基于碳酸氢钠活化的氮掺杂水稻秸秆生物炭的制备及其对镉的吸附

doi:10.3969/j.issn.1004-1524.20250062

浙江农业学报 ›› 2026, Vol. 38 ›› Issue (5): 944-954.DOI: 10.3969/j.issn.1004-1524.20250062

基于碳酸氢钠活化的氮掺杂水稻秸秆生物炭的制备及其对镉的吸附

程凯¹^,²(), 李飞跃¹, 何莉莉²^,³, 杨承虎², 汪玉瑛²^,³, 吕豪豪²^,³, 杨生茂²^,³, 刘玉学¹^,²^,³^,^*()

¹ 安徽科技学院资源与环境学院, 安徽凤阳 233100
² 浙江省农业科学院环境资源与土壤肥料研究所, 农产品质量安全全国重点实验室, 浙江杭州 310021
³ 浙江省生物炭工程技术研究中心, 浙江杭州 310021

收稿日期:2025-01-18 出版日期:2026-05-25 发布日期:2026-06-02
作者简介:程凯,研究方向为生物炭与重金属污染修复。E-mail:18155089603@163.com
通讯作者: *刘玉学,E-mail:liuyuxue505@163.com
基金资助:
国家重点研发计划子课题(2023YFD1902903)

Preparation of nitrogen-doped rice straw biochar activated by sodium bicarbonate and its adsorption of cadmium

CHENG Kai¹^,²(), LI Feiyue¹, HE Lili²^,³, YANG Chenghu², WANG Yuying²^,³, LYU Haohao²^,³, YANG Shengmao²^,³, LIU Yuxue¹^,²^,³^,^*()

¹ College of Resource and Environment, Anhui Science and Technology University, Fengyang 233100, Anhui, China
² State Key Laboratory for Quality and Safety of Agro-Products, Institute of Soil, Fertilizer and Environmental Resources, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China
³ Engineering Research Center of Biochar of Zhejiang Province, Hangzhou 310021, China

Received:2025-01-18 Published:2026-05-25 Online:2026-06-02

摘要/Abstract

摘要：

以水稻秸秆为原料,分别以尿素和碳酸氢钠为氮源和化学活化剂,制备基于碳酸氢钠活化的氮掺杂水稻秸秆生物炭,开展生物炭吸附溶液中镉离子(Cd²⁺)的系列实验,研究溶液pH值、生物炭添加量、溶液中Cd²⁺初始质量浓度、温度、离子强度、共存离子等对生物炭吸附溶液中Cd²⁺的影响,并从动力学角度探究生物炭吸附Cd²⁺的机制。结果表明,尿素掺杂和碳酸氢钠活化的共同作用,提高了生物炭对Cd²⁺的吸附性能。相较于未改性的水稻秸秆生物炭(BC),将水稻秸秆粉、碳酸氢钠、尿素以2∶1∶1的比例改性制备的生物炭BC2-1-1对Cd²⁺的饱和吸附量为45.322 6 mg·g^-1,是BC的5.27倍。生物炭对Cd²⁺的等温吸附行为符合朗缪尔(Langmuir)等温吸附模型,动力学行为符合准二级动力学方程,说明是以化学吸附为主导的单分子层吸附机制。研究结果可为水稻秸秆的高值化利用和镉污染水体的修复提供理论依据和技术支撑。

关键词: 水稻秸秆生物炭, 氮掺杂, 化学活化, 镉, 吸附

Abstract:

Nitrogen-doped rice straw biochar activated by sodium bicarbonate was prepared using rice straw as the biomass precursor, with urea and sodium bicarbonate serving as the nitrogen source and chemical activator, respectively. A series of adsorption experiments were conducted to investigate the cadmium ions (Cd²⁺) adsorption in aqueous solutions using the prepared rice straw biochar. The effects of various factors, including solution pH value, biochar addition amount, initial Cd²⁺ mass concentration in solution, temperature, ionic strength and coexisting ions, on the adsorption performance were systematically examined. Additionally, the adsorption mechanism was explored from the kinetic perspective. The results demonstrated that the combined effect of urea doping and sodium bicarbonate activation enhanced Cd²⁺ adsorption. Compared with the conventional rice straw biochar (BC), the biochar prepared with a mixing ratio of 2∶1∶1 for rice straw powder, sodium bicarbonate and urea (marked as BC2-1-1) exhibited a maximum Cd²⁺ adsorption capacity of 45.322 6 mg·g^-1, which was 5.27 times as that of BC. The adsorption of Cd²⁺ by biochar fitted well with the Langmuir isothermal adsorption model, and followed the pseudo-second-order kinetic equation, indicating a monolayer adsorption mechanism dominated by chemical adsorption. This study provided theoretical basis and technical support for the high-value utilization of rice straw and the remediation of cadmium-contaminated water.

Key words: rice straw biochar, nitrogen doping, chemical activation, cadmium, adsorption

中图分类号:

TQ424
X52

程凯, 李飞跃, 何莉莉, 杨承虎, 汪玉瑛, 吕豪豪, 杨生茂, 刘玉学. 基于碳酸氢钠活化的氮掺杂水稻秸秆生物炭的制备及其对镉的吸附[J]. 浙江农业学报, 2026, 38(5): 944-954.

