原料种类和热解温度对生物炭吸附Cd2+的影响

doi:10.16085/j.issn.1000-6613.2018-2494

化工进展 ›› 2019, Vol. 38 ›› Issue (9): 4183-4190.DOI: 10.16085/j.issn.1000-6613.2018-2494

原料种类和热解温度对生物炭吸附Cd²⁺的影响

曹健华¹(),刘凌沁¹(),黄亚继¹(),陶圣年²,秦文慧¹,任海斌²

1. 东南大学能源热转换及其过程控制教育部重点实验室，江苏南京 210096
2. 南京年达炉业科技有限公司，江苏南京 210059

收稿日期:2018-12-29 出版日期:2019-09-05 发布日期:2019-09-05
通讯作者: 黄亚继
作者简介:曹健华（1994—），男，硕士研究生，研究方向为固体废弃物处理。E-mail：478410873@qq.com。刘凌沁（1990—）女，博士研究生，研究方向为固体废弃物处理。E-mail：lq.liu@hotmail-com。|曹健华（1994—），男，硕士研究生，研究方向为固体废弃物处理。E-mail：478410873@qq.com。刘凌沁（1990—）女，博士研究生，研究方向为固体废弃物处理。E-mail：lq.liu@hotmail-com。
基金资助:
国家重点研发计划(2018YFC1901205);国家自然科学基金(51676040);江苏省自然科学基金(BK20181280);江苏省科技支撑计划(BE2013705)

Effects of feedstock type and pyrolysis temperature on Cd²⁺ adsorption by biochar

Jianhua CAO¹(),Lingqin LIU¹(),Yaji HUANG¹(),Shengnian TAO²,Wenhui QIN¹,Haibin REN²

1. Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, Nanjing 210096, Jiangsu, China
2. Nanjing Nianda Furnace Science and Technology Co. , Ltd. , Nanjing 210059, Jiangsu, China

Received:2018-12-29 Online:2019-09-05 Published:2019-09-05
Contact: Yaji HUANG

摘要/Abstract

摘要：

以稻秆（RS）、稻壳（RH）、木屑（SD）为原料，在小型流化床实验台上制备生物炭，分析了原料种类和热解温度（400℃、500℃、600℃）对生物炭理化性质及吸附Cd²⁺性能的影响规律，并定性和定量分析了吸附过程中的作用机制。实验结果表明：准二级动力学方程和Langmuir方程能够较好地描述生物炭样品对Cd²⁺的吸附过程。生物炭RS500的平衡吸附量达到30.19mg/g，远远高于生物炭SD500，其中无机矿物的离子交换和沉淀反应吸附贡献值为24.95mg/g，是主导吸附机制；而生物炭SD500吸附Cd²⁺过程中，无机矿物和π键的贡献百分比分别为49.70%和38.21%。随着热解温度的升高，生物炭吸附Cd²⁺过程中含氧官能团的络合反应不断削弱而Cd²⁺-π键作用不断增强；稻秆炭和稻壳炭中无机矿物的吸附贡献值则呈先上升后下降的趋势，并在500℃热解温度下达到最大值。生物炭样品吸附Cd²⁺的作用机制中，离子交换和沉淀反应占比最大，Cd²⁺-π键作用次之，络合反应最小。

关键词: 生物质, 吸附, 废水, 镉, 定量分析

Abstract:

The biochars were prepared in a lab-scale fluidized bed reactor, using rice straw(RS), rice husk(RH) and sawdust(SD) as raw materials. The influences of feedstock type and pyrolysis temperature(400℃, 500℃, 600℃) on the physicochemical properties and Cd²⁺ adsorption of biochar were researched, and the qualitative and quantitative analysis of adsorption mechanism was conducted. The adsorption process could be preferably described by the Pseudo-second-order kinetic equation and the Langmuir equation. The adsorption capacity at equilibrium of RS500 was up to 30.19mg/g, which was much higher than that of SD500. The ion exchange and precipitation with inorganic minerals contributed 24.95mg/g， serving as the dominant adsorption mechanism. However, the contribution percentages of inorganic minerals and π electrons were 49.70% and 38.21% respectively in the Cd²⁺ adsorption by SD500. With the increase of pyrolysis temperature, the complexation with oxygen-containing functional groups was weakened while the Cd²⁺-π interaction was strengthened. At the same time, the ion exchange and precipitation with inorganic minerals in the Cd²⁺ adsorption by rice straw biochar and rice husk biochar were strengthened firstly and then weakened as the pyrolysis temperature increasing, and the contribution of them reached the maximum at 500℃. Furthermore, the contribution of each adsorption mechanism in the process of Cd²⁺ adsorption by biochar followed this order: ion exchange and precipitation were the largest, followed by Cd²⁺-π interaction, and complexation was the least.

