Using iron promoted manganese oxide ore for simultaneous flue gas desulfurization and Mn leaching: a process study

doi:10.16085/j.issn.1000-6613.2020-1067

Abstract

Abstract:

In order to remove SO₂ from manganese slag calcination process, and combine with the production features of electrolytic manganese production enterprises, the manganese oxide ore was used as the raw material, and the wastewater anode solution of electrolytic manganese was used to prepare the ore pulp (desulfurizer). The influences of processing parameters and FeSO₄ added on desulfurization and manganese leaching were studied. The results indicated that the introduction of FeSO₄ promoted the Mn leaching via the redox reaction between MnO₂ and FeSO₄, and then, the product (Fe³⁺) and the Mn²⁺ in solution could act as the catalyst to catalyze the desulfurization reaction. The desulfurization activity and the Mn leaching rate increased with the decrease of the ore particle size. With the increase of reaction temperature, the desulfurization activity decreased, and the Mn leaching rate increased at first and then decreased which reached the maximum value at 60℃. When the liquid-solid ratio and the inlet flow rate increases, the desulfurization efficiency decreased, but the Mn leaching rate was enhanced. The 5-stage manganese oxide slurry desulfurization of the 7% flue gas with FeSO₄ added showed that the outlet SO₂ was 293μL/L, and the Mn²⁺ concentration of lixivium was 44.72g/L, which met the requirements of electrolytic manganese. The present flue gas desulfurization system could recycle the wastewater anode solution of electrolytic manganese, and provide a new technology for sulfur dioxide removal from flue gas and Mn extraction form manganese oxide ore simultaneously. The present study provides theoretical basis and technical reference for clean production and comprehensive utilization of resources in electrolytic manganese industry.

Key words: flue gas, leaching, environment, desulfurization, manganese oxide ore, iron

摘要：

结合电解锰生产工艺，以氧化锰矿为原料，以电解锰生产过程产生的电解阳极液废水配置烟气脱硫浆液，在其中添加FeSO₄强化电解锰阳极液体系下氧化锰矿烟气脱硫及浸锰能力，探讨铁强化氧化锰矿烟气脱硫和浸锰的工艺条件对烟气SO₂脱除和锰浸出的影响机制。研究发现FeSO₄的加入，通过FeSO₄与MnO₂之间的氧化还原反应以及产物三价铁离子和二价锰离子的协同催化作用，可同时提高锰矿烟气脱硫效率和锰的浸出率。锰矿粒径越小，脱硫及浸锰效率越高。温度升高，氧化锰矿浆液烟气脱硫率逐渐下降，浸锰率则先升高后下降，并在60℃时达到最大。浆液液固比和烟气流量的增大均会导致烟气脱硫率的下降，但会提高氧化锰矿浸锰率。进口SO₂浓度过高会导致脱硫率下降，但更有利于浸锰。采用5级逆流吸收对7%的烟气进行铁离子强化氧化锰浆脱硫，得到最终SO₂出口浓度293μL/L，溶液Mn²⁺浓度为44.72g/L，满足电解要求。铁强化电解锰阳极液体系有效回收利用了电解锰生产废水，不仅集脱硫浸锰工艺为一体，且可实现脱硫和浸锰效率的同时提升，为电解锰行业的清洁生产和资源综合利用提供理论依据和技术参考。

关键词: 烟道气, 浸取, 环境, 脱硫, 氧化锰矿, 铁

CLC Number:

X701.3

YAO Lu, XIN Guangzhi, YANG Lin, PU Pengyan, JIANG Xia, JIANG Wenju. Using iron promoted manganese oxide ore for simultaneous flue gas desulfurization and Mn leaching: a process study[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2859-2866.

姚露, 辛广智, 杨林, 蒲鹏燕, 江霞, 蒋文举. 铁强化电解锰阳极液体系中氧化锰矿烟气脱硫和锰浸出工艺[J]. 化工进展, 2021, 40(5): 2859-2866.

