草酸改性甘蔗渣炭的制备及其对Cr(Ⅵ)的吸附特性

doi:10.3969/j.issn.1673-5854.2019.04.006

摘要/Abstract

摘要：

以甘蔗渣（OB）为原料，先在空气氛围下高温炭化制得甘蔗渣炭（CB），再经草酸改性制得草酸改性甘蔗渣炭（COB），采用SEM、FT-IR和氮气吸附-脱附等温线对3种样品进行表征，并考察了OB、CB和COB对模拟废水中的Cr（Ⅵ）的吸附效果。结果显示：3种样品比表面积大小为COB>CB>OB，其中COB的比表面积为240.67 m²/g，总孔容为0.138 cm³/g，平均孔径为2.30 nm；CB以及COB较OB的孔隙结构更发达、含氧官能团种类及数量明显增加，吸附能力提高。吸附实验结果表明：对Cr（Ⅵ）的吸附量表现为COB>CB>OB，在pH值1、投加量0.6 g、吸附时间100 min、吸附温度25℃和Cr（Ⅵ）质量浓度50 mg/L条件下COB对Cr（Ⅵ）的去除率为99.1%。吸附热力学及动力学结果显示：Langmuir等温吸附模型能更好地反映吸附过程，吸附过程遵循准二级动力学模型，表明甘蔗渣炭对Cr（Ⅵ）的吸附主要为化学吸附的单分子层吸附。

关键词: 改性, 炭化, 吸附, 甘蔗渣, Cr(Ⅵ)

Abstract:

Using bagasse(OB) as raw material, carbon bagasse carbon(CB) was obtained by carbonization at high temperature in air atmosphere, and then oxalic acid modified bagasse carbon(COB) was prepared by oxalic acid modification. The three kinds of samples were characterized by SEM, FT-IR and nitrogen adsorption-desorption isotherms, and the adsorption effect of Cr(Ⅵ) in simulated wastewater was simulated. The characterization results showed that the specific surface area was COB>CB>OB, the specific surface area of COB was 240.67 m²/g, the total pore volume was 0.138 cm³/g, and the average pore diameter was 2.30 nm. The pore structures of CB and COB were more than that of OB. The types and quantities of developed and oxygen-containing functional groups of CB and COB were significantly increased, and the adsorption capacities of CB and COB were improved. The results of adsorption experiments showed that the adsorption capacities of Cr(Ⅵ) were COB>CB>OB. Under the conditions of pH value 1, dosage of COB 0.6 g, adsorption time 100 min, adsorption temperature 25℃ and Cr(Ⅵ) mass concentration 50 mg/L, the removal rate of Cr(Ⅵ) by COB was 99.1%. The adsorption thermodynamics and kinetics results showed that the Langmuir isotherm adsorption model could better reflect the adsorption process, and the adsorption process followed the pseudo-second-order kinetics model, indicating that the adsorption process of Cr(Ⅵ) by bagasse carbon was mainly monolayer adsorption of chemisorption.

Key words: modification, carbonization, adsorption, bagasse, Cr(Ⅵ)

中图分类号:

TQ35
TQ424

刘雪梅,马闯,陶嘉熙. 草酸改性甘蔗渣炭的制备及其对Cr(Ⅵ)的吸附特性[J]. 生物质化学工程, 2019, 53(4): 37-44.

Xuemei LIU,Chuang MA,Jiaxi TAO. Preparation of Oxalic Acid Modified Bagasse Carbon and Its Adsorption Characteristics for Cr(Ⅵ)[J]. Biomass Chemical Engineering, 2019, 53(4): 37-44.