Key words: biomass, adsorption, wastewater, cadmium, quantitative analysis

中图分类号:

曹健华,刘凌沁,黄亚继,陶圣年,秦文慧,任海斌. 原料种类和热解温度对生物炭吸附Cd²⁺的影响[J]. 化工进展, 2019, 38(9): 4183-4190.

Jianhua CAO,Lingqin LIU,Yaji HUANG,Shengnian TAO,Wenhui QIN,Haibin REN. Effects of feedstock type and pyrolysis temperature on Cd²⁺ adsorption by biochar[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4183-4190.

图/表 8

图1 生物炭对Cd2+吸附动力学曲线

表1 准一级动力学方程和准二级动力学方程拟合参数

样品	准一级动力学方程			准二级动力学方程
样品	平衡吸附量/mg·g^-1	速率常数×10²/min^-1	回归系数	平衡吸附量/mg·g^-1	速率常数×10²/g·mg^-1·min^-1	回归系数
RS400	23.75	1.94	0.9341	25.77	0.11	0.9816
RS500	27.51	1.42	0.9434	30.19	0.06	0.9878
RS600	15.61	1.09	0.9001	17.20	0.09	0.9638
RH400	11.42	2.19	0.9003	12.33	0.26	0.9650
RH500	14.17	2.60	0.9125	15.21	0.25	0.9738
RH600	8.49	3.48	0.9050	9.05	0.57	0.9722
SD400	8.19	4.85	0.9068	8.65	0.88	0.9757
SD500	7.14	4.76	0.9082	7.51	1.03	0.9755
SD600	6.34	3.22	0.8827	6.75	0.74	0.9584

图2 生物炭对Cd2+等温吸附曲线

表2 Langmuir方程和Freundlich方程拟合参数

样品	Langmuir方程			Freundlich方程
样品	亲和常数/L·mg^-1	饱和吸附量/mg·g^-1	回归系数	容量参数/mg^1- ⁿ ·L ⁿ ·g^-1	指数	回归系数
RS400	0.30	28.19	0.9920	9.52	0.24	0.8616
RS500	0.39	32.33	0.9937	11.76	0.23	0.8635
RS600	0.15	19.74	0.9887	5.73	0.26	0.9011
RH400	0.23	13.01	0.9836	4.38	0.23	0.9408
RH500	0.32	15.65	0.9645	5.70	0.22	0.8899
RH600	0.21	9.87	0.9879	3.55	0.21	0.9122
SD400	0.31	9.24	0.9919	3.68	0.20	0.9440
SD500	0.27	7.83	0.9931	3.15	0.19	0.9429
SD600	0.15	7.22	0.9980	2.41	0.22	0.9199

表3 生物炭的理化性质

样品	灰分/%	元素分析/%				元素摩尔比/mol·mol^-1			可溶性组分/mg·g^-1
样品	灰分/%	C	H	O	N	H/C	O/C	(O+N)/C	K⁺	Ca²⁺	Mg²⁺	$P O 4 3 -$
RS400	30.40	61.60	4.41	31.67	1.85	0.86	0.39	0.41	38.83	1.11	0.60	0.59
RS500	40.66	70.74	3.56	23.54	1.70	0.60	0.25	0.27	44.23	0.94	0.61	0.53
RS500-X	—	—	—	—	—	—	—	—	61.45	1.43	1.03	0.19
RS600	47.06	78.50	2.10	17.36	1.64	0.32	0.17	0.18	41.16	0.73	0.56	0.42
RH400	32.5	70.30	7.33	21.47	0.49	1.25	0.23	0.24	15.37	0.23	0.15	0.43
RH500	41.08	83.21	3.12	12.90	0.42	0.45	0.12	0.12	16.29	0.13	0.11	0.31
RH600	44.06	88.76	1.70	8.83	0.38	0.23	0.07	0.07	10.10	0.10	0.05	0.23
SD400	7.68	63.50	4.46	31.38	0.51	0.84	0.37	0.38	7.82	0.22	0.95	0.35
SD500	10.89	75.44	3.16	20.86	0.43	0.50	0.21	0.21	4.98	0.16	0.93	0.26
SD600	20.7	81.79	2.41	15.34	0.36	0.35	0.14	0.15	3.62	0.07	0.69	0.13

