铁锰改性桑枝生物炭的构筑及其对水体磷的吸附

doi:10.19965/j.cnki.iwt.2024-0103

摘要/Abstract

摘要：

含磷废水排放引起的水体富营养化为水环境生态带来了诸多危害，吸附法能有效处理含磷废水。以废弃桑枝为原料制备磁性桑枝生物炭，并负载铁锰氧化物制备铁锰改性桑枝生物炭复合材料，对复合材料进行XRD、FTIR、SEM、BET、VSM表征并研究其吸附除磷性能及循环使用性能。结果表明，复合材料具备Fe-Mn复合氧化物结构，具有较强的磁性，吸附除磷主要通过磷酸盐与金属活性位点吸附以及与表面羟基的配位交换作用。在温度25 ℃、吸附剂投加量0.20 g、吸附时间260 min、废水磷质量浓度7.5 mg/L、溶液pH=6时，复合材料对磷的吸附率达到98.08%，溶液剩余磷质量浓度为0.14 mg/L，达到了《城镇污水处理厂污染物排放标准》（GB 18918—2002）一级A标准的排放要求。共存离子Cl^-和NO₃ ^-对吸附磷酸盐干扰较小，而CO₃ ^2-影响较大；通过磁性回收和酸洗再生5次，复合材料对磷的吸附率仍保持在67%以上；复合材料对磷的吸附过程符合准二级反应动力学方程和Langmuir等温线模型，反应自发进行且为放热反应。铁锰改性桑枝生物炭复合材料为含磷废水的净化提供了有效解决方案。

关键词: 磁性桑枝生物炭, 复合吸附剂, 除磷性能, 铁锰氧化物

Abstract:

The water eutrophication caused by the discharge of phosphorus-containing wastewater brings a lot of harm to the water environment and ecology, and the adsorption method can effectively alleviate the pollution. A composite material was prepared by using waste mulberry as raw materials, magnetic biochar as carrier and loaded with iron-manganese oxide. The adsorption and phosphorus removal and recycling properties were studied and the characterization of the composite material was studied by XRD, FTIR, SEM, BET, and VSM. The results showed that the composite adsorbent had Fe-Mn composite oxide structure and good magnetism. The adsorption and removal of phosphorus were mainly through the adsorption of phosphate to metal active sites and the coordination exchange with surface hydroxyl groups. When the temperature was 25 ℃, the dosage of adsorbent was 0.20 g, the adsorption time was 260 min, the mass concentration of phosphorus in wastewater was 7.5 mg/L, and the solution pH was 6, the adsorption rate of phosphorus on the composite material reached 98.08%, and the mass concentration of residual phosphorus was 0.14 mg/L, which met the Class A standard of Pollutant Discharge Standard of Urban Sewage Treatment Plant (GB 18918-2002). The co-existing ions Cl^- and NO₃ ^- had less interference on the adsorption of phosphate, while CO₃ ^2- had more influence. After magnetic recovery and pickling regeneration for 5 times, the adsorption rate of phosphorus was kept above 67%. The adsorption process conformed more to the pseudo-second-order kinetic and the Langmuir isotherm models, and the reaction was a spontaneous and exothermic process. The preparation of iron-manganese modified mulberry branch biochar composite provided an effective solution for the purification of phosphorus-containing wastewater.

Key words: magnetic mulberry biochar, composite adsorbent, phosphorus removal performance, iron-manganese oxide

中图分类号:

X703

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.

Xiuling LI, Bing BIN, Yingying GONG, Zhe WU, Xiangchu ZENG. Construction of iron-manganese modified mulberry branch biochar and the adsorption of aqueous phosphorus[J]. Industrial Water Treatment, 2025, 45(3): 175-184.

https://www.iwt.cn/CN/Y2025/V45/I3/175

图/表 13

图1 吸附材料的表征

Fig.1 Characterization of adsorption material

表1 磁性生物炭和复合材料的孔结构参数

Table 1 Pore structure parameters of the magnetic biochar and composite material

物质	比表面积/（m²·g^-1）	孔径/nm	孔容/（cm³·g^-1）
复合材料	269.58	10.09	0.15
磁性生物炭	329.79	10.06	0.21

图2 磁性生物炭和复合材料的吸附性能

Fig.2 Adsorption performance of magnetic biochar and composite materials

图3 投加量对复合材料吸附性能的影响

Fig.3 Effect of adsorbent dosage on adsorption performance of composite materials

