混合细菌浸出铁矿石中磷的研究
摘要
我国虽然铁矿资源丰富、储量大,但贫矿多、富矿少,绝大多数铁矿石都需要进行选矿处理以满足冶炼要求,尤其是我国储量丰富的高磷赤铁矿石资源尚未得到利用。研究铁矿石脱磷技术,对提高国内铁矿质量和促进我国钢铁工业的发展具有重要的现实意义。传统的物理分选法脱磷效果并不理想,化学方法由于成本高且对环境的高污染也使其应用受到限制,而微生物湿法冶金技术因其经济性及环保性而备受关注。嗜酸氧化亚铁硫杆菌(Acidithiobacillusferrooxidans,简称At.f菌)以及嗜酸氧化硫硫杆菌(Acidithiobacillus thiooxidans,简称At.t菌)能利用空气中的氧气来氧化还原态的铁或硫,从而获得能量并浸出矿石中的有用物质,因此已成为湿法冶金的主要浸矿细菌。由于各种浸矿菌在矿物浸出中所起的作用不同,且混合菌的使用又可起到优势互补的作用,因此利用混合菌的协同作用进行脱磷研究是可行的。
本文对At.t菌和At.f菌进行了初步的研究,然后利用两种细菌的混合协同作用进行浸矿,研究了不同浸矿工艺条件对浸矿效果的影响。通过摇瓶试验结果表明:单独的At.f菌和At.t菌都对赤铁矿有一定的脱磷作用,当它们按照体积比At.f菌:At.t菌为1:2混合浸矿时脱磷效果较单独菌种浸矿好,脱磷率可以达到84%;10%的细菌接种量对混合菌浸矿比较适宜,更高的接种量并不能增强除磷效果;矿浆初始pH值的大小对脱磷效果影响较大,在pH值为1.8～2.5条件下,细菌脱磷能力较强,当初始pH值＞4时,几乎没有脱磷效果;摇瓶试验中矿浆浓度对细菌的脱磷效果有着很大的影响,当矿浆浓度超过5%时,细菌生长明显受到抑制作用。
由于At.t菌与At.f菌对亚铁离子、元素硫的不同作用,为了优化混合菌的培养基组份,本文研究了在不同亚铁含量,单质S含量及添加黄铁矿条件下的混合菌的浸矿情况。试验结果表明:亚铁离子作为At.f菌的能源物质直接影响了浸矿效果,当培养基中亚铁含量为零时,细菌脱磷率仅为36%,随着亚铁离子的增多,脱磷率也随之增加;在不影响脱磷率的情况下,培养基中S的含量可以减少为原来的75%;黄铁矿也能作为混合菌的能源物质,对矿石脱磷有促进作用,当黄铁矿的配比占原矿质量的20%时,浸矿效果较好,但浸矿周期增加。
The iron ore resources are abundant in our country,but lean ore is much more than the rich,and most iron ore needs mineral dressing before smelting.The studies of removing phosphorus are vital for improving the quality of domestic iron ore and have great practical significance for promoting the development of Chinese iron and steel industry.Traditional physical methods are not effective,the costs of the chemical method is very high and makes it limited for it's high pollution to the environment,but microbial hydrometallurgical technology is received much concern because of it's economical efficiency and being environmentally friendly. Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans can make use of oxygen to oxidize reduced iron or sulfur to gain energy,and leach the available materials,and so they have become the main bacteria in the process of hydrometallurgy.As the result of the different effects of various bacteria,mixed microorganisms have complementary advantages,hence,it's feasible for mixed microorganisms to remove the phosphorus in iron ore.
