Biological stirring cobalt-dipping technique for concentrate containing cobalt and sulfur
Technical Field The invention relates to a use of medium thermophillus Acidophilic leaching concentrate containing cobalt and sulfur agitation leaching cobalt in the new process, high-efficiency recovery of valuable in sulphide ore cobalt metal, raises the synthetic mine utilization level, which belongs to the field of microbial metallurgy technology. Background Art Cobalt is a strategic metal, it has a high melting point, good wear resistance, high strength, magnetic and the like, the kind of high-temperature alloy, magnetic material, an important material for anti-corrosive alloy. Widely used in aviation, space, electrical, mechanical and manufacturing, chemical, industrial ceramics or the like. China is a country of cobalt lack of resources, the exploitation of the reserves of the significance is only 3.9 million tons, also only reserves basis of 5.98 million tons. The cobalt raw material and waste material from the inlet of the total production of the cobalt accounts for about 65%. My cobalt deposits more lean, the high-grade ore are few , and the lack of separate cobalt deposits, most symbiodinium or associated, from the nickel ore smelting system import or cobalt residue of extracting cobalt in the cobalt raw materials, such as the recovery of cobalt Jinchuan Company. However, there is also a part of the concentrate containing cobalt and sulfur cobalt-grade low, origin in remote, industrial basis is not developed areas, the traditional Sulfogen ore roasting acid-leaching raises the cobalt process, sulfuric acid without use, it is very difficult to realize commercial application. For example, cobalt ore qinghai [...] is a proven belongs to the large copper deposits containing cobalt, the plateau region is in a remote, wherein the beneficial associated element cobalt sulphide ore of the coexistence of the pyrites and the like. Wherein the copper sulfide ore flotation process of recovery, containing cobalt copper flotation tailings 0.02%-0.1%, the flotation obtain cobalt-containing 0.1%-1% of sulfur concentrate, the concentrate if the traditional Sulfogen ore roasting acid-leaching raises the cobalt process, the problem can not be solved use of sulfuric acid, will be non-viable, at present there is no good use of. Therefore, in order to efficiently utilize the resources of the cobalt with sulfur in the concentrate ore, it is necessary to provide a new process for recovering sulfur concentrate cobalt, further improving the comprehensive utilization of mineral resources of the mine level. Content of the invention The aim of this invention is to provide a cobalt-containing sulfur concentrate from biological stirring cobalt extraction in the new process, the new process flow is short, bicycle, the operation is simple, low energy consumption, do not need the high-temperature smelting, without discharge of polluting dust and sulfur dioxide gas, can realize fast leaching and efficient cobalt recovery. In order to achieve the above-mentioned purpose, this invention adopts the following technical proposal: this kind of cobalt-containing sulfur concentrate biological stirring cobalt-dipping the new process comprises the following steps: (1), cobalt-containing sulfur concentrate for re-grinding; (2), the (1) after fine grinding-heated concentrate powder washing removal of the concentrated processing; (3), the (2) in the slurry after the concentration treatment of sulphuric acid to adjust pH value, improving temperature, inoculating bacteria and adding the growth of bacteria after leaching system is pumped into the biological stirring, bacterial oxidation leach; (4), is continuously circulated leachate, when the leaching fluid cobalt concentration after separation can be achieved, through the calcium carbonate containing cobalt lixivium pre-iron, sodium sulfide or sodium hydrosulfide or hydrogen sulfide obtained after sinks the cobalt cobalt sulfide product. The new process the medium thermophillus Acidophilic leaching Retech-MTC-1 named Sulfobacillus thermosulfidooxidans, are registered and preserved in China typical culture collection center (Wuhan University campus), preserving registration number CCTCC No: M206029. 28 March 2006 date. The culture preservation admissibility of the application for the original number of the notice "200610078976.6 the name [...] for" medium thermophiles and low-grade native copper sulfide ore chemical and biological joint heap leaching process " in the application file. Leaching biological stirring the slurry concentration is 15%-35%, of the slurry in the leaching process pH value is 1.2-1.8, the leaching temperature control in 40-55 the between [...] , leaching process needs to be charged in the reaction tank rich in O2 air and carbon dioxide. The cobalt-containing sulfur concentrate can be a cobalt-containing pyrite concentrate; The biological stirring the solid-liquid separation to leaching pulp, the separating medium can be returned to pool. Lean solution to leach the leachate in the pool in the circulating process, according to the required pH value, iron ion concentration of iron-sedimentation of calcium carbonate. Bacterial growth temperature is 40-50 the [...]