氧化铝改性污泥生物炭粒制备及其对Pb(Ⅱ)的吸附特性

doi:10.16085/j.issn.1000-6613.2019-1003

摘要/Abstract

摘要：

为拓展城市剩余污泥资源化利用途径，本文以剩余污泥球粒为原料在高温限氧条件下制备污泥生物炭粒（SBC），同时以氢氧化铝溶胶为前体浸渍污泥球粒后在500℃下热解获得氧化铝改性污泥生物炭粒（SBC-Al）。使用BET、XRD、FTIR和SEM对生物炭粒进行了表征，并研究了生物炭粒改性前后对Pb(Ⅱ)的吸附特征及效果。结果表明：SBC-Al比表面积和总孔容分别达到83.266m²/g和0.158cm³/g，相比于SBC分别增大了142.42%和167.80%；XRD显示氢氧化铝溶胶浸渍使SBC-Al表面负载了γ-Al₂O₃粒子，FTIR红外谱图说明氧化铝改性可能会增加炭粒表面官能团数量，同时SEM显示出SBC-Al表面相较于SBC具有更多的层片状结构，从而增加生物炭粒的吸附性能。Pb(Ⅱ)的吸附动力学符合二级动力学方程和Elovich方程，同时用二阶段颗粒内扩散模型可以较好地拟合。吸附等温线以Freundlich模型为主，且SBC和SBC-Al对低浓度（＜50mg/L）Pb(Ⅱ)的去除率均较高，分别在95%和99%以上，实测最大吸附量可分别达626.73mg/g和663.97mg/g，但SBC-Al提高了对更高浓度（50～100mg/L）Pb(Ⅱ)的去除率。热力学计算数据表明吸附过程为吸热反应；脱附解吸试验说明，生物炭粒具有良好的循环再生利用性能。

关键词: 生物炭, 颗粒物料, 复合材料, 剩余污泥, 氧化铝, 吸附, 吸附剂, 铅

Abstract:

In order to expand the utilization of municipal excess sludge, activated sludge biochar particles (SBC) were prepared by using excess sludge pellets as raw materials under high temperature and oxygen limitation. At the same time, activated sludge biochar particles modified by alumina (SBC-Al) were obtained by impregnating sludge pellets with alumina hydroxide sol as precursor at 500°C. Biochar particles were characterized by BET, XRD, FTIR and SEM. The adsorption characteristics and effects of Pb(Ⅱ) on biochar particles before and after modification were studied. The results showed that the specific surface area and total pore volume of SBC-Al were 83.266m²/g and 0.158cm³/g, respectively, which increased by 142.42% and 167.80% compared with SBC. XRD showed that alumina sol impregnation loaded the SBC-Al surface with γ-Al₂O₃ particles. FTIR spectra showed that alumina modification might increase the number of functional groups on the surface of carbon particles. Meanwhile, SEM showed that SBC-Al surface had more lamellar structure than SBC, thus increasing the adsorption performance of biochar particles. The adsorption kinetics of Pb(Ⅱ) conforms to the second-order kinetics equation and Elovich equation. At the same time, the two-stage intraparticle diffusion model can be used to fit the adsorption kinetics of Pb(Ⅱ). The adsorption isotherm is based on Freundlich model, and the removal rates of low concentration (＜50mg/L) Pb(Ⅱ) by SBC and SBC-Al are higher than 95% and 99%, respectively. The maximum adsorption amounts can reach 626.73mg/g and 663.97mg/g, respectively. However, SBC-Al improves the removal rates of higher concentration (50—100mg/L) Pb(Ⅱ). Thermodynamic calculation data showed that the adsorption process is endothermic reaction. Desorption and desorption experiments showed that biochar particles have good recycling performance.

Key words: biochar, granular materials, composites, sludge, alumina, adsorption, adsorbents, lead (Pb)

中图分类号:

X705

徐大勇,张苗,杨伟伟,刘婷婷,姚巧凤,洪亚军. 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.

