Study on deep denitrification of autotrophic denitrification with sulfur-iron base substrate

doi:10.19965/j.cnki.iwt.2021-1116

Abstract

Abstract:

The nitrogen removal performance of sulfur autotrophic denitrification， iron autotrophic denitrification and sulfur-iron synergistic denitrification systems were investigated by static batch experiments. The experimental results showed that pH decreased from 8.46 to 5.46 during sulfur autotrophic denitrification， and NO₂ ^--N accumulated up to 7.14 mg/L in the early stage of the reaction. TN and NO₃ ^--N showed a decreasing trend with denitrification. The TN removal rate was up to 100% after 5 days of reaction. The addition of zero-valent iron powder can effectively play a role in buffering pH. In the sulfur-iron synergistic denitrification system， pH of the system could be maintained between 6.54 and 7.12 when the sulfur iron volume ratio was 2∶1 and 1∶1. The best denitrification effect was achieved when the sulfur iron volume ratio was 2∶1， and the TN removal rate could reach 98.5% and NO₃ ^--N removal rate could reach 100% after 72 hours of reaction. In the process of iron autotrophic denitrification， the pH showed a trend of slow increase and then gradual stabilization， from 8.46 to 10.02. Compared with the sulfur autotrophic denitrification system and the sulfur-iron synergistic denitrification system， the iron autotrophic denitrification system had the worst denitrification performance， and the removal rates of TN and NO₃ ^--N were 40.52% and 48.96%， respectively， after 9 days of reaction. NH₄ ⁺-N was accumulated in the reaction system. The sulfur autotrophic denitrification was dominant in the sulfur-iron synergistic denitrification system， and the proportions of NO₃ ^--N removal by sulfur autotrophic denitrification were 96%， 95%， and 88% when the sulfur iron volume ratios were 1∶1， 2∶1， and 1∶2， respectively.

Key words: sulfur autotrophic denitrification, iron autotrophic denitrification, synergism, denitrification

摘要：

通过静态批次实验，探讨了硫自养反硝化、铁自养反硝化和硫铁协同脱氮系统的脱氮性能。实验结果表明，单质硫自养反硝化过程中pH由8.46降至5.46，反应前期NO₂ ^--N发生积累，最高达7.14 mg/L。TN和NO₃ ^--N随反硝化的进行呈不断降低趋势。反应5 d时TN去除率可达100%。零价铁粉的加入可以有效起到缓冲pH的作用。在硫铁协同脱氮系统中，硫铁体积比为2∶1、1∶1时，反应体系的pH可维持在6.54~7.12之间。硫铁体积比为2∶1时脱氮效果最佳，反应72 h时TN去除率可达98.5%，NO₃ ^--N去除率可达100%。在铁自养反硝化过程中，pH呈缓慢升高后逐渐稳定的趋势，由8.46增至10.02。与硫自养反硝化系统和硫铁协同脱氮系统相比，铁自养反硝化系统的脱氮性能最差，反应9 d时TN和NO₃ ^--N的去除率分别为40.52%、48.96%，且在该体系中NH₄ ⁺-N有所积累。硫铁协同脱氮系统中以硫自养反硝化为主，当硫铁体积比分别为1∶1、2∶1、1∶2时，硫自养反硝化对NO₃ ^--N去除量所占比例分别为96%、95%、88%。

关键词: 硫自养反硝化, 铁自养反硝化, 协同, 脱氮

CLC Number:

X703

Yanfang LIU, Xiaoshuai LIU, Sijie YIN, Wei GAO, Miaoyu ZHANG, Jianwei LÜ, Zaixing LI. Study on deep denitrification of autotrophic denitrification with sulfur-iron base substrate[J]. Industrial Water Treatment, 2022, 42(8): 136-141.