. In the course of leaching in order to maintain high activity of the bacteria, the need to maintain the temperature in the system the 40-55 [...] , pH value 1.2-1.8 and certain Fe concentration (1-15g/L). The electric potential of the present invention is to measure mv (SCE) of the oxidation-reduction potential of the reaction solution to a reference mode, that is, the measured potential of the relative to the saturated calomel electrode is the measurement value. Description of drawings Figure 1 is the process flow diagram of the invention Figure 2 is flow chart of the embodiment of the invention For comprehensive utilization of sulfur containing cobalt of the cobalt in the concentrate ore, the invention adopts the following design scheme (see fig. 1): Figure 1 in, the fine ore concentrate containing cobalt and sulfur 1 processing, so that the mineral concentrates the requirements of the follow-up treatment process; After the fine grinding by the thickener concentrate containing cobalt and sulfur machine concentration 2, overflow after concentrating enter the sewage treatment system, the underflow enter the mixing 3 process. Thickening machine by the high-concentration slurry by adding a dilute sulfuric acid solution to pH value preconditioning, preconditioning the pH value in a range of 1.6-1.8 between, the slurry concentration after regulating 20%-40%. Preconditioning of the pulp after adding 10%-30% (v/v) bacterium solution of high concentration, a high concentration of bacteria solution for densitiy 107-109/ml; in addition, the need to add nitrogen source for the growth of bacteria (for example, ammonium sulphate 1-3g/L) and phosphorus source (for example, potassium dihydrogen phosphate 0.1-0.5 g/l). After mixing inoculation of feeding the pulp density is 15%-35% (w/w). After mixing the cobalt-containing sulfur concentrate leaching system biological stirring 4, bacterial oxidation of cobalt-dipping treatment. Leaching in the process of controlling the pH of the leaching tank 1.2-1.8 between, pulp potential control in 450mv -600mv (SCE), the pulp temperature through the cooling or heating the 40-50 the [...][...] , the dissolved oxygen concentration in the pulp > 4 mg/L, the carbon dioxide is dissolved amount holding > 15 mg/L. Furthermore, also need for regular monitoring of bacterial concentration in the pulp, by adjusting the pH value, temperature or air flow concentration of bacteria > 106/ml. Bacterial oxidation that the pulp after leaching cobalt is concentrated 5 after the underflow of the filter 7 process, the solid-liquid separation, the filter residue into the tail mine; all the filtrate concentrated overflow and enter the pool 8. The pool of liquid in the containing liquid, a portion of the liquid to return to mixing, inoculation system, bacterial stirring oxidation cobalt-dipping cycle. When the lean solution of the cobalt concentration in the pool after treatment, extracting wherein the liquid enters the rich solution tank 9 ; rich solution tank in-cobalt-containing solution 10, sink cobalt 11 processing; cobalt-containing precipitate obtained after solid-liquid separation of the products of the cobalt may sell , the separating medium to return to pool 8. The above concentrate containing cobalt and sulfur content of cobalt in > 0.1%, cobalt-containing sulfur concentrate ore grinding fineness is less than 76 microns, concentrated underflow solid concentration of greater than 50% (w/w), the mixing part of the bacterial inoculum 10%-30% (v/v), leaching biological stirring the slurry concentration is 15%-35% (w/w), the leaching time biological stirring 3-10 days, cobalt leaching rate ≥ 80%, for producing cobalt products leaching solution contains cobalt ≥ 2 g/l. Iron in advance using calcium carbonate, sodium sulfide precipitation of cobalt, of-sale market can be cobalt sulfide product. Mode of execution Examples of the following operation for further description of the present invention. For example, a western part of the country for containing a large amount of iron ore, associated a small amount of cobalt sulfide deposits, mainly copper mineral as chalcopyrites, tsugio copper sulfide and copper oxide ore less content of; the mineralogical analysis shows that, in the ore mineral cobalt does not have an independent, creates conditions to element cobalt sulfide iron ore in mixed form. The average content of the copper the mine 1.6%, sulfur the average content of 36%, cobalt average content is 0.1%, main gangue mineral is a quartz, feldspar, chlorite, sericite and carbonate mineral. (1) as shown in Figure 