Dayong XU,Miao ZHANG,Weiwei YANG,Tingting LIU,Qiaofeng YAO,Yajun HONG. 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.

图/表 21

参考文献 53

53	ZHANG Lianke,LIU Xinyu,WANG Weida,et al.Characteristics and mechanism of lead adsorption from aqueous solutions by oil crops straw-derived biochar[J].Transactions of the Chinese Society of Agricultural Engineering,2018,34(7):218-226.
54	秦婷婷,王兆炜,朱俊民,等.花椰菜基生物炭对水中Pb(Ⅱ)的吸附性能[J].环境科学学报,2017,37(8):2977-2988.
	QIN Tingting,WANG Zhaowei,ZHU Junmin,et al.Adsorption characteristics of Pb(Ⅱ) by biochars derived from cauliflower (Brassica oleracea L. ) from aqueous solution[J].Acta Scientiae Circumstantiae,2017,37(8):2977-2988.
55	ZHUANG Fuqiang,TAN Ruiqin,SHEN Wenfeng,et al.Monodisperse magnetic hydroxyapatite/Fe₃O₄ microspheres for removal of lead(Ⅱ) from aqueous solution[J].Journal of Alloys & Compounds,2015,637:531-537.
56	ZHAO Yueling,ZHANG Ruyu,LIU Haibo,et al.Green preparation of magnetic biochar for the effective accumulation of Pb(Ⅱ): performance and mechanism[J].Chemical Engineering Journal,2019,375:122011.
57	YIN Weiqin,DAI Dian,HOU Jianhua,et al.Hierarchical porous biochar-based functional materials derived from biowaste for Pb(Ⅱ) removal[J].Applied Surface Science,2019,465:297-302.
1	杨珂玲,张宏志,张志刚,等.铅暴露的环境健康风险评估模型的本土化研究[J].中国人口·资源与环境,2016,26(2):163-169.
	YANG Keling,ZHANG Hongzhi,ZHANG Zhigang,et al.Localization study of environmental health risk assessment model for lead exposure[J].China Population,Resources and Environment,2016,26(2):163-169.
2	陈林,钱秀荣,赵秋妮,等.铅暴露健康危害风险评估研究进展[J].中国职业医学,2018,45(3):401-405.
	CHEN Lin,QIAN Xiurong,ZHAO Qiuni,et al.Research progress on health hazard risk assessment of lead exposure[J].China Occupational Medicine,2018,45(3):401-405.
3	蔡蕊,宋黎明,庞长泷,等.利用农业废弃物处理水体重金属污染的研究进展[J].中国给水排水,2014,30(24):61-65.
	CAI Rui,SONG Liming,PANG Changlong,et al.Advances in research on agricultural waste material for treatment of heavy metal ions in water[J].China Water & Wastewater,2014,30(24):61-65.
4	GHAEDI M,MOSALLANEJAD N.Removal of heavy metal ions from polluted waters by using of low cost adsorbents[J].Journal of Chemical Health Risks,2018,3:1.
5	刘金燕,刘立华,薛建荣,等.重金属废水吸附处理的研究进展[J].环境化学,2018,37(9):2016-2024.
	LIU Jinyan,LIU Lihua,XUE Jianrong,et al.Research progress on treatment of heavy metal wastewater by adsorption[J].Environmental Chemistry,2018,37(9):2016-2024.
6	GODWIN P,PAN Yuanfeng,XIAO Huining,et al.Progress in the preparation and application of modified biochar for improving heavy metal ion removal from wastewater[J].Journal of Bioresources and Bioproducts,2019,4:31-42.
7	MIAN M M,LIU Guijian.Recent progress in biochar-supported photocatalysts: synthesis, role of biochar, and applications[J].RSC Advances,2018,8:14237-14248.
8	O'CONNOR D,PENG Tianyue,ZHANG Junli,et al.Biochar application for the remediation of heavy metal polluted land: a review ofin situ field trials[J].Science of the Total Environment,2018,619:815-826.
9	WANG Shengsen,GAO Bin,LI Yuncong,et al.Manganese oxide-modified biochars: preparation, characterization, and sorption of arsenate and lead: biomass, bioenergy, biowastes, conversion technologies, biotransformations, production technologies[J].Bioresour Technol.,2015,181:13-17.