In this paper,the preliminary physiology of At.t and At.f has been studied,and then these two kinds of bacteria were mixed to leach ore by synergistic action of them, and the effect of different processing conditions on the leaching has been studied.The shaking flask tests showed that At.f and At.t have a certain effect of dephosphorus on hematite when used separately.And when they are mixed in accordance with the volume ratio(At.f bacteria:At.t bacteria mixed 1:2),dephosphorization effect of leaching is better than single bacteria leaching,with a dephosphorization rate of up to 84%.The optimum bacterial inoculum is 10%,but higher inoculum does not enhance the dephosphorization.The initial slurry pH has greater impact on the dephosphorization.At pH 1.8～2.5,the ability of bacteria dephosphorization is stronger,but when the initial pH＞4,almost no dephosphorization can be seen. Shaking-flask tests showed that pulp concentration has a great impact on bacteria dephosphorization,and when the pulp concentration is more than 5%,it significantly inhibits the growth of bacteria.
As At.t and At.f play different roles on ferrous iron and elemental sulfur,in order to optimize the mixed bacteria culture medium components,the leaching of iron ore with mixed bacteria was studied at different levels of ferrous,elemental S and added pyrite content.The results show that ferrous ions as the energy of material has a direct impact on the leaching effects of At.f When the ferrous content of the medium is zero, the dephosphorization rate of At.f was only 36%.As the content of ferrous ions increases,dephosphorization rate also increases.Without affecting the dephosphorization rate,the content of the medium S can be reduced to 75%of the original.Pyrite can also be a mixed-strain energy of material.Dephosphorization of the ore can be promoted,when the ratio of pyrite ore quality accounted for 20%,the leaching effect is better,but the leaching cycle is increased.
本文对At.t菌和At.f菌进行了初步的研究,然后利用两种细菌的混合协同作用进行浸矿,研究了不同浸矿工艺条件对浸矿效果的影响。通过摇瓶试验结果表明:单独的At.f菌和At.t菌都对赤铁矿有一定的脱磷作用,当它们按照体积比At.f菌:At.t菌为1:2混合浸矿时脱磷效果较单独菌种浸矿好,脱磷率可以达到84%;10%的细菌接种量对混合菌浸矿比较适宜,更高的接种量并不能增强除磷效果;矿浆初始pH值的大小对脱磷效果影响较大,在pH值为1.8～2.5条件下,细菌脱磷能力较强,当初始pH值＞4时,几乎没有脱磷效果;摇瓶试验中矿浆浓度对细菌的脱磷效果有着很大的影响,当矿浆浓度超过5%时,细菌生长明显受到抑制作用。
由于At.t菌与At.f菌对亚铁离子、元素硫的不同作用,为了优化混合菌的培养基组份,本文研究了在不同亚铁含量,单质S含量及添加黄铁矿条件下的混合菌的浸矿情况。试验结果表明:亚铁离子作为At.f菌的能源物质直接影响了浸矿效果,当培养基中亚铁含量为零时,细菌脱磷率仅为36%,随着亚铁离子的增多,脱磷率也随之增加;在不影响脱磷率的情况下,培养基中S的含量可以减少为原来的75%;黄铁矿也能作为混合菌的能源物质,对矿石脱磷有促进作用,当黄铁矿的配比占原矿质量的20%时,浸矿效果较好,但浸矿周期增加。
The iron ore resources are abundant in our country,but lean ore is much more than the rich,and most iron ore needs mineral dressing before smelting.The studies of removing phosphorus are vital for improving the quality of domestic iron ore and have great practical significance for promoting the development of Chinese iron and steel industry.Traditional physical methods are not effective,the costs of the chemical method is very high and makes it limited for it's high pollution to the environment,but microbial hydrometallurgical technology is received much concern because of it's economical efficiency and being environmentally friendly. Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans can make use of oxygen to oxidize reduced iron or sulfur to gain energy,and leach the available materials,and so they have become the main bacteria in the process of hydrometallurgy.As the result of the different effects of various bacteria,mixed microorganisms have complementary advantages,hence,it's feasible for mixed microorganisms to remove the phosphorus in iron ore.
