CN100398677C - Method of bacterial eliminating sulfur in high sulfur bauxite - Google Patents

Method of bacterial eliminating sulfur in high sulfur bauxite Download PDF

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CN100398677C
CN100398677C CNB2006101408668A CN200610140866A CN100398677C CN 100398677 C CN100398677 C CN 100398677C CN B2006101408668 A CNB2006101408668 A CN B2006101408668A CN 200610140866 A CN200610140866 A CN 200610140866A CN 100398677 C CN100398677 C CN 100398677C
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sulfur
type bauxite
ore
sulfur type
bauxite
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CN1924042A (en
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李花霞
周吉奎
李军亮
曹慧君
王淑华
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Aluminum Corp of China Ltd
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Abstract

The invention discloses a desulfurizing method in the high-sulfur alumina ore through alumina bacteria, which comprises the following steps: adopting Acidithiobacillus ferrooxidans to immerse high-sulfur alumina ore; breaking alumina ore; grinding; adopting water culture medium to immerse ore with density at 5-30%; setting the immersing temperature at 25-35 deg.c and rotary speed of shaker at 150-250r/min; making the bulk density of vaccination quantity of enriched bacterial liquid at 5%-10%; leaching for 10-20d; extracting leached ore; washing; desulfurizing.

Description

The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite
Technical field
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite.The method that relates to the desulfurization of a kind of bauxite bacterial leaching.
Background technology
The main sulfide mineral that high-sulfur type bauxite contains has pyrite (FeS 2) and isomer white pyrite and melnikovite and gypsum CaSO4 one class vitriol.In the higher bauxite of corpus luteum mineral content, pyrite is in the reaction of 180 ℃ of beginnings and alkaline solution, and aggravates with the raising of temperature and alkali concn, and particularly melnikovite is easier is decomposed by alkaline solution for white pyrite.Its reaction mechanism is: the sulfide of iron at first resolves into sodium disulfide, and sodium disulfide is unstable in sodium aluminate solution under the high temperature, decomposes again to generate sodium sulphite and Sulfothiorine, finally is oxidized to sodium sulfate and enters into solution.Because sulphur can be oxidized to vitriol gradually and accumulate on stream in alumina producing, bring many difficulties and harm for alumina producing and operation, therefore also untapped utilization.
Sulphur content in the Bayer process production requirement ore is lower than 0.7%, even low more good more.Effectively get rid of the sulphur impurity in the high-sulfur type bauxite, seem very necessary opening up new alumina producing resource.
Microorganism can be by number of ways to the mineral effect, and the valuable element in the mineral is converted into ion in the solution.The research object of biological metallurgy mainly is to utilize iron, sulfur-oxidizing bacteria to carry out the almost leachings of used sulphide ores such as copper, uranium, gold, nickel at present.Reported that the microorganism microorganism that can be used for soaking the ore deposit has kind more than 20, mainly contains thiobacillus ferrooxidant (Thiobacillusferrooxidans (T.f)), thiobacillus thiooxidans (Thiobacillus thiooxidans (T.t)), iron protoxide hook end spirillum (Leptospirillum ferrooxidans (L.f).Be mainly used in the biological metallurgy deposit impregnating technology of metals such as coal desulfurization, flue gas desulfurization (FGD), process gas desulfurization and copper, gold, nickel, cobalt at present, obtain unusual effect, but do not appearing in the newspapers as yet aspect the high-sulfur type alumyte desulfuration, bacterium is leached can remove most sulfur impurity in the high-sulfur type bauxite.Efficient utilization to high-sulfur type bauxite has very significant meaning.
Summary of the invention
The objective of the invention is in the above-mentioned prior art, sulfur impurity in the high-sulfur type bauxite that exists is at the aluminum oxide technical barrier, provide a kind of can effective elimination high-sulfur type bauxite in sulfur impurity, realize utilizing the method for sulfur impurity in the bacterial eliminating high-sulfur type bauxite of high-sulfur type bauxite into alumina purpose.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite is characterized in that be adopting iron protoxide thiobacillus ferrooxidans Acidithiobacillus ferrooxidans that the screening domestication obtains that high-sulfur type bauxite is soaked the ore deposit desulfurization.