表3 生物炭的理化性质

样品	灰分/%	元素分析/%				元素摩尔比/mol·mol^-1			可溶性组分/mg·g^-1
样品	灰分/%	C	H	O	N	H/C	O/C	(O+N)/C	K⁺	Ca²⁺	Mg²⁺	$P O 4 3 -$
RS400	30.40	61.60	4.41	31.67	1.85	0.86	0.39	0.41	38.83	1.11	0.60	0.59
RS500	40.66	70.74	3.56	23.54	1.70	0.60	0.25	0.27	44.23	0.94	0.61	0.53
RS500-X	—	—	—	—	—	—	—	—	61.45	1.43	1.03	0.19
RS600	47.06	78.50	2.10	17.36	1.64	0.32	0.17	0.18	41.16	0.73	0.56	0.42
RH400	32.5	70.30	7.33	21.47	0.49	1.25	0.23	0.24	15.37	0.23	0.15	0.43
RH500	41.08	83.21	3.12	12.90	0.42	0.45	0.12	0.12	16.29	0.13	0.11	0.31
RH600	44.06	88.76	1.70	8.83	0.38	0.23	0.07	0.07	10.10	0.10	0.05	0.23
SD400	7.68	63.50	4.46	31.38	0.51	0.84	0.37	0.38	7.82	0.22	0.95	0.35
SD500	10.89	75.44	3.16	20.86	0.43	0.50	0.21	0.21	4.98	0.16	0.93	0.26
SD600	20.7	81.79	2.41	15.34	0.36	0.35	0.14	0.15	3.62	0.07	0.69	0.13

