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黄钾铁矾类矿物作为一种典型次生矿物,在微生物湿法冶金、湿法炼锌及酸性矿山废水(Acid mine drainage, AMD)等环境广泛存在[1-3]。例如,在微生物湿法冶金领域,黄钾铁矾类矿物的生成不仅会消耗大量的三价铁浸出剂,导致生产成本增加;还会形成覆盖层,影响浸出矿物的后续再利用,导致大量浸出物废弃堆置[4-5]。而在湿法炼锌领域,黄钾铁矾类矿物为除铁的主要生成物,一方面生成量巨大,需要占用大量的土地进行堆置;另一方面,由于黄钾铁矾类矿物生成过程的共沉淀、吸附效应,会导致部分锌、铟等金属转移到黄钾铁矾类矿物废渣中,难以回收,造成资源浪费[6-8]。因此,探究绿色、经济可行的黄钾铁矾类矿物处理方式对实现黄钾铁矾类矿物减量化、资源化等有重要意义。
黄钾铁矾类矿物主要处理方法包括固定法、火法与湿法[9]。其中,固定法是将黄钾铁矾类矿物作为建筑级配材料,在与水泥、石膏等混合后固化实现减量化,但此法消纳量少,不能回收黄钾铁矾类矿物中的有价金属,因此运用不多[10]。火法是将黄钾铁矾类矿物进行单一或多元煅烧,能够回收黄钾铁矾类矿物中的有价金属,但是能耗高、渣量减量化效果不明显。湿法是采用强酸或微生物厌氧还原的方式将黄钾铁矾类矿物溶解,进行工艺组合能回收黄钾铁矾类矿物中的有价金属、硫酸盐、铁盐等,当进一步采用微生物厌氧还原处置时,其环境友好、能耗低,近年来受到广泛关注[7, 11]。在黄钾铁矾类矿物晶格中,含有Fe3+与SO42-。因此,通过还原其中的Fe3+(铁还原途径)与SO42-(硫酸盐还原途径),均能实现黄钾铁矾类矿物的溶解[12]。例如,采用硫酸盐还原细菌(Desulfovibrio vulgaris)将黄钾铁矾类矿物中的SO42-还原为S2-,能够实现黄钾铁矾类矿物的溶解(如式(1)所示)[13]。同样,采用希瓦氏菌(Shewanella putrefaciens)将黄钾铁矾类矿物中的Fe3+还原为Fe2+,亦能实现黄钾铁矾类矿物的溶解(如式(2)所示)[14]。从式(1)与式(2)可知,采用硫酸盐还原途径,每还原1 mol的黄钾铁矾类矿物,将消耗16 mol的电子;而还原同样的黄钾铁矾类矿物,采用铁还原途径,将仅需要3 mol电子,显然更具优势。
对微生物湿法冶金而言,好氧浸出多采样自养微生物如氧化亚铁硫杆菌、氧化硫硫杆菌等,导致有机底物存在往往会抑制自养微生物好氧浸出活性,因而,探究自养、铁还原微生物对黄钾铁矾类矿物处置有重要意义[15-16]。有研究发现,氧化亚铁硫杆菌在厌氧环境下,能够利用H2作为电子供体,将黄钾铁矾类矿物还原溶解,实现了通过单一菌株、控制“厌氧-好氧”环境变化,完成微生物湿法冶金中铁离子的循环利用[17-19]。由于H2在液相中溶解度较低,且H2易燃特性限制通过高压顶空方式供应氢气,因此,如何安全可靠地提高厌氧环境中氧化亚铁硫杆菌的H2可及性,是该工艺方法需要解决的关键问题。鉴于此,拟以2种典型中空纤维膜(无泡出气与微气泡出气)搭建中空纤维膜反应器(Hollow fiber membrane reactor, HfMR),探讨在强酸性环境下(pH在2左右)运用中空纤维膜向液相供应H2,并分析不同气体传质方式下氧化亚铁硫杆菌厌氧还原溶解黄钾铁矾类矿物特性,以为促进氧化亚铁硫杆菌厌氧还原溶解技术发展提供参考。
中空纤维膜传质H2对氧化亚铁硫杆菌还原溶解黄钾铁矾类矿物的影响
Effect of H2 mass transfer by hollow fiber membrane on anaerobic bio-dissolution of jarosites using Acidithiobacillus ferrooxidans
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摘要: 为强化氧化亚铁硫杆菌厌氧还原溶解黄钾铁矾类矿物过程中的H2传质,以2种典型中空纤维膜(无泡出气与微气泡出气)搭建中空纤维膜反应器,研究中空纤维膜传质H2对氧化亚铁硫杆菌厌氧还原溶解黄钾铁矾类矿物的影响。结果表明,采用无泡出气中空纤维膜,黄钾铁矾类矿物最大还原溶解速率为5.82 mmol·(L·d)−1,16 d后黄钾铁矾类矿物还原溶解量达到86.6%;而采用微气泡中空纤维膜,黄钾铁矾类矿物最大还原溶解速率为3.18 mmol·(L·d)−1,16 d后黄钾铁矾类矿物还原溶解量仅达到53.9%。进一步地,无泡出气中空纤维膜相比微气泡出气中空纤维膜,在显著降低H2消耗的同时,能够让氧化亚铁硫杆菌更易获取H2,进而分泌更多胞外有机物,提高浸出效率。本研究结果可为无泡出气中空纤维膜在氧化亚铁硫杆菌还原溶解黄钾铁矾类矿物的应用提供参考。Abstract: To improve the H2 mass transfer during the jarosites anaerobic reduction dissolution process by Acidithiobacillus ferrooxidans, two typical hollow fiber membranes, including bubble free type and microbubble type as research objects, and the characteristics of anaerobic reduction dissolution of jarosites by Acidithiobacillus ferrooxidans in the hollow fiber membrane reactor were studied. The results showed that the maximum reduction dissolution rate of jarosites was 5.82 mmol·(L·d)−1 using the bubble free type of hollow fiber membrane, and the anaerobic reduction dissolution amount of jarosites reached 86.6% after 16 days. However, the maximum reduction dissolution rate of jarosites was 3.18 mmol·(L·d)−1 when using the microbubble type of hollow fiber membrane, and the anaerobic reduction dissolution amount of jarosites only reached 53.9%. Furthermore, compared with the microbubble type of hollow fiber membrane, the H2 consumption of reduction bio-dissolution process was reduced when using the bubble free type of hollow fiber membrane, and made it easier for Acidithiobacillus ferrooxidans to get H2 and secreted more extracellular organic matter. The results of this study can provide a reference for the application of bubble free type of hollow fiber membrane in the reduction and dissolution of jarosites by Acidithiobacillus ferrooxidans.