图4 吸附时间对复合材料吸附性能的影响

Fig.4 Effect of adsorption time on adsorption performance of composite materials

图5 pH对复合材料吸附性能的影响

Fig.5 Effect of pH on adsorption performance of composite materials

图6 初始磷质量浓度对复合材料吸附性能的影响

Fig.6 Effect of phosphorus mass concentration on adsorption performance of composite materials

图7 共存离子对复合材料吸附性能的影响

Fig.7 Effect of co-existing ions on adsorption performance of composite materials

表2 正交实验结果

Table 2 Results of orthogonal experiments

序号	pH	初始磷质量浓度/（mg·L^-1）	吸附剂投加量/g	吸附时间/min	吸附率/%
1	6	2.5	0.12	60	99.98
2	6	5.0	0.16	160	98.72
3	6	7.5	0.20	260	98.08
4	7	2.5	0.16	260	99.84
5	7	5.0	0.20	60	99.52
6	7	7.5	0.12	160	75.15
7	8	2.5	0.20	160	97.44
8	8	5.0	0.12	260	88.32
9	8	7.5	0.16	60	81.55
K ₁	296.78	297.26	263.45	281.05
K ₂	274.51	286.56	280.11	271.31
K ₃	267.31	254.77	295.04	286.24
k _1平均	98.93	99.09	87.82	93.68
k _2平均	91.50	95.52	93.37	90.44
k _3平均	89.10	84.92	98.35	95.41
极差R	9.83	14.16	10.53	4.98

表3 吸附动力学拟合参数

Table 3 Adsorption kinetics fitting parameters

初始磷质量浓度C ₀/（mg·L^-1）	q _e，exp/（mg·g^-1）	准一级反应动力学			准二级反应动力学
初始磷质量浓度C ₀/（mg·L^-1）	q _e，exp/（mg·g^-1）	k ₁/min^-1	q _e，1/（mg·g^-1）	R ²	k ₂/（g·mg^-1·min^-1）	q _e，2/（mg·g^-1）	R ²
5	1.982	0.24	1.948	0.843 98	0.26	1.977	0.999 97

表4 不同温度下Langmuir、Freundlich模型拟合参数

Table 4 Fitting parameters of Langmuir model and Freundlich model at different temperatures

温度/℃	Langmuir模型			Freundlich模型
温度/℃	q _m/（mg·g^-1）	K _L	R ²	1/n	K _F	R ²
25	3.68	1.23	0.999	0.17	2.01	0.961
45	3.47	1.30	0.997	0.16	2.18	0.825
60	4.64	0.49	0.966	0.16	2.37	0.919

表5 不同温度下复合材料的吸附热力学常数

Table 5 Thermodynamic constants of composite materials at different temperatures

温度/K	lnk	ΔG/（kJ·mol^-1）	ΔH/（kJ·mol^-1）	ΔS/（J·mol^-1·K^-1）
298.15	11.70	-29.00	-20.16	31.09
318.15	11.76	-31.11
333.15	10.77	-29.83

