nZVI/BC与(Cu-Pd)/BC协同提高硝酸盐的去除和氮气的选择性

doi:10.16085/j.issn.1000-6613.2021-0663

化工进展 ›› 2022, Vol. 41 ›› Issue (2): 981-989.DOI: 10.16085/j.issn.1000-6613.2021-0663

nZVI/BC与(Cu-Pd)/BC协同提高硝酸盐的去除和氮气的选择性

潘伟亮¹^,²(), 吴齐叶², 曹云鹏², 张先炳², 古励³(), 何强³

^1.重庆交通大学环境水利工程重庆市工程实验室，重庆 400074
^2.重庆交通大学河海学院, 重庆 400074
^3.重庆大学三峡库区生态环境教育部重点实验室, 重庆 400045

收稿日期:2021-03-31 修回日期:2021-05-06 出版日期:2022-02-05 发布日期:2022-02-23
通讯作者: 古励
作者简介:潘伟亮（1985—），男，博士，副教授，从事污水处理技术与产业化研究。E-mail：pan0316@126.com。
基金资助:
重庆市科技局社会民生基金(cstc2017shmsA20011);住房和城乡建设部科学技术计划(2016-K6-025);重庆交通大学研究生科研创新基金(YC2019003)

Improvement of nitrate removal and nitrogen selectivity by the synergy of nZVI/BC and (Cu-Pd)/BC

PAN Weiliang¹^,²(), WU Qiye², CAO Yunpeng², ZHANG Xianbing², GU Li³(), HE Qiang³

^1.Engineering Laboratory of Environmental Hydraulic Engineering of Chongqing Municipal, Chongqing Jiaotong University, Chongqing 400074, China
^2.School of River and Ocean Engineering, Chongqing Jiaotong University, Chongqing 400074, China
^3.Key laboratory of the Three Gorges Reservoir Region’s Eco-environments, Ministry of Education, Chongqing University, Chongqing 400045, China

Received:2021-03-31 Revised:2021-05-06 Online:2022-02-05 Published:2022-02-23
Contact: GU Li

摘要/Abstract

摘要：

为探明纳米零价铁（nZVI）/BC与(Cu-Pd)/BC联合作用对水中硝酸盐的去除机理，分别负载纳米金属于小麦秸秆生物炭上，制得nZVI/BC与(Cu-Pd)/BC两种复合材料，并通过SEM、TEM、EDS、XRD对材料进行表征分析，从nZVI/BC的SEM中可以看出，纳米零价铁较好地分散在生物炭（BC）上面；从(Cu-Pd)/BC的TEM图中看出，纳米铜钯均有效地负载于BC上且分布均匀。结果表明，nZVI/BC:(Cu-Pd)/BC体系中硝酸盐的去除率可达100%，氮气转化率达到42%。当pH为4.05时硝酸盐去除效果最佳；硝酸盐去除率随着初始浓度的升高而降低；溶解氧的存在会降低硝酸盐去除率；存在PO $4 3 -$ 对去除效率的影响最大，去除率降低至15.8%，而CO $3 2 -$ 和SO $4 2 -$ 的存在对去除氮的影响不大，去除率接近100%。动力学研究表明：在最佳条件下，nZVI/BC与(Cu-Pd)/BC联合作用对NO $3 -$ -N、NO $2 -$ -N的去除均符合准二级吸附动力学模型，反应过程以还原反应为主。

关键词: 硝酸盐, 氮气选择性, 纳米零价铁, 动力学, 生物炭

Abstract:

To investigate the mechanism of nitrate removal from water by the combined action of nano zero-valent iron (nZVI)/BC and (Cu-Pd)/BC, nZVI/BC and (Cu-Pd)/BC composites were produced by loading nano-metals on wheat straw biochar, and the materials were characterized by SEM, TEM, EDS, and XRD. The results showed that the nano-zero valent iron was well dispersed on the biochar (BC) and the nano-Cu-Pd was effectively loaded on the BC with uniform distribution. The nitrate removal rate of nZVI/BC: (Cu-Pd)/BC systems could reach 100% and the nitrogen conversion rate reached 42%. The best nitrate removal was achieved at pH 4.05; nitrate removal decreased with increasing initial concentration; the presence of dissolved oxygen reduced the nitrate removal; the presence of PO $4 3 -$ had the greatest effect on the removal efficiency and reduced the removal rate to 15.8%, while the presence of CO $3 2 -$ and SO $4 2 -$ had little effect on nitrogen removal and the removal rate was close to 100%. Kinetic studies showed that the removal of NO $3 -$ -N and NO $2 -$ -N by the combined action of nZVI/BC and (Cu-Pd)/BC under optimal conditions was in accordance with the quasi-secondary adsorption kinetic model, and the reaction process was dominated by the reduction reaction.

Key words: nitrate, nitrogen selectivity, nano-zero-valent iron, kinetics, biochar

中图分类号:

X524

潘伟亮, 吴齐叶, 曹云鹏, 张先炳, 古励, 何强. nZVI/BC与(Cu-Pd)/BC协同提高硝酸盐的去除和氮气的选择性[J]. 化工进展, 2022, 41(2): 981-989.

PAN Weiliang, WU Qiye, CAO Yunpeng, ZHANG Xianbing, GU Li, HE Qiang. Improvement of nitrate removal and nitrogen selectivity by the synergy of nZVI/BC and (Cu-Pd)/BC[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 981-989.

图/表 14

图1 nZVI和nZVI/BC的SEM谱图

图2 （Cu-Pd）/BC的TEM和EDS谱图

图3 不同材料反应前后的XRD谱图

a—BC；b—(Cu-Pd)/BC；c—nZVI；d—nZVI/BC； e—nZVI/BC:(Cu-Pd)/BC

图4 去除硝酸氮的准二级动力学曲线

表1 不同材料对硝酸氮的去除反应动力学参数

材料	准一级动力学		准二级动力学
材料	k₁/min^-1	R₁²	k₂/min^-1	R₂²
BC	0.00015	0.5908	0.66451	0.9026
nZVI	0.00329	0.9457	0.06513	0.9533
nZVI/BC	0.01610	0.9681	0.04022	0.8664
nZVI/BC：Cu-Pd	0.02190	0.8978	0.04358	0.9555
nZVI/BC：（Cu-Pd）/BC	0.01953	0.8931	0.04535	0.9628

图5 去除亚硝酸氮的准二级动力学曲线

表2 不同材料对亚硝酸氮的去除反应动力学参数

吸附材料	准一级动力学		准二级动力学
吸附材料	k₁/min^-1	R₂	k₂/min^-1	R₂
nZVI	0.00011	0.3711	0.06665	0.9999
nZVI/BC	0.00020	0.4269	0.03048	0.9996
nZVI/BC：Cu-Pd	0.00052	0.6170	0.01635	0.9989
nZVI/BC：（Cu-Pd）/BC	0.00101	0.8217	0.01189	0.9989

图6 不同材料对NO3--N、NO2--N的去除效率及氮气选择性

图7 不同比例铜钯生物炭对去除效率的影响及氮气选择性[nZVI/BC: (Cu-Pd)/BC（1∶1）为Cu∶Pd=1∶1[Cu、Pd分别占(Cu-Pd)/BC质量的5%、5%]；nZVI/BC: (Cu-Pd)/BC（1∶2）为Cu∶Pd=1∶2[Cu、Pd分别占(Cu-Pd)/BC质量的5%、10%]；nZVI/BC: (Cu-Pd)/BC（1∶3）为Cu∶Pd=1∶3[Cu、Pd分别占(Cu-Pd)/BC质量的5%、15%]；nZVI/BC: (Cu-Pd)/BC（1∶4）为Cu∶Pd=1∶4[Cu、Pd分别占(Cu-Pd)/BC质量的5%、20%]