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表 1 微量元素厌氧培养基组成
Table 1. Component content of anaerobic medium
mg·L−1 成分 质量浓度 (NH4)2SO4 132 K2HPO4 41 CuSO4·5H2O 2 CoCl2·6H2O 0.5 MgSO4·7H2O 490 CaCl2·2H2O 9 MnSO4·H2O 1 Na2SeO4·10H2O 1 KCl 52 ZnSO4·7H2O 1 NaMoO4·5H2O 0.5 NiCl2·6H2O 1 -
[1] HAN H, SUN W, HU Y, et al. Anglesite and silver recovery from jarosite residues through roasting and sulfidization-flotation in zinc hydrometallurgy[J]. Journal of Hazardous Materials, 2014, 278: 49-54. doi: 10.1016/j.jhazmat.2014.05.091 [2] DAS G, ACHARYA S, ANAND S, et al. Jarosites: a review[J]. Mineral Processing and Extractive Metullargy Review, 1996, 16(3): 185-210. doi: 10.1080/08827509708914135 [3] 周佳兴, 董燕, 刘奋武, 等. NaBH4对施氏矿物-黄铁矾生物化学合成的影响及矿物在催化降解甲基橙中的应用[J]. 环境工程学报, 2021, 15(4): 1242-1251. doi: 10.12030/j.cjee.202010103 [4] KAKSONEN A, MORRIS C, REA S, et al. Biohydrometallurgical iron oxidation and precipitation: Part II — Jarosite precipitate characterisation and acid recovery by conversion to hematite[J]. Hydrometallurgy, 2014, 147-148: 264-272. doi: 10.1016/j.hydromet.2014.04.015 [5] 辛靖靖, 刘金艳, 伍赠玲, 等. 黄铜矿生物浸出过程中的钝化作用研究进展[J]. 金属矿山, 2018(9): 15-21. doi: 10.19614/j.cnki.jsks.201809003 [6] MARTINEZ M, SOLAN A, HIDALGO A, et al. Characterization and mobilization of toxic metals from electrolytic zinc waste[J]. Chemosphere, 2019, 233: 414-421. [7] 刘鹏飞, 张亦飞, 游韶玮, 等. 热酸浸出回收黄钾铁矾渣中有价元素[J]. 过程工程学报, 2016, 16(4): 584-589. doi: 10.12034/j.issn.1009-606X.216125 [8] 薛佩毅, 巨少华, 张亦飞, 等. 焙烧-浸出黄钾铁矾渣中多种有价金属[J]. 过程工程学报, 2011, 11(1): 56-60. [9] ASOKAN P, SAXENA M, ASOLEKAR S. Hazardous jarosite use in developing non-hazardous product for engineering application[J]. Journal of Hazardous Materials, 2006, 137(3): 1589-1599. [10] 魏甲明, 杨斌 李若贵. 西北铅锌厂152 m2流态化焙烧炉与改良黄钾铁矾法炼锌项目的创新[J]. 中国有色冶金, 2018, 47(2): 11-13. doi: 10.3969/j.issn.1672-6103.2018.02.003 [11] OUYANG B, LU X, LIU H, et al. Reduction of jarosite by Shewanella oneidensis MR-1 and secondary mineralization[J]. Geochimica et Cosmochimica Acta, 2014, 124: 54-71. doi: 10.1016/j.gca.2013.09.020 [12] 王文静, 高坤, 叶翰, 等. 希瓦氏菌还原作用下黄钾铁矾的相转变特征及其负载铬的迁移转化规律[J]. 环境科学学报, 2021, 41(4): 1323-1332. [13] ZHOU C, ZHOU Y, RITTMANN B. Reductive precipitation of sulfate and soluble Fe(III) by Desulfovibrio vulgaris: Electron donor regulates intracellular electron flow and nano-FeS crystallization[J]. Water Research, 2017, 119: 91-101. doi: 10.1016/j.watres.2017.04.044 [14] CASTRO L, BLAZQUEZ M L, GONZALEZ F, et al. Anaerobic bioleaching of jarosites by Shewanella putrefaciens, influence of chelators and biofilm formation[J]. Hydrometallurgy, 2017, 168: 56-63. doi: 10.1016/j.hydromet.2016.08.002 [15] 赵尚明, 何环, 于忠琦, 等. 