10	曹玮,周航,邓贵友,等.改性谷壳生物炭负载磁性Fe去除废水中Pb²⁺的效果及机制[J].环境工程学报,2017,11(3):1437-1444.
	CAO Wei,ZHOU Hang,DENG Guiyou,et al.Effects and mechanisms of magnetic iron supported on rice husk biochar removing Pb²⁺ in wastewater[J].Chinese Journal of Environmental Engineering,2017,11(3):1437-1444.
11	于长江,董心雨,王苗,等.海藻酸钙/生物炭复合材料的制备及其对Pb(Ⅱ)的吸附性能和机制[J].环境科学,2018,39(8):3719-3728.
	YU Changjiang,DONG Xinyu,WANG Miao,et al.Preparation and characterization of a calcium alginate/biochar microsphere and its adsorption characteristics and mechanisms for Pb(Ⅱ)[J].Environmental Science,2018,39(8):3719-3728.
12	张连科,王洋,王维大,等.生物炭负载纳米羟基磷灰石复合材料的制备及对铅离子的吸附特性[J].化工进展,2018,37(9):3492-3501.
	ZHANG Lianke,WANG Yang,WANG Weida,et al.The preparation of biochar-supported nano-hydroxyapatite and its adsorption of Pb²⁺[J].Acta Scientiae Circumstantiae,2018,37(9):3492-3501.
13	BISHNOI N R,BAJAJ M,SHARMA N,et al.Adsorption of Cr(Ⅵ) on activated rice husk carbon and activated alumina[J].Bioresource Technology,2004,91:305-307.
14	刘宋文.活性炭负载活性氧化铝复合除氟材料的制备及其除氟性能的研究[D].武汉:武汉理工大学,2014.
	LIU Songwen.Preparation of activated carbon supported activated alumina composite adsorbent and its defluoridation properties [D].Wuhan:Wuhan University of Technology,2014.
15	LANDERS J,GOR G Y,NEIMARK A V.Density functional theory methods for characterization of porous materials[J].Colloids and Surfaces A: Physicochemical and Engineering Aspects,2013,437:3-32.
16	ONOREVOLI B,SILVA M G P DA,MACHADO M E,et al.Characterization of feedstock and biochar from energetic tobacco seed waste pyrolysis and potential application of biochar as an adsorbent[J].Journal of Environmental Chemical Engineering,2018,6:1279-1287.
17	ASENCIOS Y J,SUN-KOU M R.Synthesis of high-surface-area γ-Al₂O₃ from aluminum scrap and its use for the adsorption of metals: Pb(Ⅱ), Cd(Ⅱ) and Zn(Ⅱ)[J].Applied Surface Science,2012,258:10002-10011.
18	MUTTAKIN M,MITRA S,THU K,et al.Theoretical framework to evaluate minimum desorption temperature for IUPAC classified adsorption isotherms[J].International Journal of Heat and Mass Transfer,2018,122:795-805.
19	BURHAN M,SHAHZAD M W,NG K C.Energy distribution function based universal adsorption isotherm model for all types of isotherm[J].International Journal of Low-Carbon Technologies,2018,13:292-297.
20	王彤彤,王晓琳,任志胜,等.不同原料制备的生物炭形貌结构及表面特性研究[J].环境科学与技术,2017,40(1):42-48.
	WANG Tongtong,WANG Xiaolin,REN Zhisheng,et al.Microscopic morphology and surface features of biochars derived from different raw materials[J].Environmental Science & Technology,2017,40(1):42-48.
21	ZHU Ningyuan,YAN Tingmei,QIAO Jun,et al.Adsorption of arsenic, phosphorus and chromium by bismuth impregnated biochar: Adsorption mechanism and depleted adsorbent utilization[J].Chemosphere,2016,164:32-40.
22	SUN Yong,ZHANG Jing Ping,WEN Chao,et al.An enhanced approach for biochar preparation using fluidized bed and its application for H₂S removal[J].Chemical Engineering and Processing: Process Intensification,2016,104:1-12.
23	LIANG Hui,LIU Ling,YANG Hongxiao,et al.Controllable synthesis of γ-AlOOH micro/nanoarchitecturesvia a one-step solution route[J].CrystEngComm,2011,13:2445-2450.
