2907-2914.

References

1	刘阳, 朱宗强, 朱义年, 等. 桉树遗态Fe/C复合材料对水中磷的动态吸附研究[J]. 离子交换与吸附, 2018, 34(2): 137-148.
1	LIU Y, ZHU Z Q, ZHU Y N, et al. Studies on the dynamic adsorption of P(Ⅴ) in aqueous solution using the porous biomorph-genetic Fe/C composites with eucalyptus templates[J]. Ion Exchange and Adsorption, 2018, 34(2): 137-148.
2	彭进平, 郭建维, 崔亦华. 改性硅藻土对富营养化水体中磷的吸附行为[J]. 离子交换与吸附, 2012, 28(1): 35-45.
2	PENG J P, GUO J W, CUI Y H. Phosphorus sorption behavior in eutrophication water by modified diatomite[J]. Ion Exchange and Adsorption, 2012, 28(1): 35-45.
3	王志刚, 贾中原, 吕喜军, 等. 含磷废水处理技术研究现状[J]. 天津化工, 2014, 28(3): 7-10.
3	WANG Z G, JIA Z Y, LYU X J, et al. Research status of phosphorus wastewater treatment technology[J]. Tianjin Chemical Industry, 2014, 28(3): 7-10.
4	郑俊, 马露露, 刘宝河. 多孔硅酸钙滤料吸附床除磷试验研究[J]. 环境污染与防治, 2013, 35(8): 28-32.
4	ZHENG J, MA L L, LIU B H. Study on the removal of phosphate by porous calcium silicate adsorption bed[J]. Environmental Pollution and Prevention, 2013, 35(8): 28-32.
5	MAHAR F K, HE L L, WEI K, et al. Rapid adsorption of lead ions using porous carbon nanofibers[J]. Chemosphere, 2019, 225: 360-367.
6	钱程, 袁基刚, 张峰榛, 等. 钙改性膨润土对磷的动态吸附及其再生研究[J].中国给水排水, 2018, 34(17): 108-111.
6	QIAN C, YUAN J G, ZHANG F Z, et al. Dynamic adsorption of phosphate by calcium modified bentonite and its regeneration[J]. China Water & Wastewater, 2018, 34(17): 108-111.
7	徐颖, 叶志隆, 叶欣, 等. 给水污泥对水中磷的吸附性能[J]. 环境工程学报, 2018, 12(3): 712-719.
7	XU Y, YE Z L, YE X, et al. Phosphorus adsorption performance[J].Chinese Journal of Environment Engineering, 2018, 12(3): 712-719.
8	施薇, 严素定, 唐大平. 改性花生壳对Cu²⁺的吸附[J]. 离子交换与吸附, 2012, 28(5): 442-448.
8	SHI W, YAN S D, TANG T P. Adsorption of copper (Ⅱ) on modifide peanut shells[J]. Ion Exchange and Adsorption, 2012, 28(5): 442-448.
9	莫蔚明, 唐庆松, 李旺, 等. 改性木薯秸秆对硝酸根的动态吸附及脱附[J].环境化学, 2013, 32(9): 1668-1673.
9	MO W M, TANG Q S, LI W, et al. Dynamic adsorption and desorption of nitrate on modified cassava stalk[J]. Environmental Chemistry, 2013, 32(9): 1668-1673.
10	覃发梅, 邱学青, 孙川, 等. 纳米纤维素去除水体系重金属离子的研究进展[J]. 化工进展, 2019, 38(7): 3390-3401.
10	TAN F M, QIU X Q, SHUN Z, et al. Research progress in nanocellulose for the removal of heavy metal ions in water[J]. Chemical Industry and Engineering Progress, 2019, 38(7): 3390-3401.
11	唐丽荣, 王炜彬, 王清华, 等. 基于芳香基双硫键的乙酸酯化纳米纤维素/聚(脲-氨酯)自愈合材料[J].化工进展, 2017, 36(4): 1381-1387.
11	TANG L R, WANG W B, WANG Q H, et al. Esterified cellulose nanocrystals/poly(urea-urethane) self-healing materials based on aromatic disulfide bonds[J]. Chemical Industry and Engineering Progress, 2017, 36(4): 1381-1387.
12	TAN K W, HEO S K, FOO M L, et al. An insight into nanocellulose as soft condensed matter: challenge and future prospective toward environmental sustainability[J]. Science of the Total Environment, 2019, 650(1): 1306-1329.
13	郄冰玉, 唐亚丽, 卢立新, 等. 纳米纤维素在可降解包装材料中的应用[J]. 包装工程, 2017, 38(1): 19-25.
13	QIE B Y, TANG L Y, LU L X, et al. Application of nano-cellulose in degradable packaging materials[J]. Packaging Engineering, 2017, 38(1): 19-25.
14	LEE S Y, CHUN S J, KANG I A, et al. Preparation of cellulose nanofibrils by high-pressure homogenizer and cellulose-based composite films[J]. Journal of Industrial and Engineering Chemistry, 2009, 15(1): 50-55.
15	CUI G R, LIU M, CHEN X, et al. Synthesis of a ferric hydroxide-coated cellulose nanofiber hybrid for effective removal of phosphate from wastewater[J]. Carbohydrate Polymers, 2016, 154: 40-47.
16	王婷庭, 刘敏, 崔桂榕, 等. 五种改性纳米纤维素吸附剂的制备及除磷性能比较[J]. 化工进展, 2017, 36(11): 4279-4285.
16	WANG T T, LIU M, CUI G R, et al. Preparation of several modified cellulose nanofiber hybrid adsorbents and performance comparison of phosphate removals[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4279-4285.
17	罗莹, 刘敏, 陈滢,等. 吸附磷饱和的铁改性纳米纤维素的再生条件与效果研究[J]. 黑龙江大学自然科学学报, 2019, 36(4): 1-6.
17	LUO Y, LIU M, CHEN Y, et al. Study on regeneration conditions and effect iron modified nanocellulose saturated with phosphorus adsorption[J]. Journal of Natural Science of Heilongjiang University, 2019, 36(4): 1-6.
18	ZHANG X F, ZHAO J Q, HE X, et al. Mechanically robust and highly compressible electrochemical supercapacitors from nitrogen-doped carbon aerogels[J]. Carbon, 2018, 127: 236-244.
19	LUO Y, LIU M, CHENG Y, et al. Preparation and regeneration of iron-modified nanofibres for low-concentration phosphorus-containing wastewater treatment[J]. Royal Society Open Science, 2019, 6(9): 190764.
20	HASAN S H, RANJAN D, TALAT M. Agro-industrial waste “wheat bran” for the biosorptive remediation of selenium through continuous up-flow fixed-bed column[J]. Journal of Hazardous Materials, 2010, 181(1/2/3): 1134-1142.
21	CARRILLOM SOLANO M A, DUSSAUZE M, VINATIER P, et al. Phosphate structure and lithium environments in lithium phosphorus oxynitride amorphous thin films[J]. Ionics, 2016, 22: 471-481.
22	MATTOGNO G, FERRAGINA C, MASSUCCI M A, et al. X-ray photoelectron spectroscopic evidence of interlayer complex formation between Co(Ⅱ) and N-heterocycles in α-Zr(HPO₄)₂·H₂O[J]. Journal of Electron Spectroscopy and Related Phenomena, 1988, 46(2): 285-295.
23	FRANKE R, MEISEL A, STREUBEL P, et al. Auger parameters and relaxation energies of phosphorus in solid compounds[J]. Journal of Electron Spectroscopy and Related Phenomena, 1991, 56(4): 381-388.

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