图3 生物炭吸附前后红外谱图

图4 生物炭吸附前后X射线能谱图

图5 生物炭吸附Cd2+过程中各作用机制吸附贡献值及贡献比例

参考文献 21

1	LI H , DONG X , SILVA E B DA , et al . Mechanisms of metal sorption by biochars: biochar characteristics and modifications[J]. Chemosphere, 2017, 178: 466-478.
2	何昱轩, 张黎明, 郭飞飞, 等 . 硅基吸附剂处理含镉废水的研究进展[J]. 化工进展, 2018, 37(2): 724-736.
	HE Yuxuan , ZHANG Liming , GUO Feifei , et al . Advances in cadmium removal from wastewater by silica-based materials[J]. Chemical Industry and Engineering Progress, 2018, 37(2): 724-736.
3	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.
4	ZHOU N , CHEN H , XI J , et al . Biochars with excellent Pb(II) adsorption property produced from fresh and dehydrated banana peels via hydrothermal carbonization[J]. Bioresource Technology, 2017, 232: 204-210.
5	CUI X , FANG S , YAO Y , et al . Potential mechanisms of cadmium removal from aqueous solution by Canna indica derived biochar[J]. Science of the Total Environment, 2016, 562: 517-525.
6	AHMAD M , RAJAPAKSHA A U , LIM J E, et al . Biochar as a sorbent for contaminant management in soil and water: a review[J]. Chemosphere, 2014, 99: 19-33.
7	INYANG M I , GAO B , YAO Y , et al . A review of biochar as a low-cost adsorbent for aqueous heavy metal removal[J]. Critical Reviews in Environmental Science & Technology, 2016, 46(4): 406-433.
8	TAG A T, DUMAN G , UCAR S , et al . Effects of feedstock type and pyrolysis temperature on potential applications of biochar[J]. Journal of Analytical & Applied Pyrolysis, 2016, 120: 200-206.
9	ZHANG F , WANG X , YIN D , et al . Efficiency and mechanisms of Cd removal from aqueous solution by biochar derived from water hyacinth (Eichornia crassipes)[J]. Journal of Environmental Management, 2015, 153: 68-73.
10	LEE S M, DAVIS A P . Removal of Cu(Ⅱ) and Cd(Ⅱ) from aqueous solution by seafood processing waste sludge[J]. Water Research, 2001, 35(2): 534-540.
11	SUN J , LIAN F , LIU Z , et al . Biochars derived from various crop straws: characterization and Cd(Ⅱ) removal potential[J]. Ecotoxicology & Environmental Safety, 2014, 106(2): 226-231.
12	XU X , CAO X , LING Z , et al . Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar[J]. Environmental Science and Pollution Research, 2013, 20(1): 358-368.
13	陈再明, 方远, 徐义亮, 等 . 水稻秸秆生物碳对重金属Pb²⁺的吸附作用及影响因素[J]. 环境科学学报, 2012, 32(4): 769-776.
	CHEN Zaiming , FANG Yuan , XU Yiliang , et al . Adsorption of Pb²⁺ by rice straw derived-biochar and its influential factors[J]. Acta Scientiae Circumstantiae, 2012, 32(4): 769-776.
14	WANG R , HUANG D , LIU Y , et al . Investigating the adsorption behavior and the relative distribution of Cd²⁺ sorption mechanisms on biochars by different feedstock[J]. Bioresource Technology, 2018, 261: 265-271.
15	ZHANG C , SHAN B , TANG W , et al . Comparison of cadmium and lead sorption by Phyllostachys pubescens biochar produced under a low-oxygen pyrolysis atmosphere[J]. Bioresource Technology, 2017, 238: 352-360.
16	王震宇, 刘国成, 李锋民, 等 . 不同热解温度生物炭对Cd(Ⅱ)的吸附特性[J]. 环境科学, 2014, 35(12): 4735-4744.
	WANG Zhenyu , LIU Guocheng , LI Fengmin , et al . Adsorption of Cd(Ⅱ) varies with biochars derived at different pyrolysis temperature[J]. Environmental Science, 2014, 35(12): 4735-4744.
17	CHENG M , ZENG G , HUANG D , et al . Hydroxyl radicals based advanced oxidation processes (AOPs) for remediation of soils contaminated with organic compounds: a review[J]. Chemical Engineering Journal, 2016, 284: 582-598.
18	徐楠楠, 林大松, 徐应明, 等 . 玉米秸秆生物炭对Cd²⁺的吸附特性及影响因素[J]. 农业环境科学学报, 2014, 33(5): 958-964.
	XU Nannan , LIN Dasong , XU Yingming , et al . Adsorption of aquatic Cd²⁺ by biochar obtained from corn stover[J]. Journal of Agro-Environment Science, 2014, 33(5): 958-964.
19	MARCO K , NICO P S , JOHNSON M G , et al . Dynamic molecular structure of plant biomass-derived black carbon (biochar)[J]. Environmental Science & Technology, 2010, 44(4): 1247-1253.
20	WANG Z , ZHENG H , LUO Y , et al . Characterization and influence of biochars on nitrous oxide emission from agricultural soil[J]. Environmental Pollution, 2013, 174(5): 289-296.
21	LIU L , FAN S . Removal of cadmium in aqueous solution using wheat straw biochar: effect of minerals and mechanism[J]. Environmental Science & Pollution Research, 2018, 25(9): 8688-8700.

[1]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[2]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[3]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[4]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[5]	赵景超, 谭明. 表面活性剂对电渗析减量化工业含盐废水的影响[J]. 化工进展, 2023, 42(S1): 529-535.
[6]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[7]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[8]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[9]	王晨, 白浩良, 康雪. 大功率UV-LED散热与纳米TiO₂光催化酸性红26耦合系统性能[J]. 化工进展, 2023, 42(9): 4905-4916.
[10]	王琦, 寇丽红, 王冠宇, 王吉坤, 刘敏, 李兰廷, 王昊. 焦化废水生物出水中可溶解性有机物的分子识别[J]. 化工进展, 2023, 42(9): 4984-4993.
[11]	史天茜, 石永辉, 武新颖, 张益豪, 秦哲, 赵春霞, 路达. Fe²⁺对厌氧氨氧化EGSB反应器运行性能的影响[J]. 化工进展, 2023, 42(9): 5003-5010.
[12]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[13]	张振, 李丹, 陈辰, 吴菁岚, 应汉杰, 乔浩. 吸附树脂对唾液酸的分离纯化[J]. 化工进展, 2023, 42(8): 4153-4158.
[14]	王帅晴, 杨思文, 李娜, 孙占英, 安浩然. 元素掺杂生物质炭材料在电化学储能中的研究进展[J]. 化工进展, 2023, 42(8): 4296-4306.
[15]	姜晶, 陈霄宇, 张瑞妍, 盛光遥. 载锰生物炭制备及其在环境修复中应用研究进展[J]. 化工进展, 2023, 42(8): 4385-4397.

原料种类和热解温度对生物炭吸附Cd²⁺的影响

Effects of feedstock type and pyrolysis temperature on Cd²⁺ adsorption by biochar

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价