图8 不同pH对NO3--N的去除率及氮气选择性的影响

图9 不同初始NO3--N浓度对水中硝酸盐去除的影响

图10 脱氧和未脱氧下硝酸盐的去除

图11 共存阴离子对NO3--N去除的影响

图12 硝酸盐还原反应机理

参考文献 25

1	ZHAI Y Z, ZHAO X B, TENG Y G, et al. Groundwater nitrate pollution and human health risk assessment by using HHRA model in an agricultural area, NE China[J]. Ecotoxicology and Environmental Safety, 2017, 137: 130-142.
2	王博, 叶春, 李法云, 等. 水生植物制生物炭对硝态氮的吸附规律研究[J]. 中国环境科学, 2017, 37(1): 116-122.
	WANG Bo, YE Chun, LI Fayun, et al. Studies on adsorption of nitrate from modified hydrophyte biochars[J]. China Environmental Science, 2017, 37(1): 116-122.
3	张雯, 尹琳, 周念清. 地下水氮污染原位修复缓释碳源材料的研发与物化-生境协同特性[J]. 环境科学, 2018, 39(9): 4150-4160.
	ZHANG Wen, YIN Lin, ZHOU Nianqing. Development and evaluation of a sustainable long-release carbon material applied for in situ remediation of groundwater nitrogen pollution[J]. Environmental Science, 2018, 39(9): 4150-4160.
4	LUBPHOO Y, CHYAN J M, GRISDANURAK N, et al. Nitrogen gas selectivity enhancement on nitrate denitrification using nanoscale zero-valent iron supported palladium/copper catalysts[J]. Journal of the Taiwan Institute of Chemical Engineers, 2015, 57: 143-153.
5	WANG S Q, CHEN S Y, WANG Y, et al. Integration of organohalide-respiring bacteria and nanoscale zero-valent iron (bio-nZVI-RD): a perfect marriage for the remediation of organohalide pollutants?[J]. Biotechnology Advances, 2016, 34(8): 1384-1395.
6	ARSHADI M, ABDOLMALEKI M K, MOUSAVINIA F, et al. Nano modification of NZVI with an aquatic plant Azolla filiculoides to remove Pb(Ⅱ) and Hg(Ⅱ) from water: aging time and mechanism study[J]. Journal of Colloid and Interface Science, 2017, 486: 296-308.
7	LI Y R, ZHAO H P, ZHU L Z. Remediation of soil contaminated with organic compounds by nanoscale zero-valent iron: a review[J]. Science of the Total Environment, 2021, 760: 143413.
8	STEFANIUK M, OLESZCZUK P, OK Y S. Review on nano zerovalent iron (nZVI): from synthesis to environmental applications[J]. Chemical Engineering Journal, 2016, 287: 618-632.
9	BOLADE O P, WILLIAMS A B, BENSON N U. Green synthesis of iron-based nanomaterials for environmental remediation: a review[J]. Environmental Nanotechnology, Monitoring & Management, 2020, 13: 100279.
10	WEI A L, MA J, CHEN J J, et al. Enhanced nitrate removal and high selectivity towards dinitrogen for groundwater remediation using biochar-supported nano zero-valent iron[J]. Chemical Engineering Journal, 2018, 353: 595-605.
11	SHI J L, LONG C, LI A M. Selective reduction of nitrate into nitrogen using Fe-Pd bimetallic nanoparticle supported on chelating resin at near-neutral pH[J]. Chemical Engineering Journal, 2016, 286: 408-415.
12	樊明德, 袁鹏, 何宏平, 等. 化学液相还原法制备零价铁纳米颗粒研究进展及展望[J]. 化工进展, 2012, 31(7): 1542-1548, 1580.
	FAN Mingde, YUAN Peng, HE Hongping, et al. Review and prospect of zerovalent iron nanoparticles synthesized by chemical solution reduction process[J]. Chemical Industry and Engineering Progress, 2012, 31(7): 1542-1548, 1580.
13	阚连宝, 刘泽. 纳米零价铁制备与应用的研究进展[J]. 环境科学与技术, 2019, 42(6): 215-223.