2, the ore mining through crushing and grinding ore flotation process, after copper recovery in the ore, to obtain high sulfur containing cobalt A the tailings. The high-sulfur containing cobalt sulfur flotation tail mine flotation machine 13, to obtain cobalt-containing 1% of sulfur concentrate C; mine tailing B into flotation tailings. (2) according to the cobalt-containing sulfur concentrate the particle size distribution of the ore grinding test data, to ball mill grinding 2 processing, so that the cobalt-containing sulfur concentrate particle size of less than 38 microns. (3) after the ore concentrate containing cobalt and sulfur by the three layers of the counter-current washing and dewatering medicine concentration 2 rear, concentrated overflow E enter the sewage treatment system, concentrating the slurry concentration to reach an underflow D 65% mixing pond accent the slurry 3. (4) concentrating the underflow D adjusts the stuff chest 3 with dilute sulfuric acid, bacterial nutrient solution, bacterial cultivation workshop 12 F cultured bacteria liquid, lean liquid pool 8 to return to the bacteria mixing lixivium, get pH1.2-1.8, the solid concentration is about 20% of the slurry the bacteria. (5) containing the leaching tank leaching biological stirring 4, after the multi-stage series biological aerated stirring leaching 5 days, the leaching rate of the cobalt to reach 95%. After the bacterial leaching into the three layer of the pulp thickening machine concentration 5. Biological stirring in the leaching process, need to monitor pH value of the pulp, pulp potential, the oxygen content of the pulp, the solubility of carbon dioxide slurry, pulp temperature and parameters such as the bacterial content in the pulp. The pH value control in the 1.2-1.8 between, pulp potential control in 450mv -600mv (SCE), the pulp temperature through the cooling or heating the 40-50 the [...][...] , the dissolved oxygen concentration in the pulp > 4 mg/L, the carbon dioxide is dissolved amount holding > 15 mg/L, and the stirring leaching tank bacteria maintain a relatively high oxidation activity and growth active, finally obtain high cobalt leaching rate. (6) by leaching pulp thickening machine concentration 5 rear, overflow H enter the pool 8, the underflow G into the filter press filter 7. (7) filter press filter 7 production of filter cake I into the tail mine, filtrate J return to the pool 8, pool 8 soaks the ore fluid including the fungusadjusts the stuff chest in the return. (8) when the pool 8 cobalt concentration in 2 g/l the rear, extracting liquid enters the rich solution tank 9. Rich solution tank solution in iron removal step the calcium carbonate precipitate 10, then Na2S precipitation process 11 to obtain cobalt sulfide product. Cobalt sulfide product cobalt-containing up to 10% or more. (9) the concentrate containing cobalt and sulfur new process for leaching biological stirring of the ore leaching bacteria, is in a certain high-sulphur mining pit water separated from the culture, the strain of laboratory domesticating improved. The bioassays to identify its for medium-thermophilic acidophilic bacteria, Sulfobacillus to such. The inorganic salt culture medium of this fungus into divided into : (NH1)2 SO4 0.5 g/l, KCl 0.1 g/l, K2 HPO4 0.2 g/l, MgSO4 · 7H2 O 0.5 g/l, Ca (NO3)2 0.01 g/l, yeast extract 0.02% ; energy matrix is: simple substance S. Domesticating of the bacteria containing the above-mentioned nutrient substance is added in the tap water of the particle size of less than 76 microns of powdered ore concentrate containing cobalt and sulfur, after adding ore powder is formed to the slurry concentration is 1-20% weight percentage, the pH value of 1.5-2.5 between; domesticating for the oxidation-reduction potential of a bacterial 550-650mV (SCE), bacterial concentration is 107 -109/ml; the growth temperature of the bacterium the 4-55 [...] , the optimal growth temperature 45-50 the [...]. In this embodiment the medium thermophillus Acidophilic leaching Retech-MTC-1 named Sulfobacillus thermosulfidooxidans, are registered and preserved in China typical culture collection center (Wuhan University campus), preserving registration number CCTCC No: M206029. 