酸改性酒糟生物炭对Cr（Ⅵ）的去除性能研究

doi:10.19965/j.cnki.iwt.2024-0107

摘要/Abstract

摘要：

利用白酒酒糟制备生物炭，采用KHCO₃活化后，再利用酸溶液浸渍进行改性，制备了酸改性酒糟生物炭（H-BC）。对H-BC的制备参数（热解温度、活化剂比例、改性酸种类及浓度）进行优化，得到热解温度为700 ℃，酒糟生物炭与活化剂（KHCO₃）为1∶1.5，采用0.5 mol/L硝酸改性制备的H-BC对Cr（Ⅵ）的吸附性能最优。探讨了初始pH（2.0~6.0）、初始Cr（Ⅵ）质量浓度（100~600 mg/L）、吸附时间（0~27 h）、吸附温度（20~60 ℃）、背景离子等因素对H-BC吸附Cr（Ⅵ）效果的影响，结果表明，在pH=2.0时吸附性能最好，其吸附量为171.05 mg/g，去除率为86%；生物炭投加量为2.5 g/L时，Cr（Ⅵ）初始质量浓度为100~400 mg/L范围内酒糟生物炭表现出较好的吸附性能，H-BC的吸附量为151.36 mg/g，去除率为94.54%；吸附过程可分为快速吸附阶段（0~1 h）、缓慢吸附阶段（1~20 h）、平衡阶段（20~27 h）；H-BC对Cr（Ⅵ）的吸附是一个吸热过程，吸附温度升高，吸附量随之增加；背景电解质（NaCl、KCl）浓度对Cr（Ⅵ）的吸附具有较大影响；吸附过程更符合Langmuir等温模型与准二级吸附动力学模型。H-BC对Cr（Ⅵ）的吸附机理涉及静电引力与氧化还原作用。

关键词: 酒糟生物炭, 改性, 吸附, Cr（Ⅵ）

Abstract:

The acid modified biochar (H-BC) was prepared with distillers’ grains, which was activated by KHCO₃ and modified by dipping in acid solution. By optimizing the preparation parameters of H-BC (pyrolysis temperature, activator ratio, type and concentration of modified acid), it was found that H-BC prepared at a pyrolysis temperature of 700 ℃ and a mass ratio of distillers’ grains biochar to activator (KHCO₃) of 1∶1.5, and modified with 0.5 mol/L nitric acid had the best adsorption performance for Cr(Ⅵ). The effects of initial pH (2.0-6.0), initial Cr(Ⅵ) mass concentration (100-600 mg/L), adsorption time (0-27 h), adsorption temperature (20-60 ℃), background ions on the adsorption efficiency of H-BC for Cr(Ⅵ) were investigated. The results showed that the best adsorption performance was achieved at pH 2.0, with the adsorption capacity of 171.05 mg/g and the removal rate of 86%. When the initial mass concentration of Cr(Ⅵ) was 100-400 mg/L and the dosage of biochar was 2.5 g/L, the adsorption capacity of H-BC could reach 151.36 mg/g, with removal rate of 94.54%, demonstrating good adsorption performance within this concentration range. The adsorption process could be divided into rapid adsorption stage (0-1 h), slow adsorption stage (1-20 h), and equilibrium stage (20-27 h). The adsorption of Cr(Ⅵ) by H-BC was an endothermic process, and the adsorption amount increased with the increase of adsorption temperature. The concentration of background electrolytes(NaCl, KCl) had a significant impact on the adsorption of Cr(Ⅵ). The adsorption process was more in line with the Langmuir isotherm model and quasi second order kinetic model. The adsorption mechanism of H-BC for Cr(Ⅵ) involved electrostatic attraction and redox reactions.

Key words: distillers’ grains biochar, modified, adsorption, Cr(Ⅵ)

中图分类号:

X703

唐恒军, 邱彪, 司马卫平, 唐建. 酸改性酒糟生物炭对Cr（Ⅵ）的去除性能研究[J]. 工业水处理, 2025, 45(3): 144-151.