图/表 8

表1

图1

图2

图3

图4

表2

图5

表3

参考文献 25

1	白春, 成浪, 罗霞娟, 等. 不同方式干燥的香蕉皮吸附六价铬性能研究[J]. 广东化工, 2016, 43 (20): 26- 27, 31. doi: 10.3969/j.issn.1007-1865.2016.20.012
2	丁绍兰, 常娥, 齐建敏. 废弃皮革制品屑对六价铬的吸附性能研究[J]. 中国皮革, 2012, 41 (3): 1- 3, 12.
3	张庆乐, 董建, 张丽青, 等. 草酸改性杨树叶对六价铬的吸附性能[J]. 环境工程, 2015, 33 (5): 64- 69, 94.
4	PARK D , LIM S , YUN Y , et al. Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction[J]. Chemosphere, 2007, 70 (2): 298- 305. doi: 10.1016/j.chemosphere.2007.06.007
5	MUTHUSAMY S , VENKATACHALAM S , JEEVAMANI P M K , et al. Biosorption of Cr(Ⅵ) and Zn(Ⅱ) ions from aqueous solution onto the solid biodiesel waste residue:Mechanistic, kinetic and thermodynamic studies[J]. Environmental Science and Pollution Research, 2014, 21 (1): 593- 608. doi: 10.1007/s11356-013-1939-8
6	SINGHA B , DAS S K . Biosorption of Cr(Ⅵ) ions from aqueous solutions:Kinetics, equilibrium, thermodynamics and desorption studies[J]. Colloids and Surfaces B:Biointerfaces, 2011, 84 (1): 221- 232. doi: 10.1016/j.colsurfb.2011.01.004
7	何忠明, 王琼, 付宏渊, 等. 柚子皮吸附去除水中的六价铬和砷[J]. 环境工程, 2016, 34 (增刊): 299- 302.
8	韦学玉, 刘志刚, 万耀强, 等. 磁性壳聚糖纳米材料对水中Cu(Ⅱ)吸附性能的研究[J]. 华东交通大学学报, 2017, 34 (4): 129- 136.
9	张明明.生物炭改性材料的制备及其对水体中六价铬的吸附机理研究[D].长沙:湖南大学, 2016.
10	朱银涛, 李业东, 王明玉, 等. 玉米秸秆碱化处理制备的生物炭吸附锌的特性研究[J]. 农业环境科学学报, 2018, 37 (1): 179- 185.
11	李江兵, 夏明, 丁纯梅, 等. 酸改性活性炭对废水中六价铬吸附效果的研究[J]. 环境与健康杂志, 2013, 30 (1): 69- 71.
12	刘超, 杨永哲, 宛娜. 铝污泥吸附六价铬的特征和机理[J]. 环境工程学报, 2013, 7 (1): 97- 102.
13	周晓倩, 郭华明, 赵凯. 改性天然菱铁矿去除水中六价铬[J]. 环境工程学报, 2015, 9 (9): 4171- 4177.
14	谭秋荀, 张可方, 赵焱, 等. 活性氧化铝对六价铬的吸附研究[J]. 环境科学与技术, 2012, 35 (6): 130- 133. doi: 10.3969/j.issn.1003-6504.2012.06.028
15	郭方颖.改性磁性氧化石墨烯材料制备及其对水中六价铬离子的吸附机理研究[D].长沙:湖南大学, 2016.
16	刘中华, 范传芳, 张记市, 等. 啤酒糟及其生物炭吸附废水中Cr(Ⅵ)[J]. 齐鲁工业大学学报(自然科学版), 2017, (4): 19- 24.
17	KWAK H W , KIM M K , LEE J Y , et al. Preparation of bead-type biosorbent from water-soluble Spirulina platensis extracts for chromium(VI) removal[J]. Algal Research, 2015, 7, 92- 99. doi: 10.1016/j.algal.2014.12.006
18	黄增尉, 周泽广. 交联壳聚糖处理电镀废水中铬(Ⅵ)的研究[J]. 广西民族大学学报(自然科学版), 2006, 12 (4): 100- 103. doi: 10.3969/j.issn.1673-8462.2006.04.022
19	GAGRAI M K , DAS C , GOLDER A K . Reduction of Cr(Ⅵ) into Cr(Ⅲ) by Spirulina dead biomass in aqueous solution:Kinetic studies[J]. Chemosphere, 2013, 93 (7): 1366- 1371. doi: 10.1016/j.chemosphere.2013.08.021
20	张双杰, 邢宝林, 黄光许, 等. 柚子皮水热炭对六价铬的吸附[J]. 环境工程学报, 2017, 11 (5): 2731- 2737.
21	鲁秀国, 段建菊, 黄林长, 等. 炭化核桃壳对废水中Cr(Ⅵ)的吸附[J]. 化工环保, 2016, 36 (6): 611- 616. doi: 10.3969/j.issn.1006-1878.2016.06.005
22	鲁秀国, 段建菊, 黄林长, 等. 氮炭化核桃壳对Cr(Ⅵ)的吸附特性与机理[J]. 环境工程学报, 2017, 11 (6): 3446- 3452.
23	张双杰, 邢宝林, 黄光许, 等. 核桃壳水热炭对六价铬的吸附特性[J]. 化工进展, 2016, 35 (3): 950- 956.
24	刘莹, 刘晓晖, 王炜亮, 等. 棉花秸秆黑炭对Cd²⁺的吸附特性研究[J]. 环境污染与防治, 2018, (3): 291- 295, 300.
25	张鹏会, 李艳春, 胡浩斌, 等. 银杏叶生物炭对亚甲基蓝的吸附特性[J]. 环境污染与防治, 2017, (11): 1229- 1234.