28 March 2006 date. The effect of the present invention is: the concentrate containing cobalt and sulfur opened up new processing technology for, full use of the cobalt resources in remote areas, the comprehensive utilization of mineral resources level, reduces environmental pollution, the economic benefit is improved. The invention is particularly suitable for being applied in the western part of the country of the plateau in remote areas containing cobalt sulphide ore of the development resources. The invention relates to a biological mixing cobalt leaching novel technique for cobaltiferous sulfide ore concentrates. Cobalt sulphate which can be sold in the market are produced after procedures of fine grinding, washing and reagent removal, conditioning, biological mixing and leaching, solid-liquid separation, iron removal, cobalt precipitation and so on of the cobaltiferous sulfide ore concentrates. During the leaching process, the temperature of 40 to 55 DEG C, the PH value of 1.2 to 1.8 and certain ferrum concentration (1 to 15 grams per liter) in a system are needed to maintain in order to keep high activity of bacteria. The invention has the advantages of capability of fully utilizing mineral resources, improvement of comprehensive utilization level of mines, conservation of cost and improvement of profit, and is particularly suitable for development of cobaltiferous sulfide ore resources in remote areas. 1, a cobalt-containing sulfur concentrate biological stirring cobalt-dipping the new process, characterized in that it comprises the following steps: (1), cobalt-containing sulfur concentrate for re-grinding; (2), the (1) after fine grinding-heated concentrate powder washing removal of the concentrated processing; (3), the (2) in the slurry after the concentration treatment of sulphuric acid to adjust pH value, improving temperature, inoculating bacteria and adding the growth of bacteria after leaching system is pumped into the biological stirring, bacterial oxidation leach; (4), is continuously circulated leachate, when the leaching fluid cobalt concentration after separation can be achieved, through the calcium carbonate containing cobalt lixivium pre-iron, sodium sulfide or sodium hydrosulfide or hydrogen sulfide obtained after sinks the cobalt sulfurizes the drill product. 2, cobalt-containing sulfur concentrate biological stirring cobalt-dipping the new process according to Claim 1, characterized in that the bacteria used for medium thermophillus Acidophilic leaching, its named sulfobacillus thermosulfidooxidans Retech-MTC-1, are registered and preserved in China typical culture collection center, address: Wuhan University campus, CCTCC No to preserve the registration number: M206029, 28 March 2006 date, the medium thermophillus Acidophilic leaching from high sulfur mining is culturing separated from the pit water, and the strain of laboratory domesticating improved, the inorganic salt culture medium of this fungus into divided into : (NH4)2 SO4 0.5 g/l, KCl 0.1 g/l, K2 HPO4 0.2 g/l, MgSO4 · 7H2 O 0.5 g/l, Ca (NO3)2 0.01 g/l, yeast extract 0.02% ; energy matrix is: simple substance S; domesticating of the bacteria containing the above-mentioned nutrient substance is added in the tap water of the particle size of less than 76 microns of powdered ore concentrate containing cobalt and sulfur, powdered ore concentrate containing cobalt and sulfur is added after the concentration of the pulp 1-20% weight percentage, the pH value of 1.5-2.5 between; domesticating for the oxidation-reduction potential of a bacterial 550-650mV, relative to the measured value of the saturated calomel electrode, the bacterium concentration 107 -109/ml; the growth temperature of the bacterium the 4-55 [...]. 3, cobalt-containing sulfur concentrate biological stirring immersion drill new process as in Claim 1 or Claim 2, characterized in that the leaching biological stirring the slurry concentration is 15%-35%, of the slurry in the leaching process pH value is 1. 2-1.8, leaching temperature control in 40-55 the between [...] , leaching process needs to be charged in the reaction tank rich in O2 air and carbon dioxide. 4, containing drill sulfur concentrate biological stirring cobalt-dipping the new process as in Claim 1 or Claim 2, characterized in that the cobalt-containing sulfur concentrate as a cobalt-containing pyrite concentrate. 5, containing cobalt-sulfur concentrate biological stirring immersion drill new process as in Claim 1 or Claim 2, characterized in that the concentrate containing cobalt and sulfur of the cobalt content is greater than 0.1%. 6, cobalt-containing sulfur concentrate biological stirring immersion drill new process as in Claim 1 or Claim 2, characterized in that the cobalt-containing sulfur concentrate after the fine grinding ;, of the ore particle size of less than 76 microns. 7, cobalt-containing sulfur concentrate biological stirring cobalt-dipping the new process as in Claim 1 or Claim 2, characterized in that the biological stirring the solid-liquid separation to leaching pulp, the separating medium return to the pool. 8, cobalt-containing sulfur concentrate biological stirring cobalt-dipping the new process as in Claim 1 or Claim 2, characterized in that lean solution to leach the leachate in the pool in the circulating process, according to the required pH value, iron ion concentration of iron-sedimentation of calcium carbonate. 9, cobalt-containing sulfur concentrate biological stirring cobalt-dipping the new process according to Claim 2, characterized in that the growth temperature of the bacterium the 40-50 [...].