刘艳芳, 刘晓帅, 尹思婕, 高玮, 张妙雨, 吕建伟, 李再兴. 以硫-铁为基质的自养反硝化深度脱氮性能研究[J]. 工业水处理, 2022, 42(8): 136-141.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-1116

https://www.iwt.cn/EN/Y2022/V42/I8/136

Figures/Tables 8

Table 1 The ratio of sulfur to iron in different experimental groups

项目	S-Fe系统
硫磺粉/mL	15	20	10
零价铁粉/mL	15	10	20
硫铁体积比	1∶1	2∶1	1∶2

Fig. 1 Change curve of various parameters with time under SAD system

Fig. 2 Change curve of various parameters with time under the IAD system

Fig. 3 Change curve of various nitrogen content with time in S-Fe system

Fig. 4 Change curve of pH with time in S-Fe system

Fig. 5 Change curve of SO₄ ^2- mass concentration with time in S-Fe system

Fig. 6 Change curves of Fe²⁺ and TFe mass concentrations with time in S-Fe system

Table 2 Proportion of NO₃ ^--N removal of iron and sulfur in S-Fe system

硫铁比	1∶1		2∶1		1∶2
硫铁比	铁粉	硫磺	铁粉	硫磺	铁粉	硫磺
NO₃ ^--N去除量占比/%	4	96	5	95	12	88

References 21

1	李文超，石寒松，王琦，等. 硫自养反硝化技术在污废水处理中应用研究进展［J］. 水处理技术， 2017， 43（8）： 1-6.
	LI Wenchao， SHI Hansong， WANG Qi， et al. Application progress of sulfur-autotrophic denitrification technology in wastewater treatment［J］. Technology of Water Treatment， 2017， 43（8）： 1-6.
2	邓旭亮，王爱杰，荣丽丽，等. 硫自养反硝化技术研究现状与发展趋势［J］. 工业水处理， 2008， 28（3）： 13-16. doi:10.11894/1005-829x.2008.28(3).13
	DENG Xuliang， WANG Aijie， RONG Lili， et al. Present state of the sulfur-autotrophic denitrification technique and its developing trend［J］. Industrial Water Treatment， 2008， 28（3）： 13-16. doi:10.11894/1005-829x.2008.28(3).13
3	LIU L H， KOENIG A. Use of limestone for pH control in autotrophic denitrification： Batch experiments［J］. Process Biochemistry， 2002， 37（8）： 885-893. doi:10.1016/s0032-9592(01)00302-8
4	XU Yaxian， CHEN Nan， FENG Chuanping， et al. Sulfur-based autotrophic denitrification with eggshell for nitrate-contaminated synthetic groundwater treatment［J］. Environmental Technology， 2016， 37（24）： 3094-3103. doi:10.1080/09593330.2016.1176077
5	赵爽，汪晓军，杨永愿. 化学法处理低浓度硝酸盐氮废水的试验研究［J］. 工业水处理， 2018， 38（1）： 79-82. doi:10.11894/1005-829x.2018.38(1).079
	ZHAO Shuang， WANG Xiaojun， YANG Yongyuan. Experimental research on the chemical treatment of wastewater containing low content of nitrate nitrogen by zero-valent iron and sodium hypochlorite［J］. Industrial Water Treatment， 2018， 38（1）： 79-82. doi:10.11894/1005-829x.2018.38(1).079
6	DENG Shihai， LI Desheng， YANG Xue， et al. Novel characteristics on micro-electrolysis mediated Fe（0）-oxidizing autotrophic denitrification with aeration： Efficiency， iron-compounds transformation， N₂O and NO₂ ^- accumulation， and microbial characteristics［J］. Chemical Engineering Journal， 2020， 387： 123409. doi:10.1016/j.cej.2019.123409
7	范潇梦，关小红，马军. 零价铁还原水中硝酸盐的机理及影响因素［J］. 中国给水排水， 2008， 24（14）： 5-9. doi:10.3321/j.issn:1000-4602.2008.14.002
	FAN Xiaomeng， GUAN Xiaohong， MA Jun. Mechanisms and affecting factors of nitrate reduction by zero-valent iron［J］. China Water & Wastewater， 2008， 24（14）： 5-9. doi:10.3321/j.issn:1000-4602.2008.14.002
8	ZHANG Meng， ZHANGZHU Gucheng， WEN Shuxian， et al. Chemolithotrophic denitrification by nitrate-dependent anaerobic iron oxidizing （NAIO） process： Insights into the evaluation of seeding sludge［J］. Chemical Engineering Journal， 2018， 345： 345-352. doi:10.1016/j.cej.2018.03.156