	KAN Lianbao, LIU Ze. Research progress in preparation and application of nano-zero-valent iron[J]. Environmental Science & Technology, 2019, 42(6): 215-223.
14	LI P J, LIN K R, FANG Z Q, et al. Enhanced nitrate removal by novel bimetallic Fe/Ni nanoparticles supported on biochar[J]. Journal of Cleaner Production, 2017, 151: 21-33.
15	赵云, 祝方, 任文涛. 绿色合成纳米零价铁镍去除地下水中硝酸盐的动力学研究[J]. 环境工程, 2018, 36(7): 71-76.
	ZHAO Yun, ZHU Fang, REN Wentao. Kinetics of nitrate removal in groundwater using green synthesized nanoscale zero valent iron-nickel[J]. Environmental Engineering, 2018, 36(7): 71-76.
16	郭兵毅, 刘桂梅, 曾玉彬, 等. 磁性石墨烯负载纳米铁铜去除硝态氮动力学研究[J]. 水处理技术, 2017, 43(7): 38-43.
	GUO Bingyi, LIU Guimei, ZENG Yubin, et al. Study on kinetics of nitrate nitrogen removing by magnetic graphene supported nano iron-copper[J]. Technology of Water Treatment, 2017, 43(7): 38-43.
17	马溶涵, 王英刚, 李小川, 等. 硅藻土负载纳米铁去除地下水硝酸盐氮污染[J]. 沈阳大学学报(自然科学版), 2019, 31(1): 22-27.
	MA Ronghan, WANG Yinggang, LI Xiaochuan, et al. Removal of nitrate and nitrogen pollution from groundwater by nano-iron supported on diatomite[J]. Journal of Shenyang University (Natural Science), 2019, 31(1): 22-27.
18	闫奇, 郑乾送, 周江敏, 等. 生物炭负载羧甲基纤维素钠稳定化纳米铁对水中六价铬的去除[J]. 环境工程学报, 2020, 14(3): 579-587.
	YAN Qi, ZHENG Qiansong, ZHOU Jiangmin, et al. Removal of hexavalent chromium from water by biochar supported with sodium carboxymethyl cellulose-stabilized nano-iron[J]. Chinese Journal of Environmental Engineering, 2020, 14(3): 579-587.
19	查晓松, 冯智梁, 金苏雯. 铁-铜双金属还原去除水中硝酸盐研究[J]. 水处理技术, 2020, 46(8): 44-48.
	ZHA Xiaosong, FENG Zhiliang, JIN Suwen. Removal of nitrate in water by reduction of iron-based bimetal[J]. Technology of Water Treatment, 2020, 46(8): 44-48.
20	张星星, 孟凡生, 王业耀, 等. 零价铁修复硝酸盐污染地下水的影响因素[J]. 环境工程, 2010, 28(S1): 70-73.
	ZHANG Xingxing, MENG Fansheng, WANG Yeyao, et al. Research on influencing factors of nitrate removal of groundwater by ZVI[J]. Environmental Engineering, 2010, 28(S1): 70-73.
21	KHALIL A M E, ELJAMAL O, JRIBI S, et al. Promoting nitrate reduction kinetics by nanoscale zero valent iron in water via copper salt addition[J]. Chemical Engineering Journal, 2016, 287: 367-380.
22	马锋锋, 赵保卫, 钟金魁, 等. 牛粪生物炭对磷的吸附特性及其影响因素研究[J]. 中国环境科学, 2015, 35(4): 1156-1163.
	MA Fengfeng, ZHAO Baowei, ZHONG Jinkui, et al. Characteristics phosphate adsorption onto biochars derived from dairy manure and its influencing factors[J]. China Environmental Science, 2015, 35(4): 1156-1163.
23	吴丽瑞, 陈进峰, 王海玲, 等. 秸秆基Li/Al层状双金属氢氧化物纳米复合吸附剂的制备及其除磷性能研究[J]. 环境污染与防治, 2019, 41(2): 155-159.
	WU Lirui, CHEN Jinfeng, WANG Hailing, et al. Development of Li/Al LDH-loaded nanocomposite for removal of phosphorus from water[J]. Environmental Pollution & Control, 2019, 41(2): 155-159.
24	GAO W L, GUAN N J, CHEN J X, et al. Titania supported Pd-Cu bimetallic catalyst for the reduction of nitrate in drinking water[J]. Applied Catalysis B: Environmental, 2003, 46(2): 341-351.
25	ARAMI M, LIMAEE N Y, MAHMOODI N M. Evaluation of the adsorption kinetics and equilibrium for the potential removal of acid dyes using a biosorbent[J]. Chemical Engineering Journal, 2008, 139(1): 2-10.