Hengjun TANG, Biao QIU, Weiping SIMA, Jian TANG. Study on the removal of Cr(Ⅵ) by acid-modified distillers’ grains biochar[J]. Industrial Water Treatment, 2025, 45(3): 144-151.

https://www.iwt.cn/CN/Y2025/V45/I3/144

图/表 10

图1 制备参数对酒糟生物炭吸附Cr（Ⅵ）性能的影响

Fig.1 Effect of preparation parameters on Cr（Ⅵ） adsorption by distillers’ grains biochar

图2 N₂吸附/解吸等温线与孔径分布

Fig.2 N₂ adsorption/desorption isotherm and pore size distribution

表1 吸附剂的比表面积及孔隙结构数据

Table 1 Specific surface area and pore structure data of adsorbents

吸附剂	比表面积/（m²·g^-1）	孔容积/（cm³·g^-1）	平均孔径/nm
BC	217.23	0.151 4	2.79
KH-BC	919.42	0.668 9	2.91
H-BC	1 286.79	0.872 7	2.71

图3 BC（a~c）、KH-BC（d~f）与H-BC（g~i）的SEM

Fig.3 SEM images of BC（a-c），KH-BC（d-f），and H-BC（g-i）

图4 吸附条件对生物炭吸附Cr（Ⅵ）性能的影响

Fig.4 Effect of adsorption conditions on the adsorption performance of Cr（Ⅵ） by biochar

图5 H-BC，KH-BC与BC吸附Cr（Ⅵ）的反应动力学特性

Fig.5 Kinetic model of Cr（Ⅵ） removal by H-BC，KH-BC and BC

表2 反应动力学拟合参数

Table 2 Kinetic fitting parameters

生物炭	准一级反应动力学模型			准二级反应动力学模型			内扩散模型									Elovich模型
生物炭	Q _e/（mg·g^-1）	k ₁	R ²	Q _e/（mg·g^-1）	k ₂	R ²	K _d，1	C ₁	R ²	K _d，2	C ₂	R ²	K _d，3	C ₃	R ²	α	β	R ²
H-BC	60.16	0.004	0.919 8	178.89	0.000 2	0.9996	2.385	121.85	0.986 4	0.975	141.60	0.982 5	0.352	163.14	0.505 1	6.86×10⁴	0.090	0.935 6
KH-BC	36.16	0.003	0.934 7	157.98	0.000 3	0.999 7	2.263	122.67	0.941 5	0.828	128.04	0.983 8	0.185	149.09	0.298 7	1.49×10⁶	0.124	0.993 7
BC	1.61	0.002	0.908 6	9.94	0.065	0.999 5	0.194	6.72	0.683 5	0.048	8.45	0.995 3	0.056	7.71	0.855 1	9.82×10⁴	1.957	0.935 6

表3 等温吸附模型参数

Table 3 Fitting parameters of isothermal model

吸附剂	Langmuir			Freundlich
吸附剂	Q _m/（mg·g^-1）	K _L/（L·mg^-1）	R²	1/n	K _F/（mg^1-1/ ⁿ ·L^1/ ⁿ ·g^-1）	R²
H-BC	181.25	0.332	0.976 8	0.204	71.53	0.937 1
KH-BC	156.60	3.08	0.987 4	0.125	89.95	0.925 3
BC	16.10	0.029	0.899 2	0.325	2.57	0.949 0