样品 sample	比表面积/(m²·g^-1) specific surface area	总孔容积/(cm³·g^-1) total pore volume	平均孔径/nm average pore size
OB	0.87	0.002	7.15
CB	162.29	0.091	2.23
COB	240.67	0.138	2.30

吸附剂 adsorbent	实验吸附量/(mg·g^-1) experimental adsorption	准一级动力学模型 pseudo first-order kinetic model			准二级动力学模型 pseudo second-order kinetic model			颗粒内部扩散模型 particle internal diffusion equation
吸附剂 adsorbent	实验吸附量/(mg·g^-1) experimental adsorption	q_e/ (mg·g^-1)	k₁/ min^-1	R²	q_e/ (mg·g^-1)	k₂/ (g·mg^-1·min^-1)	R²	k/ (mg·g^-1·min^-0.5)	R²
COB	4.2	5.06	0.054	0.8174	4.505	0.0189	0.9963	0.1389	0.8665
CB	3.6	2.438	0.0412	0.8413	3.664	0.0332	0.9994	0.0762	0.8821

吸附剂 adsorbent	Langmuir等温吸附方程 Langmuir isothermal adsorption equation			Freundlich等温吸附方程 Freundlich isothermal adsorption equation
吸附剂 adsorbent	q_m/(mg·g^-1)	b/(L·mg^-1)	R²	K_F	1/n	R²
COB	5.893	1.081	0.9859	2.677	0.778	0.6687
CB	5.013	1.034	0.9985	0.821	0.371	0.7685

[1]	吕鹏,王光辉,王冰,胡德玉. 热解温度和生物质类型对生物炭吸附U(Ⅵ)性能的影响[J]. 生物质化学工程, 2020, 54(5): 15-24.
[2]	王盟盟,刘乐群,刘震涛,赵莹. 竹材液化墙体泡沫材料的阻燃改性[J]. 生物质化学工程, 2020, 54(5): 25-32.
[3]	建晓朋,许伟,侯兴隆,刘石彩. 活性炭改性技术研究进展[J]. 生物质化学工程, 2020, 54(5): 66-72.
[4]	任杰,万力,陈楠纬,杨帆,孙水裕,任随周. 咖啡渣活性炭的制备、表征及其对Cr(Ⅵ)的吸附机制研究[J]. 生物质化学工程, 2020, 54(4): 1-8.
[5]	孙琳,刘华玉,刘坤,张筱仪,解洪祥,张蕊,李海明,司传领. 纳米纤维素的疏水改性及应用研究进展[J]. 生物质化学工程, 2020, 54(4): 57-66.
[6]	李瑶,于淼,吕冬,王立娟. 蒲草叶基活性炭的制备及性能研究[J]. 生物质化学工程, 2020, 54(3): 9-17.
[7]	常帅帅,张学杨,王洪波,李梅,谭珍珍. 木屑生物炭的制备及其对Pb²⁺的吸附特性研究[J]. 生物质化学工程, 2020, 54(3): 37-44.
[8]	杨浩,陈琪,赵慧敏,顾浩杰,阎杰,林海琳. 甘蔗渣综纤维素膜的制备和性能研究[J]. 生物质化学工程, 2020, 54(2): 6-14.
[9]	王佳楠,羿颖,边勇军,马媛媛,刘志明. 羟甲基化木质素/纤维素气凝胶粒子的制备、表征及吸附性能[J]. 生物质化学工程, 2020, 54(1): 16-22.
[10]	孙万里. 茶皂素提取条件的优化及纯化研究[J]. 生物质化学工程, 2019, 53(6): 39-44.
[11]	邵金涛,余彩莉,张发爱. 松香基聚氨酯的研究进展[J]. 生物质化学工程, 2019, 53(6): 59-66.
[12]	邓丛静,马欢欢,周建斌. 改性杏壳活性炭的制备、表征及其吸附乙烯性能[J]. 生物质化学工程, 2019, 53(5): 1-8.
[13]	马红亮,陈健,孔振武. 复合材料用天然植物纤维改性研究进展[J]. 生物质化学工程, 2019, 53(4): 50-58.
[14]	谭文英,程晓红,李硕,杨宇翔. KOH活化法制备棉秆基活性炭及其对含苯酚废水的吸附[J]. 生物质化学工程, 2019, 53(2): 13-18.
[15]	黎克纯,卢建芳,雷福厚,周菊英,许海棠,赵彦芝. 松香基磁性微球的结构表征及其对Cr(Ⅵ)的吸附性能[J]. 生物质化学工程, 2019, 53(1): 17-24.