图8 复合材料的重复利用性

Fig.8 Reusability of composite materials

参考文献 37

1	ZENG Xiangchu， ZHANG Guanghua， ZHU Junfeng. Selective adsorption of heavy metals from water by a hyper-branched magnetic composite material：Characterization，performance，and mechanism［J］. Journal of Environmental Management，2022，314：114979. doi:10.1016/j.jenvman.2022.114979
2	ZENG Xiangchu， ZHANG Guanghua， WEN Jia，et al. Simultaneous removal of aqueous same ionic type heavy metals and dyes by a magnetic chitosan/polyethyleneimine embedded hydrophobic sodium alginate composite：Performance，interaction and mechanism［J］. Chemosphere，2023，318：137869.
3	YANG Yuxiao， ZHU Junfeng， ZENG Qingzhu，et al. Enhanced activation of peroxydisulfate by regulating pyrolysis temperature of biochar supported nZVI for the degradation of oxytetracycline［J］. Journal of the Institute of Chemical Engineers，2023，145：104775.
4	YANG Yuxiao， ZHU Junfeng， ZENG Qingzhu，et al. Activation of persulfate by iron-loaded soybean straw biochar for efficient degradation of dye contaminants：Synthesis，performance，and mechanism［J］. Environmental Progress & Sustainable Energy，2023，42（5）：e14190.
5	CAI Ru， WANG Xin， JI Xionghui，et al. Phosphate reclaim from simulated and real eutrophic water by magnetic biochar derived from water hyacinth［J］. Journal of Environmental Management，2017，187：212-219.
6	ZENG Xiangchu， ZHANG Guanghua， LI Xiuling，et al. Selective removal of aqueous Hg²⁺ by magnetic composites sulfur-containing on the hyper-branched surface：Characterization，performance and mechanism［J］. Journal of Environmental Management，2023，325（Pt B）：116621.
7	ZENG Xiangchu， ZHANG Guanghua， ZHU Junfeng，et al. Adsorption of heavy metal ions in water by surface functionalized magnetic composites：A review［J］. Environmental Science：Water Research & Technology，2022，8（5）：907-925.
8	吴梦，张大超，徐师，等. 废水除磷工艺技术研究进展［J］. 有色金属科学与工程，2019，10（2）：97-103. doi:10.13264/j.cnki.ysjskx.2019.02.014
	WU Meng， ZHANG Dachao， XU Shi，et al. Research progress of dephosphorization technology on wastewater［J］. Nonferrous Metals Science and Engineering，2019，10（2）：97-103. doi:10.13264/j.cnki.ysjskx.2019.02.014
9	曾湘楚，莫镇榕，武哲，等. N/S共掺杂磁性生物炭对水体Cu（Ⅱ）和四环素的协同吸附机制［J/OL］. 化工进展，2024. DOI：10. 16085/j.issn.1000-6613.2023-1973 .
	ZENG Xiangchu， MO Zhenrong， WU Zhe，et al. Synergistic adsorption mechanism of aqueous Cu（Ⅱ） and TC by N/S co-doped biochar［J/OL］. Chemical Industry and Engineering Progress，2024. DOI：10.16085/j.issn.1000-6613.2023-1973 .
10	ZENG Xiangchu， ZHANG Guanghua， WU Zhe. Preparation and characterization of Schiff-base modified Fe₃O₄ hybrid material and its selective adsorption for aqueous Hg²⁺ ［J］. Environmental Science and Pollution Research，2022，29（20）：30324-30336.
11	刘项，南红岩，安强. 刺桐生物炭对水中氨氮和磷的吸附［J］. 农业资源与环境学报，2018，35（1）：66-73.
	LIU Xiang， Hongyan NAN， AN Qiang. The erythrina variegate biochar’s adsorption to NH₄ ⁺-N and P from aqueous solution［J］. Journal of Agricultural Resources and Environment，2018，35（1）：66-73.
12	ZENG Xiangchu， ZHU Junfeng， ZHANG Guanghua，et al. Molecular-level understanding on complexation-adsorption-degradation during the simultaneous removal of aqueous binary pollutants by magnetic composite aerogels［J］. Chemical Engineering Journal，2023，468：143536.
13	郅蒙蒙，王鹏飞，侯泽英，等. NH₄ ⁺对镁改性生物炭除磷效果的影响［J］. 环境科学，2019，40（2）：669-676.
	ZHI Mengmeng， WANG Pengfei， HOU Zeying，et al. Effect of nitrogen on magnesium modified biochar adsorption to phosphorus［J］. Environmental Science，2019，40（2）：669-676.