图6 H-BC、KH-BC和BC的等温吸附模型

Fig.6 Adsorption isotherm model of H-BC，KH-BC，and BC

图7 H-BC吸附Cr（Ⅵ）前后的FTIR

Fig.7 FTIR of H-BC before and after Cr（Ⅵ） adsorption

参考文献 30

1	SUN Qian， ZHANG Lixin， WANG Changlong，et al. High nitrogen content bimolecular co-functionalized graphene nanoflakes for hypertoxic Cr（Ⅵ） removal：Insights into adsorption behavior and mechanisms［J］. Chemosphere，2023，340：139804. doi:10.1016/j.chemosphere.2023.139804
2	YANG Xiaoyang， WANG Baofeng， ZHANG Peng，et al. Adsorption and reduction of Cr（Ⅵ） by N，S co-doped porous carbon from sewage sludge and low-rank coal：Combining experiments and theoretical calculations［J］. Science of the Total Environment，2024，912：169265.
3	TANG Hengjun， QIU Biao， TANG Jian，et al. Enhanced removal of Cr（Ⅵ） of effectiveness and mechanism from wastewater using modified distiller grains-based biochar［J］. Desalination and Water Treatment，2023，295：166-176.
4	ZHANG Xin， XU Hongxing， XI Min，et al. Removal/adsorption mechanisms of Cr（Ⅵ） and natural organic matter by nanoscale zero-valent iron-loaded biochar in their coexisting system［J］. Journal of Environmental Chemical Engineering，2023，11（3）：109860.
5	MOHAMMED Y A Y A， ABDEL-MOHSEN A M， ZHANG Qijun，et al. Facile synthesis of ZIF-8 incorporated electrospun PAN/PEI nanofibrous composite membrane for efficient Cr（Ⅵ） adsorption from water［J］. Chemical Engineering Journal，2023，461：141972.
6	PAK T， GOMARI K E， BOSE S，et al. Biochar from brown algae：Production，activation，and characterisation［J］. Bioresource Technology Reports，2023，24：101688.
7	FENG Zhengyuan， CHEN Nan， LIU Tong，et al. KHCO₃ activated biochar supporting MgO for Pb（Ⅱ） and Cd（Ⅱ） adsorption from water：Experimental study and DFT calculation analysis［J］. Journal of Hazardous Materials，2022，426：128059.
8	ZHAO Meihua， BAI Xiang， FAN Xing，et al. Structure and adsorption performance of sludge-based porous carbon materials modified by KHCO₃ ［J］. Materials Letters，2023，350：134937.
9	SINGH J， VERMA M. Waste derived modified biochar as promising functional material for enhanced water remediation potential［J］. Environmental Research，2024，245：117999.
10	ZHAO Chen， LI Yuehua， HE Zhangxing，et al. KHCO₃ activated carbon microsphere as excellent electrocatalyst for VO²⁺/VO₂ ⁺ redox couple for vanadium redox flow battery［J］. Journal of Energy Chemistry，2019，29：103-110.
11	QIU Yue， ZHANG Qian， GAO Bin，et al. Removal mechanisms of Cr（Ⅵ） and Cr（Ⅲ） by biochar supported nanosized zero-valent iron：Synergy of adsorption，reduction and transformation［J］. Environmental Pollution，2020，265：115018.
12	IMRAN M， KHAN Z U H， IQBAL M M，et al. Effect of biochar modified with magnetite nanoparticles and HNO₃ for efficient removal of Cr（Ⅵ） from contaminated water：A batch and column scale study［J］. Environmental Pollution，2020，261：114231.
13	LI Yunchao， SHAO Jingai， WANG Xianhua，et al. Characterization of modified biochars derived from bamboo pyrolysis and their utilization for target component（furfural） adsorption［J］. Energy & Fuels，2014，28（8）：5119-5127.
14	YANG Zihao， AN Qiang， DENG Shuman，et al. Efficient activation of peroxydisulfate by modified red mud biochar derived from waste corn straw for levofloxacin degradation：Efficiencies and mechanisms［J］. Journal of Environmental Chemical Engineering，2023，11（6）：111609.