[1]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[2]	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.
[3]	汪鹏, 张洋, 范兵强, 何登波, 申长帅, 张贺东, 郑诗礼, 邹兴. 高碳铬铁盐酸浸出过程工艺及动力学[J]. 化工进展, 2023, 42(S1): 510-517.
[4]	刘阳, 王云刚, 修浩然, 邹立, 白彦渊. 基于动力学分析的核桃壳最佳炭化工艺[J]. 化工进展, 2023, 42(S1): 94-103.
[5]	黄益平, 李婷, 郑龙云, 戚傲, 陈政霖, 史天昊, 张新宇, 郭凯, 胡猛, 倪泽雨, 刘辉, 夏苗, 主凯, 刘春江. 三级环流反应器中气液流动与传质规律[J]. 化工进展, 2023, 42(S1): 175-188.
[6]	董佳宇, 王斯民. 超声强化对二甲苯结晶特性及调控机理实验[J]. 化工进展, 2023, 42(9): 4504-4513.
[7]	王浩然, 殷全玉, 方明, 侯建林, 李军, 何斌, 张明月. 近临界水处理废弃烟梗工艺优化[J]. 化工进展, 2023, 42(9): 5019-5027.
[8]	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.
[9]	李艳玲, 卓振, 池亮, 陈曦, 孙堂磊, 刘鹏, 雷廷宙. 氮掺杂生物炭的制备与应用研究进展[J]. 化工进展, 2023, 42(7): 3720-3735.
[10]	王俊杰, 潘艳秋, 牛亚宾, 俞路. 分子水平催化重整装置模型构建及应用[J]. 化工进展, 2023, 42(7): 3404-3412.
[11]	杨竞莹, 施万胜, 黄振兴, 谢利娟, 赵明星, 阮文权. 改性纳米零价铁材料制备的研究进展[J]. 化工进展, 2023, 42(6): 2975-2986.
[12]	赵毅, 杨臻, 张新为, 王刚, 杨旋. 不同裂缝损伤和愈合温度条件下沥青自愈合行为的分子模拟[J]. 化工进展, 2023, 42(6): 3147-3156.
[13]	曾天续, 张永显, 严渊, 刘宏, 马娇, 党鸿钟, 吴新波, 李维维, 陈永志. 羟胺对硝化菌活性及其动力学参数的影响[J]. 化工进展, 2023, 42(6): 3272-3280.
[14]	李瑞东, 黄辉, 同国虎, 王跃社. 原油精馏塔中铵盐吸湿特性及其腐蚀行为[J]. 化工进展, 2023, 42(6): 2809-2818.
[15]	张成松, 张静, 龚斌, 李明洋, 袁佳新, 李宏业. 自吸射流柔性搅拌桨振动特性[J]. 化工进展, 2023, 42(4): 1728-1738.

nZVI/BC与(Cu-Pd)/BC协同提高硝酸盐的去除和氮气的选择性

Improvement of nitrate removal and nitrogen selectivity by the synergy of nZVI/BC and (Cu-Pd)/BC

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 25

相关文章 15

编辑推荐

Metrics

本文评价