14	曾湘楚，宁海潮，武哲，等. 耦合均相-异相类芬顿体系强化水体耐药伤寒沙门氏菌的杀灭［J/OL］. 化工进展，2024.DOI：10.16085/j.issn.1000-6613.2023-2075 .
	ZENG Xiangchu， NING Haichao， WU Zhe，et al. Coupled homogeneous/heterogeneous Fenton-like system for enhanced inactivating of tetracycline-resistance Salmonella typhiBiosorbents ［J/OL］. Chemical Industry and Engineering Progress，2024.DOI：10.16085/j.issn.1000-6613.2023-2075 .
15	刘雪梅，吴凡，章海亮，等. 农林废弃物生物吸附剂处理重金属废水的研究进展［J］. 应用化工，2019，48（11）：2703-2707.
	LIU Xuemei， WU Fan， ZHANG Hailiang，et al. Research progress on the treatment of heavy metal wastewater by agroforestry waste biological adsorbent［J］. Applied Chemical Industry，2019，48（11）：2703-2707.
16	ZENG Xiangchu， ZHANG Guanghua， SHEN Yiding. Preparation and application of a long-chain water-based polyacrylate stripper on paper［J］. Journal of Polymer Research，2021，28（7）：241.
17	陈旭，梁美娜，王敦球，等. 桑树杆活性炭/铁锰氧化物复合吸附剂对磷的吸附研究［J］. 工业安全与环保，2018，44（12）：74-78.
	CHEN Xu， LIANG Meina， WANG Dunqiu，et al. Phosphorus removal from aqueous solution by mulberry stem activated carbon/Fe-Mn oxides composite adsorbent［J］. Industrial Safety and Environmental Protection，2018，44（12）：74-78.
18	曾湘楚，张光华，武哲. 长链疏水改性苯丙共聚物乳液的合成及固沙性能［J］. 华南师范大学学报（自然科学版），2021，53（6）：34-42.
	ZENG Xiangchu， ZHANG Guanghua， WU Zhe. The synthesis and sand solidification properties of long chain hydrophobic modified styrene-acrylic copolymer emulsion［J］. Journal of South China Normal University（Natural Science Edition），2021，53（6）：34-42.
19	QU Jianhua， SHI Jiajia， WANG Yihui，et al. Applications of functionalized magnetic biochar in environmental remediation：A review［J］. Journal of Hazardous Materials，2022，434：128841.
20	刘艳艳，王洁，田质涛，等. 高效可回收吸附剂磁性生物炭研究进展［J］. 武汉理工大学学报（信息与管理工程版），2022，44（3）：389-394.
	LIU Yanyan， WANG Jie， TIAN Zhitao，et al. Research progress of efficient recyclable adsorbent magnetic biochar［J］. Journal of Wuhan University of Technology（Information & Management Engineering），2022，44（3）：389-394.
21	WANG Li， WANG Jingyi， HE Chi，et al. Development of rare earth element doped magnetic biochars with enhanced phosphate adsorption performance［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2019，561：236-243. doi:10.1016/j.colsurfa.2018.10.082
22	苏浩杰，吴俊峰，王召东，等. 金属改性生物炭及其去除水中氮、磷的研究进展［J］. 工业水处理，2022，42（11）：46-55.
	SU Haojie， WU Junfeng， WANG Zhaodong，et al. Research progress of metal-modified biochar and its removal of nitrogen and phosphorus in water［J］. Industrial Water Treatment，2022，42（11）：46-55.
23	WANG Zhanghong， SHEN Dekui， SHEN Fei，et al. Phosphate adsorption on lanthanum loaded biochar［J］. Chemosphere，2016，150：1-7.
24	程福龙，潘杰，赵嫦欣. 环境科学专业综合创新实验：改性生物炭的制备及其除磷性能测定［J］. 山东化工，2021，50（8）：237-238.
	CHENG Fulong， PAN Jie， ZHAO Changxin. Comprehensive innovation experiment for environmental sciences specialty：Modified biochar and determination of its phosphorus removal performance［J］. Shandong Chemical Industry，2021，50（8）：237-238.
25	肖作义，肖宇，肖明慧，等. 磁性水滑石/生物炭复合材料的制备及其对水溶液中磷的吸附性能［J］. 环境污染与防治，2020，42（9）：1090-1095.
	XIAO Zuoyi， XIAO Yu， XIAO Minghui，et al. Preparation of magnetic hydrotalcite/biochar composite and its adsorption performance for phosphorus in aqueous solution［J］. Environmental Pollution & Control，2020，42（9）：1090-1095.
26	武哲，曲树光，冯练享，等. 海藻酸钠/微晶纤维素复合水凝胶对水中甲基橙和亚甲基蓝的吸附性能与机理［J/OL］. 化工进展，2024. DOI：10.16085/j.issn.1000-6613.2023-1028 .