Figures/Tables 10

References 24

2	DU B, ZHOU C, DAN Z, et al. Preparation and characteristics of steam-autoclaved bricks produced from electrolytic manganese solid waste[J]. Construction and Building Materials, 2014, 50: 291-299.
3	DONG S, LIN Y, NING L, et al. Sulfur resource recovery based on electrolytic manganese residue calcination and manganese oxide ore desulfurization for the clean production of electrolytic manganese[J]. Chinese Journal of Chemical Engineering, 2020, 28: 864-870.
4	ZHAO J D, SU S J, AI N S, et al. Modelling flue gas desulfurization using pyrolusite pulp in a jet bubbling reactor[J]. Materials Science Forum, 2009, 610/611/612/613: 85-96.
5	SUN D, XIN G, YAO L, et al. Manganese leaching in high concentration flue gas desulfurization process with semi-oxidized manganese ore[J]. Chinese Journal of Chemical Engineering, 2020, 28(2): 571-578.
6	ULRICH R K, ROCHELLE G T, PRADA R E. Enhanced oxygen absorption into bisulphite solutions containing transition metal ion catalysts[J]. Chemical Engineering Science, 1986, 41(8): 2183-2191.
7	YAO L, YANG L, JIANG W, et al. Removal of SO₂ from flue gas on a copper-modified activated coke prepared by a novel one-step carbonization activation blending method[J]. Industrial & Engineering Chemistry Research, 2019, 58(34): 15693-15700.
8	GUO J X, FAN L, PENG J F, et al. Desulfurization activity of metal oxides blended into walnut shell based activated carbons[J]. Journal of Chemical Technology & Biotechnology, 2014, 89(10): 1565-1575.
9	刘洁岭, 汤争光, 陈杰, 等. 新型生物质活性炭烟气脱硫研究[J]. 环境科学, 2013, 34(4): 1623-1627.
	LIU Jieling, TANG Zhengguang, CHEN Jie, et al. Flue gas desulferization by a novel biomass activated carbon[J] .Environmental Science, 2013, 34(4): 1623-1627.
10	赵珂, 宁平, 李凯, 等. Mn/Cu-BTC催化剂同时脱硫脱硝实验研究[J].化工进展, 2020, 39(5): 1784-1791.
	ZHAO Ke, NING Ping, LI Kai, et al. Experimental study on simultaneous removal of SO₂ and NO by Mn/Cu-BTC catalyst[J]. Chemical Industry and Engineering Progress,2020, 39(5): 1784-1791.
11	李万全, 张永奎, 巫延斌, 等. 微生物代谢与Fe³⁺催化氧化脱除烟气中SO₂的研究[J]. 环境污染与防治, 2006, 28(9): 690-692.
	LI Wanquan, ZHANG Yongkui, WU Yanbin, et al. Bio-enhanced catalytic oxidation process for removing sulfur dioxide from flue gas[J]. Environmental Pollution & Control, 2006, 28(9): 690-692.
12	DAS S C, SAHOO P K, RAO P K. Extraction of manganese from low-grade manganese ores by FeSO₄ leaching[J]. Hydrometallurgy, 1982, 8(1): 35-47.
1	WANG J, PENG B, CHAI L Y, et al. Preparation of electrolytic manganese residue-ground granulated blastfurnace slag cement[J]. Powder Technology, 2013, 241: 12-18.
13	TEKIN T, BAYRAMOĜLU M. Kinetics of the reduction of MnO₂ with Fe²⁺ ions in acidic solutions[J]. Hydrometallurgy, 1993, 32(1): 9-20.
14	ZAKERI A, SHAHRIARI S, BAFGHI M S. Dissolution kinetics of manganese dioxide ore in sulfuric acid in the presence of ferrous ion[J]. Iranian Journal of Materials Science & Engineering, 2007, 4(3/4): 22-27.
15	姚露, 杨林, 邹敏杰, 等. 氧化锰矿浆脱除电解锰渣煅烧烟气二氧化硫工艺研究[J]. 工程科学与技术, 2020, 52(5):250-256.
	YAO Lu, YANG Lin, ZOU Minjie, et al. Study on Flue gas desulfurization with oxide manganese slurry for electrolytic manganese calcining[J]. Advanced Engineering Sciences, 2020, 52(5):250-256.
16	NAIK P K, SUKLA L B, DAS S C. Aqueous SO₂ leaching studies on Nishikhal manganese ore through factorial experiment[J]. Hydrometallurgy, 2000, 54(2/3): 217-228.
17	MILLER J D, WAN R Y. Reaction kinetics for the leaching of MnO₂ by sulfur dioxide[J]. Hydrometallurgy, 1983, 10(2): 219-242.
18	朱晓帆, 蒋文举, 苏仕军, 等. 软锰矿浆烟气脱硫反应机理研究[J]. 环境污染治理技术与设备, 2002(3): 44-46.
	ZHU X F, JIANG W J, SU S J, et al. The study of reaction mechanism of desulfurization in flue gas with pyrolusite pulp[J]. Technigues Equipment for Enviropollcont, 2002(3): 44-46.
19	黄妍, 王治军, 童志权. 软锰矿浆脱除烟气中SO₂的研究[J]. 环境工程, 1998, 16(4): 43-46.
	HUANG Yan, WANG Zhijun, TONG Zhiquan. Research on removing SO₂ from fume gas by pyrolusite sludge[J]. Environmental Engineering， 1998, 16(4): 43-46.
20	PASIUK-BRONIKOWSKA W, BRONIKOWSKI T. The rate equation for SO₂ autoxidation in aqueous MnSO₄ solutions containing H₂SO₄[J]. Chemical Engineering Science, 1981, 36(1): 215-219.
21	SUN W Y, DING S L, ZENG S S, et al. Simultaneous absorption of NO_x and SO₂ from flue gas with pyrolusite slurry combined with gas-phase oxidation of NO using ozone[J]. Journal of Hazardous Materials, 2011, 192(1): 124-130.
22	В.М.КАКАБАДЗЕ, 杨正莘. 锰泥和锰矿的二氧化硫炼制法[J]. 化学世界, 1955, 10(2): 23-29.
	В.М.Какабадзе, YANG Zhengxin. Sulfur dioxide refining of manganese mud and manganese ore[J]. Chemical World, 1955, 10(2): 23-29.
23	WALANDA D K, LAWRANCE G A, DONNE S W. Kinetics of Mn₂O₃ digestion in H₂SO₄ solutions[J]. Journal of Solid State Chemistry, 2009, 182(6): 1336-1342.
24	吴复忠, 蔡九菊, 张琦, 等. 软锰矿、菱锰矿吸收烧结烟气中的SO₂制取硫酸锰[J]. 钢铁, 2007, 42(4): 78-82.
	WU Fuzhong, CAI Jiuju, ZHANG Qi, et al. Study on production of manganese sulfate by absorption of SO₂ from sintering fume with pyrolusite and mild manganese[J]. Iron & Steel, 2007, 42(4): 78-82.

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