24	ZHANG Hailin,PING Li,CUI Wenwen,et al.Synthesis of nanostructured γ-AlOOH and its accelerating behavior on the thermal decomposition of AP[J].RSC Advances,2016,6:27235-27241.
25	李波,邵玲玲.氧化铝、氢氧化铝的XRD鉴定[J].无机盐工业,2008,40(2):54-57.
	LI Bo,SHAO Lingling.Appraisal of alumina and aluminium hydroxide by XRD[J].Inorganic Chemicals Industry,2008,40(2):54-57.
26	李杰,潘兰佳,余广炜,等.污泥生物炭制备吸附陶粒[J].环境科学,2017,38(9):3970-3978.
	LI Jie,PAN Lanjia,YU Guangwei,et al.Preparation of adsorption ceramsite derived from sludge biochar[J].Environmental Science,2017,38(9):3970-3978.
27	ZHANG Beiping,XIONG Sijiang,XIAO Bo,et al.Mechanism of wet sewage sludge pyrolysis in a tubular furnace[J].International Journal of Hydrogen Energy,2011,36:355-363.
28	郑凯琪,王俊超,刘姝彤,等.不同热解温度污泥生物炭对Pb²⁺、Cd²⁺的吸附特性[J].环境工程学报,2016,10(12):7277-7282.
	ZHENG Kaiqi,WANG Junchao,LIU Shutong,et al.Adsorption characteristic of Pb²⁺and Cd²⁺ with sludge biochars derived atdifferent pyrolysis temperatures[J].Chinese Journal of Environmental Engineering,2016,10(12):7277-7282.
29	卢欢亮,叶向东,汪永红,等.热解温度对污泥生物炭的表面特性及重金属安全性的影响[J].环境工程学报,2015,9(3):1433-1439.
	LU Huanliang,YE Xiangdong,WANG Yonghong,et al.Effects of pyrolysis temperature on surface propertiesand heavy metal safety of sludge-derived biochar[J].Chinese Journal of Environmental Engineering,2015,9(3):1433-1439.
30	SIMONIN J P.On the comparison of pseudo-first order and pseudo-second order rate laws in the modeling of adsorption kinetics[J].Chemical Engineering Journal,2016,300:254-263.
31	ZHOU Lu,LIU Yunguo,LIU Shaobo,et al.Investigation of the adsorption-reduction mechanisms of hexavalent chromium by ramie biochars of different pyrolytic temperatures[J].Bioresource Technology,2016,218:351-359.
32	RASHEED A,FAROOQ F,RAFIQUE U,et al.Analysis of sorption efficiency of activated carbon for removal of anthracene and pyrene for wastewater treatment[J].Desalination and Water Treatment,2016,57:145-150.
33	ZENG Guangming,LIU Yuanyuan,TANG Lin,et al.Enhancement of Cd(Ⅱ) adsorption by polyacrylic acid modified magnetic mesoporous carbon[J].Chemical Engineering Journal,2015,259:153-160.
34	ARRIS S,LEHOCINE M B,MENIAI A H.Sorption study of chromium sorption from wastewater using cereal by-products[J].International Journal of Hydrogen Energy,2016,41:10299-10310.
35	王彤彤,崔庆亮,王丽丽,等.Al改性柠条生物炭对P的吸附特性及其机制[J].中国环境科学,2018,38(6):2210-2222.
	WANG Tongtong,CUI Qingliang,WANG Lili,et al.Adsorption characteristics and mechanism of phosphate from aqueous solutions on Al modification biochar produced from Caragana KorshinskⅡ[J].China Environmental Science,2018,38(6):2210-2222.
36	WANG Hongyu,GAO Bin,WANG Shenseng,et al.Removal of Pb(Ⅱ), Cu(Ⅱ), and Cd(Ⅱ) from aqueous solutions by biochar derived from KMnO₄ treated hickory wood[J].Bioresource Technology,2015,197:356-362.
37	ZHOU Yaoyu,LIU Xiaocheng,XIANG Yujia,et al.Modification of biochar derived from sawdust and its application in removal of tetracycline and copper from aqueous solution: adsorption mechanism and modelling[J].Bioresource Technology,2017,245:266-273.
38	孙绪兵,吴雪梅,朱建发,等.羧基甲壳素对Pb(Ⅱ)的吸附性能及机理研究[J].中国环境科学,2018,38(8):3018-3028.
	SUN Xubing,WU Xuemei,ZHU Jianfa,et al.Adsorption performance and mechanism of Pb(Ⅱ) onto carboxylated chitin[J].China Environmental Science,2018,38(8):3018-3028.