15	HE Yingnan， CHEN Jianbing， Jiapei LÜ，et al. Separable amino-functionalized biochar/alginate beads for efficient removal of Cr（Ⅵ） from original electroplating wastewater at room temperature［J］. Journal of Cleaner Production，2022，373：133790. doi:10.1016/j.jclepro.2022.133790
16	CHEN Yongjun， MA Rui， PU Xunchi，et al. The characterization of a novel magnetic biochar derived from sulfate-reducing sludge and its application for aqueous Cr（Ⅵ） removal through synergistic effects of adsorption and chemical reduction［J］. Chemosphere，2022，308（Pt 1）：136258.
17	CHEN Dong， DU Xiaohu， CHEN Kunyuan，et al. Efficient removal of aqueous Cr（Ⅵ） with ferrous sulfide/N-doped biochar composites：Facile，in situ preparation and Cr（Ⅵ） uptake performance and mechanism［J］. Science of the Total Environment，2022，837：155791.
18	HERATH A， LAYNE C A， PEREZ F，et al. KOH-activated high surface area Douglas Fir biochar for adsorbing aqueous Cr（Ⅵ），Pb（Ⅱ） and Cd（Ⅱ）［J］. Chemosphere，2021，269：128409.
19	KUANG Qunfeng， LIU Kun， WANG Qikun，et al. Three-dimensional hierarchical pore biochar prepared from soybean protein and its excellent Cr（Ⅵ） adsorption［J］. Separation and Purification Technology，2023，304：122295.
20	YU Jiangdong， JIANG Chunyan， GUAN Qingqing，et al. Enhanced removal of Cr（Ⅵ） from aqueous solution by supported ZnO nanoparticles on biochar derived from waste water hyacinth［J］. Chemosphere，2018，195：632-640.
21	ZHAO Nan， TAN Xiaofei， XIONG Juan，et al. Quantitative analysis on the redox conversion mechanism of Cr（Ⅵ） and As（Ⅲ） by iron carbide based biochar composites［J］. Chemical Engineering Journal，2022，446：137417.
22	BULUT E， ÖZACAR M， ŞENGIL İ A. Adsorption of malachite green onto bentonite：Equilibrium and kinetic studies and process design［J］. Microporous and Mesoporous Materials，2008，115（3）：234-246.
23	WANG Shenwan， ZHONG Shuang， ZHENG Xiaoyan，et al. Calcite modification of agricultural waste biochar highly improves the adsorption of Cu（Ⅱ） from aqueous solutions［J］. Journal of Environmental Chemical Engineering，2021，9（5）：106215.
24	YIN Guangcai， SONG Xiaowang， TAO Lin，et al. Novel Fe-Mn binary oxide-biochar as an adsorbent for removing Cd（Ⅱ） from aqueous solutions［J］. Chemical Engineering Journal，2020，389：124465.
25	DONG Fuxin， YAN Liu， ZHOU Xinhua，et al. Simultaneous adsorption of Cr（Ⅵ） and phenol by biochar-based iron oxide composites in water：Performance，kinetics and mechanism［J］. Journal of Hazardous Materials，2021，416：125930.
26	KHAN A A， NAQVI S R，ALI I，et al. Algal-derived biochar as an efficient adsorbent for removal of Cr（Ⅵ） in textile industry wastewater：Non-linear isotherm，kinetics and ANN studies［J］. Chemosphere，2023，316：137826.
27	LIU Na， ZHANG Yuting， XU Chao，et al. Removal mechanisms of aqueous Cr（Ⅵ） using apple wood biochar：A spectroscopic study［J］. Journal of Hazardous Materials，2020，384：121371.
28	ZHANG Hongda， LI Lijuan， LI Yanjun，et al. N and S co-doped pine needle biochar activated peroxydisulfate for antibiotic degradation［J］. Journal of Cleaner Production，2022，379：134619.
29	JIN Xingyun， TANG Xiaolong， LI Huan，et al. Visible-light driven efficient elimination of organic hazardous and Cr（Ⅵ） over BiOCl modified by Chinese baijiu distillers’ grain-based biochar［J］. Journal of Industrial and Engineering Chemistry，2022，107：472-482.
30	张雨婷. 生物质炭对电镀废水中六价铬的去除及机理研究［D］. 长春：吉林大学，2020.
	ZHANG Yuting. Study on removal efficiency and mechanism of hexavalent chromium from electroplating wastewater by biochar［D］. Changchun：Jilin University，2020.

