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

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

Abstract

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

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

CLC Number:

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.

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.

Figures/Tables 8

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

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

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

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

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

原料种类和热解温度对生物炭吸附Cd²⁺的影响

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