嗜酸氧化亚铁硫杆菌脱煤矸石中硫影响因素的筛选及条件优化[J]. 环境工程学报, 2015, 9(9): 4585-4590. doi: 10.12030/j.cjee.20150979 [16] 王莉莉, 孙秀云, 李桥, 等. 废弃印刷线路板中铜的两步浸出工艺优化[J]. 环境工程学报, 2018, 12(1): 250-258. doi: 10.12030/j.cjee.201705115 [17] YANG Y, CHEN S, YANG D, et al. Anaerobic reductive bio-dissolution of jarosites by Acidithiobacillus ferrooxidans using hydrogen as electron donor[J]. Science of The Total Environment, 2019, 686: 869-877. doi: 10.1016/j.scitotenv.2019.06.071 [18] YANG Y, CHEN S, WANG B, et al. Effect of ferric ions on the anaerobic bio-dissolution of jarosites by Acidithiobacillus ferrooxidans[J]. Science of The Total Environment, 2020, 710: 136334. doi: 10.1016/j.scitotenv.2019.136334 [19] 杨远坤, 谌书, 陈梦君, 等. 氧化亚铁硫杆菌浸提废旧线路板铜的浸出率与时间的关系[J]. 环境工程学报, 2013, 7(6): 2322-2326. [20] YANG Y, CHEN S, LI S, et al. Bioleaching waste printed circuit boards by Acidithiobacillus ferrooxidans and its kinetics aspect[J]. Journal of Biotechnology, 2014, 173: 24-30. doi: 10.1016/j.jbiotec.2014.01.008 [21] ZHU N, XIANG Y, ZHANG T, et al. Bioleaching of metal concentrates of waste printed circuit boards by mixed culture of acidophilic bacteria[J]. Journal of Hazardous Materials, 2011, 192(2): 614-619. doi: 10.1016/j.jhazmat.2011.05.062 [22] WANG H, DAI K, WANG Y, et al. Mixed culture fermentation of synthesis gas in the microfiltration and ultrafiltration hollow-fiber membrane biofilm reactors[J]. Bioresource Technology, 2018, 267: 650-656. doi: 10.1016/j.biortech.2018.07.098 [23] TANG Y, ZHOU C, Van GINKEL S, et al. Hydrogen permeability of the hollow fibers used in H-2-based membrane biofilm reactors[J]. Journal of Membrane Science, 2012, 407: 176-183. [24] PRONK J T, de BRUYN J C, BOS P, et al. Anaerobic Growth of Thiobacillus ferrooxidans[J]. Applied and Environmental Microbiology, 1992, 58(7): 2227-2230. doi: 10.1128/aem.58.7.2227-2230.1992 [25] STOOKEY L L. Ferrozine--a new spectrophotometric reagent for iron[J]. Analytical Chemistry, 2002, 42(7): 779-781. [26] YU R, ZHONG D, MIAO L, et al. Relationship and effect of redox potential, jarosites and extracellular polymeric substances in bioleaching chalcopyrite by Acidithiobacillus ferrooxidans[J]. Transactions of Nonferrous Metals Society Of China, 2011, 21(7): 1634-1640. doi: 10.1016/S1003-6326(11)60907-2 [27] AMEND J, SHOCK E. Energetics of overall metabolic reactions of thermophilic and hyperthermophilic Archaea and bacteria[J]. FEMS Microbiology Reviews, 2001, 25(2): 175-243. doi: 10.1111/j.1574-6976.2001.tb00576.x [28] ZWIETERING M, JONGENBURGER I, ROMBOUTS F, et al. Modeling of the bacterial growth curve[J]. Applied and Environmental Microbiology, 1990, 56(6): 1875-1881. doi: 10.1128/aem.56.6.1875-1881.1990 [29] PHUKOETPHIM N, SALAKKAM A, LAOPAIBOON P, et al. Kinetic models for batch ethanol production from sweet sorghum juice under normal and high gravity fermentations: Logistic and modified Gompertz models[J]. Journal of Biotechnology, 2017, 243: 69-75. doi: 10.1016/j.jbiotec.2016.12.012