39	YANG Kun,JIANG Yuan,YANG Jingjing,et al.Correlations and adsorption mechanisms of aromatic compounds on biochars produced from various biomass at 700℃[J].Environmental Pollution,2018,233:64-70.
40	马锋锋,赵保卫,刁静茹.小麦秸秆生物炭对水中Cd²⁺的吸附特性研究[J].中国环境科学,2017,37(2):551-559.
	MA Fengfeng,ZHAO Baowei,DIAO Jingru.Adsorptive characteristics of cadmium onto biochar produced from pyrolysis of wheat straw in aqueous solution[J].China Environmental Science,2017,37(2):551-559.
41	KOMKIENE J,BALTRENAITE E.Biochar as adsorbent for removal of heavy metal ions [cadmium (Ⅱ), copper (Ⅱ), lead (Ⅱ), zinc (Ⅱ)] from aqueous phase[J].International Journal of Environmental Science and Technology,2016,13:471-482.
42	ZHOU Nan,CHEN Honggang,XI Junting,et al.Biochars with excellent Pb(Ⅱ) adsorption property produced from fresh and dehydrated banana peelsvia hydrothermal carbonization[J].Bioresource Technology,2017,232:204-210.
43	SUN Lei,CHEN Dongmei,WAN Shungang,et al.Performance, kinetics, and equilibrium of methylene blue adsorption on biochar derived from eucalyptus saw dust modified with citric, tartaric, and acetic acids[J].Bioresource Technology,2015,198:300-308.
44	NAUSHAD M,SHARMA G,ALA'A H,et al.Dubinin-Radushkevich (DR) isotherm studies of equilibrium sorption of metal ions onto phosphoric acid modified rice-husk[J].Heavy Metals: Sources,Toxicity and Remediation Techniques,2016:231-250
45	孔岩,庄媛,石宝友,等.活性炭/高分子复合水凝胶对水中亚甲基蓝和Cu(Ⅱ)的去除性能[J].环境科学,2018,39(2):819-827.
	KONG Yan,ZHUANG Yuan,SHI Baoyou,et al.Adsorption of methylene blue and Cu(Ⅱ) by activated carbon/macromolecule composite hydrogel[J].Environmental Science,2018,39(2):819-827.
46	DAI Lichun,ZHU Wenkun,HE Li,et al.Calcium-rich biochar from crab shell: an unexpected super adsorbent for dye removal[J].Bioresource technology,2018,267:510-516.
47	吴鸿伟,陈萌,黄贤金,等.改性生物炭对水体中头孢噻肟的吸附机制[J].中国环境科学,2018,38(7):2527-2534.
	WU Hongwei,CHEN Meng,HUANG Xianjin,et al.Preparation of modified biochar for adsorption of cefotaxime in solution[J].China Environmental Science,2018,38(7):2527-2534.
48	LUO Mingke,LIN Hai,LI Bing,et al.A novel modification of lignin on corncob-based biochar to enhance removal of cadmium from water[J].Bioresource Technology,2018,259:312-318.
49	NGUYEN C,DO D.The Dubinin-Radushkevich equation and the underlying microscopic adsorption description[J].Carbon,2001,39:1327-1336.
50	SONG Zhengguo,LIAN Fei,YU Zhihong,et al.Synthesis and characterization of a novel MnO_x-loaded biochar and its adsorption properties for Cu²⁺ in aqueous solution[J].Chemical Engineering Journal,2014,242:36-42.
51	张杰,朱晓丽,尚小清,等.生物炭固定化解磷菌对Pb²⁺的吸附特性[J].环境污染与防治,2019,41(4):387-392.
	ZHANG Jie,ZHU Xiaoli,SHANG Xiaoqing,et al.Adsorption characteristics of Pb²⁺ on biochar immobilized phosphate-solubilizing bacteria[J].Environmental Pollution & Control,2019,41(4):387-392.
52	张连科,王洋,王维大,等.磁性羟基磷灰石/生物炭复合材料的制备及对Pb²⁺的吸附性能[J].环境科学学报,2018,38(11):4360-4370.
	ZHANG Lianke,LIU Xinyu,WANG Weida,et al.Preparation of magnetic hydroxyapatite/biochar composite and its adsorption behavior of Pb²⁺ and recycling performance[J].Acta Scientiae Circumstantiae,2018,38(11):4360-4370.
53	张连科,刘心宇,王维大,等.油料作物秸秆生物炭对水体中铅离子的吸附特性与机制[J].农业工程学报,2018,34(7):218-226.