CHENG Kai, LI Feiyue, HE Lili, YANG Chenghu, WANG Yuying, LYU Haohao, YANG Shengmao, LIU Yuxue. Preparation of nitrogen-doped rice straw biochar activated by sodium bicarbonate and its adsorption of cadmium[J]. Acta Agriculturae Zhejiangensis, 2026, 38(5): 944-954.

图/表 9

表1 制备的生物炭的理化性质

Table 1 Physicochemical properties of the prepared biochar

样品 Sample	pH值 pH value	EC/ (μS·cm^-1)	w_C/%	w_N/%	w_H/%	w_O/%	H/C	O/C	SSA/ (m²·g^-1)	PV/ (cm³·g^-1)	APS/nm
BC	7.93±0.03	75.10±1.08	48.06	0.93	2.52	48.49	0.63	0.76	181.92	0.12	2.69
BC2-1-1	9.90±0.01	115.23±2.20	30.00	2.03	1.86	66.11	0.74	1.65	288.79	0.24	3.28
BC1-1-1	9.54±0.01	148.70±1.31	23.46	2.39	1.81	72.34	0.93	2.31	384.19	0.32	3.38

图1 生物炭的红外光谱 BC,本研究制备的水稻秸秆生物炭;BC2-1-1和BC1-1-1分别为由水稻秸秆粉、碳酸氢钠、尿素按2∶1∶1和1∶1∶1的比例混合制作的生物炭。下同。

Fig.1 Infrared spectrum of prepared biochar BC, Prepared rice straw biochar. BC2-1-1 and BC1-1-1 represent the biochar made from rice straw, sodium and urea at the ratio of 2∶1∶1 and 1∶1∶1, respectively. The same as below.

图2 生物炭的X射线光电子能谱(XPS)

Fig.2 X-ray photoelectron spectroscopy (XPS) of biochar a,BC;b,BC2-1-1;c,BC1-1-1。

图3 生物炭Cd2+去除率受pH值(a)、初始质量浓度(b)、生物炭添加量(c)和温度(d)的影响同一材料柱上无相同字母的表示不同温度下差异显著(p<0.05)。

Fig.3 Effects of pH value (a), initial mass concentration (b), biochar addition amount (c), and temperature (d) on the Cd2+ removal rate of biochar Bars marked without the same letters indicate significant (p<0.05) difference within varying temperature for the same biochar.

图4 BC(a)、BC2-1-1(b)和BC1-1-1(c)对溶液中Cd2+的吸附动力学模型 qe为平衡时的吸附量;qt为t时刻的吸附量。下同。

Fig.4 Adsorption kinetics models of Cd2+in solution by BC(a), BC2-1-1 (b), and BC1-1-1 (c) qe is the adsorption capacity at equilibrium; qt is the adsorption capacity at time t. The same as below.

表2 准一级和准二级动力学方程参数

Table 2 Parameters of pseudo-first-order and pseudo-second-order dynamics equations

样品 Sample	准一级动力学模型Pseudo-first-order model			准二级动力学模型Pseudo-second-order model
样品 Sample	q_e/(mg·g^-1)	R²	k₁/min^-1	q_e/(mg·g^-1)	R²	k₂/(g·mg^-1·min^-1)
BC	0.496 3	0.861 8	0.996 0	0.702 9	0.995 0	0.301 8
BC2-1-1	7.155 6	0.882 9	0.157 6	7.369 2	0.997 1	0.023 1
BC1-1-1	8.463 8	0.817 8	0.180 8	8.410 4	0.997 1	0.014 7

图5 BC(a)、BC2-1-1(b)和BC1-1-1(c)对溶液中Cd2+的等温吸附模型 Ce为平衡时溶液中的Cd2+含量,mg·L-1。

Fig.5 Isothermal adsorption models of Cd2+ in solution by BC (a), BC2-1-1 (b), and BC1-1-1 (c) Ce is the Cd2+ concentration in the solution at equilibrium, mg·L-1.

表3 拟合的等温吸附模型参数

Table 3 Fitting parameters of isothermal adsorption models

样品 Sample	朗缪尔等温吸附模型 Langmuir isothermal adsorption model			弗罗因德利希等温吸附模型 Freundlich isothermal adsorption model
样品 Sample	q_m/(mg·g^-1)	k_L/(L·mg^-1)	R²	k_F/[mg·g^-1·(mg·L^-1)^-1/ⁿ)	1/n	R²
BC	8.605 8	0.996 6	0.997 2	4.771 7	0.173 4	0.856 4
BC2-1-1	45.322 6	0.222 3	0.990 9	9.068 4	0.850 1	0.932 1
BC1-1-1	40.322 6	0.307 7	0.991 5	9.583 1	1.096 9	0.878 9

图6 溶液离子强度(a) 、共存离子(b) 和循环次数(c)对BC2-1-1吸附Cd2+的影响柱上无相同字母的表示差异显著(p<0.05)。None表示溶液中不含有共存离子。

Fig.6 Effects of solution ion strength (a),coexisting ions (b), and cycle times (c) on Cd2+ adsorption by BC2-1-1 Bars marked without the same letters indicate significant difference at p<0.05. None indicates control without coexisting ions introduced in the solution.

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基于碳酸氢钠活化的氮掺杂水稻秸秆生物炭的制备及其对镉的吸附

Preparation of nitrogen-doped rice straw biochar activated by sodium bicarbonate and its adsorption of cadmium

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