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite of the present invention, it is characterized in that screening the iron protoxide thiobacillus ferrooxidans Acidithiobacillus ferrooxidans that domestication obtains screens from the pit water of high sulphur formed coal ore deposit, in the common micro-organisms center preservation of China Committee for Culture Collection of Microorganisms of specified depositary institution of Patent Office of the People's Republic of China, preserving number is: CGMCC NO.1832, this bacterium has the ability that leaches the sulfur impurity in the high-sulfur type bauxite under acidic conditions.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite of the present invention is characterized in that its process that high-sulfur type bauxite is soaked the ore deposit desulfurization is after bauxite is carried out fragmentation, ore grinding, adopts the bacteria culture medium of water preparation to soak the ore deposit; The ore pulp weight concentration of soaking the ore deposit is 5%-30%, and soaking the ore deposit temperature is 25 ℃-35 ℃, shaking speed 150-250r/min, and the volumetric concentration 5%-10% of inoculum size enrichment bacterium liquid extraction time 10-20 days, soaks behind the ore deposit through suction filtration, washing desulphurization.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite of the present invention is characterized in that the 9K substratum of the bacteria culture medium of water preparation for improvement, and its substratum adds (NH 4) 2SO 43g, K 2HPO 40.5g, Ca (NO 3) 20.01g, MgSO 4.7H 2O 0.5g, KCl 0.1g adds H 2O 1000mL, pH is with 1: 1H 2SO 4Be adjusted to 1.5~2.0, filtration sterilization.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite of the present invention, what it is characterized in that inoculating is the enrichment bacterium liquid of logarithmic phase growth.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite of the present invention is characterized in that iron protoxide thiobacillus ferrooxidans's form and culture condition are:
1) this bacterium is a class chemoautotrophic bacteria, aerobicly has a liking for acid, Gram-negative, and wide is 0.3~0.5 μ m, and length is 1.0~2.0 μ m, and the proper growth temperature is 25~35 ℃, and pH value scope is 1.5~3.0.
2) this bacterium grows liquid nutrient medium in the 9K substratum of improvement: (NH 4) 2SO 43g, K 2HPO 40.5g, Ca (NO 3) 20.01g, MgSO 4.7H 2O 0.5g, KCl 0.1g, FeSO 4.7H 2O 22.5g adds H 2O 1000mL, pH is with 1: 1H 2SO 4Be adjusted to 1.5~2.0, filtration sterilization.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite of the present invention is characterized in that this bacterial strain is to tame greater than 3.8% high-sulfur type bauxite with the sulfur-bearing weight percent.
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite of the present invention is characterized in that bacterium is to increase to gradually under 10% the condition from 1% in bauxite ore pulp weight percent concentration to be tamed.
Method of the present invention, at the bauxite that contains pyrite and other sulfide, have iron protoxide ion with from the pit water of high sulphur formed coal ore deposit, being separated to, the iron protoxide thiobacillus ferrooxidans of elementary sulfur and sulfide ability, with the 9K substratum that does not contain ferrous ion is medium, tames cultivation with sulphur content greater than 3.8% high-sulfur type bauxite, and the domestication process increases the pulp density (1% of bauxite gradually, 2%, 5%, 10%), obtains efficient thiobacillus ore leaching strain.By domesticated strain being inoculated fresh 9K -Judge the adaptive faculty of bacterial strain in the substratum, adapt to the bacterial strain renewed vaccination to detect its leaching ability.
This hybrid bacterial strain soaks ore deposit research to high-sulfur type bauxite, and high-sulfur type bauxite is through fragmentation, and sample ore granularity-0.35mm accounts for 75% or more and just can soak the ore deposit after the fine grinding, and ore leachate is the 9K substratum that does not add ferrous ion that water is prepared, and need not to sterilize pH1.5-2.0.Get the domestication nutrient solution and be inoculated in the 9K substratum, microbial culture is used for the ore leachate inoculation during to exponential phase of growth.Controlled temperature 25-30 ℃, rotating speed 150-250r/min, pulp density 5%-30%, inoculum size 5%-10% leached 10-20 days, and sulphur content is 0.2%-0.6%, and desulfurization degree reaches more than 80%, and the X-diffracting spectrum is analyzed high-sulfur type bauxite bacterium and is leached back FeS 2Charateristic avsorption band disappear Al 2O 3The rate of recovery reaches more than 97%.
Method of the present invention is used the method that bacterium is leached, and leaches the sulfur impurity in the high-sulfur type bauxite, and the bauxite physico-chemical property does not have influence after the desulfurization, can be directly used in alumina producing Bayer process.