[1]	江惟, 蔡萧蝶, 文昕宇, 陈思莉, 王劲松, 张政科. 介孔硅/海藻酸钠复合材料的制备及其对放射性Sr²⁺的去除[J]. 工业水处理, 2025, 45(3): 90-98.
[2]	李秀玲, 宾冰, 龚盈盈, 武哲, 曾湘楚. 铁锰改性桑枝生物炭的构筑及其对水体磷的吸附[J]. 工业水处理, 2025, 45(3): 175-184.
[3]	王庆元, 张彦平, 李一兵, 李芬. 农膜-秸秆生物质炭对亚甲基蓝的吸附性能[J]. 工业水处理, 2025, 45(3): 110-120.
[4]	靳亚斌, 徐甜甜, 赵德中, 张乐, 万振杰, 张高明. Bi₂O₃基复合光催化剂的制备及其在水处理中的应用进展[J]. 工业水处理, 2025, 45(3): 10-21.
[5]	陈亚松, 苗时雨, 张驰, 李明然, 王佳琪, 张燕羽, 姜伟. 除磷吸附材料的制备及吸附机制研究进展[J]. 工业水处理, 2025, 45(2): 1-9.
[6]	王文豪, 程业兴, 王雨银, 侯婷婷, 吴晓峰, 李玉才. 不同种类活性炭对mZVI/活性炭吸附还原Cr（Ⅵ）的影响[J]. 工业水处理, 2025, 45(2): 150-158.
[7]	傅翔宇, 李亚峰, 刘奕含, 崔可清, 王玲萍. 磷酸三丁酯改性生物炭活化PMS降解双酚A的效能[J]. 工业水处理, 2025, 45(1): 87-93.
[8]	刘清, 黄健滨, 李伟凡, 招国栋, 杨景景. 单宁酸复合海藻酸钠微球富集U（Ⅵ）的性能[J]. 工业水处理, 2025, 45(1): 58-65.
[9]	张伟业, 申婧, 潘子鹤, 宋一朋, 成怀刚, 张慧荣. 饱和活性炭热再生过程残余物形成及影响因素分析[J]. 工业水处理, 2025, 45(1): 17-25.
[10]	张翠红, 王靖, 王洁, 袁文蛟. 季铵盐改性二氧化硅的制备及其吸附钒（Ⅴ）的性能[J]. 工业水处理, 2025, 45(1): 104-114.
[11]	邓志华, 刘蕊, 李碧青. 不同生物炭的制备及其对重金属和抗生素的吸附性能[J]. 工业水处理, 2025, 45(1): 94-103.
[12]	郭紫瑞, 李红艳, 张峰, 崔佳丽, 杨群, 李赟. Fe₂O₃-CuO/rCG催化降解水中苯并三氮唑的效能与机理[J]. 工业水处理, 2024, 44(9): 118-126.
[13]	邓钦, 钟溢健, 李金城, 时慧慧, 韦春满, 覃佳佳. 新型除磷填料的制备及再生能力试验[J]. 工业水处理, 2024, 44(8): 140-148.
[14]	张毅豪, 侯保林, 王佳欣, 张婷, 任志文. Fe₃O₄掺杂改性电极电化学去除Pb²⁺的效能研究[J]. 工业水处理, 2024, 44(8): 107-113.
[15]	刘畅益, 田佳旺, 张浩东, 秦哲. 改性芦苇材料的吸附脱氮性能及其资源化探究[J]. 工业水处理, 2024, 44(8): 122-132.

选择文件类型/文献管理软件名称

选择包含的内容