生物炭类型	比表面积/m²·g^-1				孔容/cm³·g^-1			孔径/nm
生物炭类型	单点BET 比表面积	多点BET 比表面积	BJH吸附累积孔内表面积	BJH脱附累积孔内表面积	最高单点吸附总孔容	BJH吸附累积孔容	BJH脱附累积孔容	单点总孔吸附平均孔直径	BJH中孔吸附平均孔直径	BJH中孔脱附平均孔直径
SBC	22.314	34.348	12.282	22.314	0.059	0.054	0.059	3.659	13.728	3.659
SBC-Al	82.022	83.266	73.382	82.022	0.158	0.156	0.158	3.731	3.076	3.731

生物炭类型	比表面积/m²·g^-1				孔容/cm³·g^-1			孔径/nm
生物炭类型	单点BET 比表面积	多点BET 比表面积	BJH吸附累积孔内表面积	BJH脱附累积孔内表面积	最高单点吸附总孔容	BJH吸附累积孔容	BJH脱附累积孔容	单点总孔吸附平均孔直径	BJH中孔吸附平均孔直径	BJH中孔脱附平均孔直径
SBC	22.314	34.348	12.282	22.314	0.059	0.054	0.059	3.659	13.728	3.659
SBC-Al	82.022	83.266	73.382	82.022	0.158	0.156	0.158	3.731	3.076	3.731

样品	平均粒径/mm	表观描述
SBC-Al	4.80	表面光泽，裂纹较宽，颗粒较圆
SBC	4.90	表面呈碳黑色，裂纹较细，颗粒偏椭圆

样品	平均粒径/mm	表观描述
SBC-Al	4.80	表面光泽，裂纹较宽，颗粒较圆
SBC	4.90	表面呈碳黑色，裂纹较细，颗粒偏椭圆

生物炭类型	拟一级动力学			拟二级动力学			Elovich
生物炭类型	Q_e/mg·g^-1	k₁	R²	Q_e/mg·g^-1	k₂	R²	a	b	R²
SBC	472.489	0.815	0.705	529.325	2.28×10^-3	0.904	3148.522	0.012	0.974
SBC-Al	467.233	0.639	0.873	538.066	1.59×10^-3	0.970	1340.482	0.010	0.993