Description of drawings
Fig. 1 is the SEM form of the thiobacillus ferrooxidant of employing of the present invention;
Fig. 2 is the X-diffracting spectrum of the raw ore among the embodiment 1;
Fig. 3 is that ore leaches X-diffracting spectrum after 20 days among the embodiment 1 under aseptic condition;
Fig. 4 is the X-diffracting spectrum that bacterium is leached the back ore among the embodiment 1.
Embodiment
The method of sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite adopts iron protoxide thiobacillus ferrooxidans Acidithiobacillus ferrooxidans that the screening domestication obtains that high-sulfur type bauxite is soaked the ore deposit desulfurization.Its process that high-sulfur type bauxite is soaked the ore deposit desulfurization is after bauxite is carried out fragmentation, ore grinding, adopt the water preparation bacteria culture medium soak the ore deposit; The ore pulp weight concentration of soaking the ore deposit is 5%-30%, and soaking the ore deposit temperature is 25 ℃-35 ℃, shaking speed 150-250r/min, and the volumetric concentration 5%-10% of inoculum size enrichment bacterium liquid extraction time 10-20 days, soaks behind the ore deposit through suction filtration, washing desulphurization.
Embodiment 1
From the pit water of high-sulfur colliery, be separated to have iron protoxide ion, the thiobacillus ferrooxidant enrichment bacterial strain of elementary sulfur and sulfide ability, not contain the 9K substratum (M9K of ferrous ion -) be medium, be that 3.83% high-sulfur type bauxite is tamed cultivation with sulphur content, the domestication process increases the pulp density (1%, 2%, 5%, 10%) of bauxite gradually, obtains efficient thiobacillus hybrid bacterial strain, and the SEM figure of bacterium sees Fig. 1.
The thiobacillus ferrooxidant enrichment bacterial strain that screening domestication obtains soaks the ore deposit to high-sulfur type bauxite, and high-sulfur type bauxite is through fragmentation, sample ore granularity after the fine grinding<40 orders, and ore leachate is the 9K substratum that does not add ferrous ion with the tap water preparation, need not sterilization.Get the domestication nutrient solution and be inoculated in the 9K substratum, microbial culture is used to soak the inoculation of ore deposit test during to exponential phase of growth.Leaching system pH 2.0, shaking speed 200r/min leaches mineral sulphur content 3.83%, soaks 30 ℃ of ore deposit temperature, and inoculum size 5% leached 10 days, soaks the ore deposit desulfurization and see Table 1 under different pulp densities.
The different pulp densities of table 1 soak the ore deposit sweetening effectiveness
Embodiment 2
Other condition is with example 1.Leaching system pH 2.0, shaking speed 250r/min leaches mineral sulphur content 3.83%, soaks 25 ℃ of ore deposit temperature, inoculum size 10%, pulp density 10% leaches that the mineral sulphur content is 0.55% after 20 days, desulfurization degree 86.96%, Al 2O 3The rate of recovery 97.21%.
Embodiment 3
Other condition is with example 1.Leaching system pH 1.5, shaking speed 150r/min leaches mineral sulphur content 3.83%, soaks 30 ℃ of ore deposit temperature, and inoculum size 10% leaches that the mineral sulphur content is 0.81% after 15 days, desulfurization degree 80.97%, Al 2O 3The rate of recovery 92.49%.
Embodiment 4
Other condition is with example 1.Leaching system pH 2.0, shaking speed 200r/min leaches mineral sulphur content 0.68%, soaks 30 ℃ of ore deposit temperature, inoculum size 5%, pulp density 10% leaches that the mineral sulphur content is 0.20% after 20 days, desulfurization degree 71.62%, Al 2O 3The rate of recovery 97.49%.
Embodiment 5
Other condition is with example 1.Leaching system pH 2.0, shaking speed 200r/min leaches mineral sulphur content 0.68%, soaks 30 ℃ of ore deposit temperature, inoculum size 5%, pulp density 10% leaches that the mineral sulphur content is 0.24% after 15 days, desulfurization degree 66.72%, Al 2O 3The rate of recovery 95.30%.
Embodiment 6
Other condition is with example 1.Leaching system pH 2.0, shaking speed 200r/min leaches mineral sulphur content 0.68%, soaks 30 ℃ of ore deposit temperature, inoculum size 10%, pulp density 10% leaches that the mineral sulphur content is 0.26% after 10 days, desulfurization degree 62.99%, Al 2O 3The rate of recovery 97.90%.
Embodiment 7
Other condition is with example 1.Leaching system pH 2.0, shaking speed 200r/min leaches mineral sulphur content 0.68%, soaks 30 ℃ of ore deposit temperature, inoculum size 5%, pulp density 5% leaches that the mineral sulphur content is 0.19% after 15 days, desulfurization degree 74.29%, Al 2O 3The rate of recovery 92.63%.