9	张文静，黄勇，毕贞，等. ANAMMOX菌铁自养反硝化工艺的稳定性［J］. 环境科学， 2019， 40（7）： 3201-3207.
	ZHANG Wenjing， HUANG Yong， BI Zhen， et al. Stability of ZVI-dependent autotrophic denitrification by ANAMMOX bacteria［J］. Environmental Science， 2019， 40（7）： 3201-3207.
10	BELLER H R. Anaerobic， nitrate-dependent oxidation of U（Ⅳ） oxide minerals by the chemolithoautotrophic bacterium Thiobacillus denitrificans［J］. Applied and Environmental Microbiology， 2005， 71（4）： 2170-2174. doi:10.1128/aem.71.4.2170-2174.2005
11	XU Xiaochen， ZHANG Rao， JIANG Hongbin， et al. Sulphur-based autotrophic denitrification of wastewater obtained following graphite production： Long-term performance， microbial communities involved， and functional gene analysis［J］. Bioresource Technology， 2020， 306： 123117. doi:10.1016/j.biortech.2020.123117
12	李璟. 生物沸石反应器去除水中硝酸盐的研究［D］. 北京：北京化工大学， 2008.
	LI Jing. Research on the removal of nitrate in water by biological zeolite reactor［D］. Beijing： Beijing University of Chemical Technology， 2008.
13	牛建敏，李睿华. 理化因素对脱氮硫杆菌自养反硝化的影响［J］. 中国环境科学， 2010， 30（1）： 76-81.
	NIU Jianmin， LI Ruihua. Effects of the physicochemical factors on autotrophic denitrification by thiobacillus denitrificans［J］. China Environmental Science， 2010， 30（1）： 76-81.
14	张晨晓，郭延凯，杜海峰，等. 硫自养反硝化反应器脱氮特性研究［J］. 河北科技大学学报， 2016， 37（1）： 96-101. doi:10.7535/hbkd.2016yx01016
	ZHANG Chenxiao， GUO Yankai， DU Haifeng， et al. Denitrification characteristics of a sulfur autotrophic denitrification reactor［J］. Journal of Hebei University of Science and Technology， 2016， 37（1）： 96-101. doi:10.7535/hbkd.2016yx01016
15	张宁博，李祥，黄勇. pH值对零价铁自养反硝化过程的影响［J］. 环境科学， 2017， 38（12）： 5208-5214.
	ZHANG Ningbo， LI Xiang， HUANG Yong. Effect of pH value on autotrophic denitrification process of zero valent iron substrate［J］. Environmental Science， 2017， 38（12）： 5208-5214.
16	刘凡. 硫铁矿自养反硝化性能及条件优化研究［D］. 北京：中国地质大学（北京）， 2018.
	LIU Fan. Study on performance and optimizing conditions for pyrite-based autotrophic denitrification［D］. Beijing： China University of Geosciences， 2018.
17	燕倩. Fe⁰/Fe²⁺自养反硝化脱氮效果及氮的归趋研究［D］. 西安：陕西科技大学， 2020. doi:10.1016/j.biortech.2020.123926
	YAN Qian. Study on denitrification removal efficiency and nitrogen fate of Fe⁰/Fe²⁺ autotrophic denitrification［D］. Xi’an： Shaanxi University of Science & Technology， 2020. doi:10.1016/j.biortech.2020.123926
18	BAALSRUD K， BAALSRUD K S. Studies on thiobacillus denitrificans［J］. Archiv Fur Mikrobiologie， 1954， 20（1）： 34-62. doi:10.1007/bf00412265
19	ZHANG Lili， SONG Yunda， ZUO Yu， et al. Integrated sulfur- and iron-based autotrophic denitrification process and microbial profiling in an anoxic fluidized-bed membrane bioreactor［J］. Chemosphere， 2019， 221： 375-382. doi:10.1016/j.chemosphere.2018.12.168
20	杨燕，朱静平. 添加零价铁的反硝化系统中发生的主要反应［J］. 工业水处理， 2021， 41（3）： 77-82.
	YANG Yan， ZHU Jingping. Main reactions in denitrification system with zero valent iron addition［J］. Industrial Water Treatment， 2021， 41（3）： 77-82.
21	李莹莹. 硫自养反硝化生物滤池脱氮效能与微生物群落特征研究［D］. 北京：北京林业大学， 2020. doi:10.1016/j.biortech.2019.122682
	LI Yingying. Research on denitrification efficiency and microbial community characteristics of sulfur autotrophic denitrification biofilter［D］. Beijing： Beijing Forestry University， 2020. doi:10.1016/j.biortech.2019.122682

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