In this paper,the preliminary physiology of At.t and At.f has been studied,and then these two kinds of bacteria were mixed to leach ore by synergistic action of them, and the effect of different processing conditions on the leaching has been studied.The shaking flask tests showed that At.f and At.t have a certain effect of dephosphorus on hematite when used separately.And when they are mixed in accordance with the volume ratio(At.f bacteria:At.t bacteria mixed 1:2),dephosphorization effect of leaching is better than single bacteria leaching,with a dephosphorization rate of up to 84%.The optimum bacterial inoculum is 10%,but higher inoculum does not enhance the dephosphorization.The initial slurry pH has greater impact on the dephosphorization.At pH 1.8～2.5,the ability of bacteria dephosphorization is stronger,but when the initial pH＞4,almost no dephosphorization can be seen. Shaking-flask tests showed that pulp concentration has a great impact on bacteria dephosphorization,and when the pulp concentration is more than 5%,it significantly inhibits the growth of bacteria.
As At.t and At.f play different roles on ferrous iron and elemental sulfur,in order to optimize the mixed bacteria culture medium components,the leaching of iron ore with mixed bacteria was studied at different levels of ferrous,elemental S and added pyrite content.The results show that ferrous ions as the energy of material has a direct impact on the leaching effects of At.f When the ferrous content of the medium is zero, the dephosphorization rate of At.f was only 36%.As the content of ferrous ions increases,dephosphorization rate also increases.Without affecting the dephosphorization rate,the content of the medium S can be reduced to 75%of the original.Pyrite can also be a mixed-strain energy of material.Dephosphorization of the ore can be promoted,when the ratio of pyrite ore quality accounted for 20%,the leaching effect is better,but the leaching cycle is increased.
引文
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[6]Akeil A.Potential bioleaehing developments towards commercial reality:Turkish Metal mining's future.Minerals Engineering,2004.17(3):477-480
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[8]宋翔宇.微生物浸出工艺特点及其历史现状和前景[J].河南地质,1999.17:75-77
[9]杨显万,沈庆峰,郭玉霞.微生物湿法冶金[M].冶金工业出版社,2003.9:3-4
[10]邓立新.绿色冶金[J].化工教学,2002.(3):20
[11]裘荣庆.微生物冶金的研究和应用现状[J].微生物学通报,1995.2(3):180-183
[12]袁欣,袁楚雄,钟康年等.非金属矿物的微生物加工技术研究[J].中国非金属矿工业导刊,2000.3:12-14
[13]魏以和,王军,钟康年.矿物生物技术的微生物学基本方法[J].国外金属矿选矿,1996.(1):14-27
[14]林启美,王华,赵小蓉等.一些细菌和真菌的解磷能力及其机理初探[J].微生物学通报,2001.28(2):26-30
[15]Comustin et.al.,Bioteehnology and Bioengneering.1992,39:1121-1127
[16]李宏煦,刘晓荣.黄铁矿和镍黄铁矿混合细菌浸出过程的原电池效应[J].有色金属,2002.54(2):47-51
[17]胡凯光.细菌浸矿机理和影响因素[J].中国矿业,2004,13(4):73-77
[18]李宏煦,王淀佐.生物冶金中的微生物及其作用[J].有色冶金,2003.55(2):58-63
[19]罗立群,张泾生.我国炼铁原料市场的分析研究[J].武汉理工大学学报,2005.27(9):67-69
[20]袁致涛,高太印,万忠,等.我国难选铁矿石资源利用的现状及发展方向[J].金属矿山,2007.(1):1-6
[21]罗立群,高志,孙洁.难选铁矿石微生物脱磷技术.金属矿山[J].2008.58-61
[22]余远兵.磷泥同收转炉蒸磷工艺.适用技术市场[J]1992.(3):10-11
[23]汤树森.高效溶磷黑曲霉株的筛选及溶磷机理与条件的研究[J].微生物通报,1983.63(4):671-678
[24]Delvasto P,V alverde A,Ballester A,et al.Diversity and activity of phosphate bioleaching bacteria from a highphosphorus iron ore[J].Hydrometallurgy,2008.92(3/4):124-129
[25]J.W.C.Wong,Xiang,L.,Gu,X.Y.,Zhou,L.X.,.Bioleaching of heavy metals from anaerobically digested sewage sludge using FeS2 as an energy source.Chemosphere,2004.55(1):101-107
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