Claims (8)

1. the method for sulfur impurity in the bacterial eliminating high-sulfur type bauxite is characterized in that being adopting iron protoxide thiobacillus ferrooxidans Acidithiobacillus ferrooxidans that the screening domestication obtains that high-sulfur type bauxite is soaked the ore deposit desulfurization.
2. the method for sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite according to claim 1, it is characterized in that screening the iron protoxide thiobacillus ferrooxidans Acidi thiobacillus ferrooxidans that domestication obtains screens from the pit water of high-sulfur colliery, in the common micro-organisms center preservation of China Committee for Culture Collection of Microorganisms of specified depositary institution of Patent Office of the People's Republic of China, preserving number is: CGMCC NO.1832, this bacterium has the ability that leaches the sulfur impurity in the high-sulfur type bauxite under acidic conditions.
3. the method for sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite according to claim 1, it is characterized in that its process that high-sulfur type bauxite is soaked the ore deposit desulfurization is after bauxite is carried out fragmentation, ore grinding, adopt the bacteria culture medium of water preparation to soak the ore deposit; The ore pulp weight concentration of soaking the ore deposit is 5%-30%, and soaking the ore deposit temperature is 25 ℃-35 ℃, shaking speed 150-250r/min, and the volumetric concentration 5%-10% of inoculum size enrichment bacterium liquid extraction time 10-20 days, soaks behind the ore deposit through suction filtration, washing desulphurization.
4. the method for sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite according to claim 1 is characterized in that the 9K substratum of the bacteria culture medium of water preparation for improvement, and its substratum adds (NH 4) 2SO 43g, K 2HPO 40.5g, Ca (NO 3) 20.01g, MgSO 4.7H 2O 0.5g, KCl 0.1g adds H 2O 1000mL, pH is with 1: 1H 2SO 4Be adjusted to 1.5~2.0, filtration sterilization.
5. the method for sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite according to claim 1, what it is characterized in that inoculating is the enrichment bacterium liquid of logarithmic phase growth.
6. the method for sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite according to claim 1 is characterized in that iron protoxide thiobacillus ferrooxidans's form and culture condition are:
1) this bacterium is a class chemoautotrophic bacteria, aerobicly has a liking for acid, Gram-negative, and wide is 0.3~0.5 μ m, and length is 1.0~2.0 μ m, and the proper growth temperature is 25~35 ℃, and pH value scope is 1.5~3.0;
2) this bacterium grows liquid nutrient medium in the 9K substratum of improvement: (NH 4) 2SO 43g, K 2HPO 40.5g, Ca (NO 3) 20.01g, MgSO 4.7H 2O 0.5g, KCl 0.1g, FeSO 4.7H 2O 22.5g adds H 2O 1000mL, pH is with 1: 1H 2SO 4Be adjusted to 1.5~2.0, filtration sterilization.
7. the method for sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite according to claim 1 is characterized in that this bacterial strain is to tame greater than 3.8% high-sulfur type bauxite with the sulfur-bearing weight percent.
8. the method for sulfur impurity in a kind of bacterial eliminating high-sulfur type bauxite according to claim 1 is characterized in that bacterium is to increase to gradually under 10% the condition from 1% in bauxite ore pulp weight percent concentration to be tamed.
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CN102363890A (en) * 2011-10-26 2012-02-29 广州有色金属研究院 Method for recovering metal copper in waste circuit board

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CN101130807A (en) * 2007-08-03 2008-02-27 中国铝业股份有限公司 Method for screening bauxite desulfurizing bacteria by using acidic pit water in high-sulfur ore zone
CN102218437B (en) * 2011-05-05 2013-02-06 广州有色金属研究院 Recovery method for waste circuit board
CN107841741B (en) * 2017-10-13 2018-11-27 乾乐欣展新材料技术(上海)有限公司 A kind of aluminum substrate surface biological processing oxidation technology
CN107987914A (en) * 2017-11-14 2018-05-04 神华集团有限责任公司 The sulfur method of coal
CN109604309A (en) * 2018-12-12 2019-04-12 上海第二工业大学 A kind of microbial process of selectively removing waste print circuit board surface component

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