	WU Zhe， QU Shuguang， ZENG Xiangchu，et al. Adsorption performances and mechanism of sodium alginate/microcrystalline cellulose composite hydrogel for aqueous methyl orange and methylene blue［J/OL］. Chemical Industry and Engineering Progress，2024. DOI：10.16085/j.issn.1000-6613.2023-1028 .
27	芦琳，颜利玲，梁美娜，等. 磁性氧化铁/桑树杆生物炭的制备及其对砷污染土壤溶解性有机碳和砷形态的影响［J］. 环境科学，2022，43（11）：5214-5223.
	LU Lin， YAN Liling， LIANG Meina，et al. Preparation of magnetic iron oxide/mulberry stem biochar and its effects on dissolved organic carbon and arsenic speciation in arsenic-contaminated soils［J］. Environmental Science，2022，43（11）：5214-5223.
28	LI Xiangping， WANG Chuanbin， ZHANG Jianguang，et al. Preparation and application of magnetic biochar in water treatment：A critical review［J］. Science of the Total Environment，2020，711：134847. doi:10.1016/j.scitotenv.2019.134847
29	BISWAS K， GUPTA K， GOSWAMI A，et al. Fluoride removal efficiency from aqueous solution by synthetic iron（Ⅲ）-aluminum（Ⅲ）- chromium（Ⅲ） ternary mixed oxide［J］. Desalination，2010，255（1/2/3）：44-51.
30	韩强，杜晓丽，崔申申，等. 颗粒态铁锰复合氧化物对磷的吸附特征及影响因素［J］. 化工进展，2017，36（6）：2311-2317.
	HAN Qiang， DU Xiaoli， CUI Shenshen，et al. Adsorptive characteristics and effect parameters of granular Fe-Mn binary oxide for phosphate［J］. Chemical Industry and Engineering Progress，2017，36（6）：2311-2317.
31	侯俊，尹雪雪，杨梓俊，等. 生物质吸附材料对水中磷酸盐的去除和回收研究进展［J］. 水资源保护，2023，39（5）：186-194.
	HOU Jun， YIN Xuexue， YANG Zijun，et al. Research progress of removal and recovery of phosphate by modified biomass adsorption materials［J］. Water Resources Protection，2023，39（5）：186-194.
32	LAI Li， XIE Qiang， CHI Lina，et al. Adsorption of phosphate from water by easily separable Fe₃O₄@SiO₂ core/shell magnetic nanoparticles functionalized with hydrous lanthanum oxide［J］. Journal of Colloid and Interface Science，2016，465：76-82.
33	FENG Zhuqing， YUAN Rongfang， WANG Fei，et al. Preparation of magnetic biochar and its application in catalytic degradation of organic pollutants：A review［J］. Science of the Total Environment，2021，765：142673.
34	YANG Xiaobing， ZENG Xiangchu， CHEN Hanchun，et al. Coupled homogeneous/heterogeneous Fenton-like system to enhance the synchronized decontamination of aqueous tetracycline and Salmonella typhi ［J］. Chemical Engineering Journal，2024，483：148697.
35	曾湘楚，张光华，张万斌，等. 希夫碱改性Fe₃O₄杂化材料的制备与表征［J］. 精细化工，2021，38（9）：1791-1797.
	ZENG Xiangchu， ZHANG Guanghua， ZHANG Wanbin，et al. Preparation and characterization of Schiff base modified Fe₃O₄ hybrid material［J］. Fine Chemicals，2021，38（9）：1791-1797.
36	蒲小平，段鹏昌，秦云，等. 氮掺杂介孔碳对含Pb（Ⅱ）隧洞施工废水的吸附性能［J］. 工业水处理，2024，44（1）：148-156.
	PU Xiaoping， DUAN Pengchang， QIN Yun，et al. Adsorption performance of Pb（Ⅱ） by nitrogen-doped mesoporous carbon in tunnel construction wastewater［J］. Industrial Water Treatment，2024，44（1）：148-156.
37	那立艳，张丽影，张凤杰，等. 固液界面吸附热力学参数的计算［J］. 材料导报，2020，34（22）：22030-22035.
	NA Liyan， ZHANG Liying， ZHANG Fengjie，et al. Calculation of adsorption thermodynamic parameters at solid-liquid interfaces［J］. Materials Reports，2020，34（22）：22030-22035.

[1]	李秀玲, 梁瀚予, 钟兰燕, 韦岩松. Ce-Zn复合吸附剂的制备及除磷性能研究[J]. 工业水处理, 2023, 43(5): 107-113.
[2]	吴礼贵,邹小明,杨方社,龚锦程,黄浩,曾庆华,张传庭. 锌对EBPR系统除磷性能的影响及其机制[J]. 工业水处理, 2020, 40(6): 22-26.
[3]	姜立萍, 朱银丽, 杨强兵, 牛常泰. 新型磁性纳米复合微凝胶吸附剂的制备及其应用[J]. 工业水处理, 2018, 38(10): 53-57.
[4]	姜立萍. 高分子纳米复合吸附剂在重金属废水处理中的应用[J]. 工业水处理, 2015, 35(12): 10-13,39.
[5]	刘荣香, 张焕祯, 刘峻平. 高岭土负载壳聚糖处理铬渣污染地下水[J]. 工业水处理, 2012, 32(5): 44-47.
[6]	黄瑾晖, 王继徽. 新型除磷剂──海泡石复合吸附剂的研制与应用[J]. 工业水处理, 1998, 18(2): 17-18,45.

选择文件类型/文献管理软件名称

选择包含的内容