CN103343242B - Method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate - Google Patents

Method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate Download PDF

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CN103343242B
CN103343242B CN201310271949.0A CN201310271949A CN103343242B CN 103343242 B CN103343242 B CN 103343242B CN 201310271949 A CN201310271949 A CN 201310271949A CN 103343242 B CN103343242 B CN 103343242B
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bismuth
ore
roasting
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pyrolusite
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CN103343242A (en
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张传福
王志坚
湛菁
夏楚平
邬建辉
黎昌俊
姚永林
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Central South University
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Abstract

The invention discloses a method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate. The method comprises the following steps: 1) grinding and mixing bismuth sulfide ore and pyrolusite; 2) placing the mixed ore in roasting equipment, wherein the roasting temperature is 400-900 DEG C and the roasting time is 1-7 hours; 3) performing neutral leaching on the roasted product through water to obtain lixivium I containing manganese sulfate and leaching residue I containing bismuth; and 4) performing acid leaching treatment on the leaching residue I through an inorganic acid to obtain lixivium II containing rich bismuth and leaching residue II. The method disclosed by the invention can be used for not only obtaining a manganese sulfate product, but also directly extracting bismuth or obtaining chemical products of bismuth. According to the method disclosed by the invention, the problems of high energy consumption, high cost and pollution of low-concentration sulfur dioxide in an existing pyrogenic smelting process of bismuth sulfide ore are overcome, the problems of severe corrosion, high equipment requirements and the like caused by strong oxidant in a wet process are solved, and therefore the method is a clean and efficient bismuth smelting process.

Description

The method of bismuth and co-producing sulfuric acid manganese is extracted in the mutual roasting of bismuth sulfide ore and pyrolusite
Technical field
The invention belongs to field of metallurgy and chemical engineering, relate to a kind of method of extracting respectively bismuth and extract manganese from bismuth sulfide ore and pyrolusite.
Background technology
Bismuth is a kind of " green " rare metal, is widely used in Wood's metal, metallurgical addition agent, medicine and military industry field.One " bismuth application and development heat " is being risen in the countries such as Japan, the U.S., Russia, Germany, so the deep processed product of bismuth product has the good market competitiveness.
Bismuth is few in nature storage, abundance and silver quite, and mostly with plumbous, tungsten and molybdenum deposit symbiosis, seldom form independent mineral deposit.For higher-grade bismuth-containing material, mostly adopt pyrogenic process reverberatory smelting at present, bismuth concentrate mixes with batchings such as reductive agent coal dust, displacer iron filings, fusing assistant soda ash, add reverberatery smelting, output slag, matte and thick bismuth, thick bismuth is produced smart bismuth through pyrorefining, and this process energy consumption is high, and environmental pollution is larger, the overstocked bismuth metal of middle slag and precious metal are more, need to again recycle; For complicated bismuth-containing material, be all generally to adopt chlorination acidleach, in process, general chlorine or the iron trichloride of adopting is as oxygenant, high to the material requirement of equipment, has unavoidably chlorine excessive in leaching process simultaneously, have a strong impact on workman's healthy and environment, and wastewater discharge is large.Under present case, along with the dilution of resource, complicated difficult selects increasing of bismuth mineral and high eulytine especially, and thermal process cannot be processed, and the advantage that wet processing is processed complex feedstock just becomes increasingly conspicuous.
In recent years, many R&D institutions both domestic and external form according to the difference of bismuth mineral and the difference of raw material, around reducing in operating cost, the regeneration that solves environmental pollution, leaching agent and solution the problems such as valuable metal enrichment, research and develop the refining bismuth flow process making new advances.Pyrolusite, due to stable in properties, is insoluble to bronsted lowry acids and bases bronsted lowry, and the extraction of manganese requires to transform into acid soluble low price Mn (II) oxide compound by reduction (interpolation reductive agent), then through operations such as sulfuric acid solution, removal of impurities, makes manganese sulfate product.The producer of domestic production at present mainly adopts reducing roasting-sulfuric acid leaching explained hereafter manganous sulfate, throughput reaches 30,000 t/a, but reducing roasting temperature requirement is up to 700～1000 ℃, also will consume a large amount of coal dusts as reductive agent simultaneously, production process energy consumption is high, long flow path, and produces a large amount of CO 2with CO waste gas.The core procedure that extracts valuable metal in sulfide mineral (as pyrite, zink sulphide, chalcopyrite) is all to carry out decomposing metal sulfide by oxygenizement, consider the comprehensive utilization of strong oxidizing property and the resource of pyrolusite, eighties of last century the seventies left and right has just started the research (Yuan Mingliang of the two ore deposit method extract technologies that flow process is short, equipment is simple, environmental pollution is little, Mei Xiangong, Zhuan Jianming, Deng. pyrolusite two ore deposit method selectivity leach [J]. China YouSe Acta Metallurgica Sinica, 1996, (3): 22-25); In recent years the metallurgical scientific and engineering of Central South University institute to utilize auriferous pyrite in milltailings (sulphur content is greater than 35%) and pyrolusite (manganese content is less than 20%) be raw material, adopt two ore deposit roasting-leaching-purification process high efficiency extraction manganese and iron, this project is successful industrialization.
The research that utilizes pyrolusite to extract bismuth is not yet seen in report.
Summary of the invention
The present invention is directed to the deficiency of bismuth extraction process in prior art, a kind of provide that flow process is short, equipment is simple, energy consumption is low, environmental pollution is little and metal comprehensive recovery is high, bismuth and co-producing sulfuric acid manganese are extracted in the bismuth sulfide ore of good product quality and the mutual roasting of pyrolusite method.Be intended to both realize the cleaner production of bismuth, realize again the comprehensive reutilization of pyrolusite simultaneously, reach energy-saving and emission-reduction and value-added object.
The technical scheme that realizes above-mentioned purpose of the present invention is:
A method for bismuth and co-producing sulfuric acid manganese is extracted in the mutual roasting of bismuth sulfide ore and pyrolusite, first bismuth sulfide ore and pyrolusite is mixed to mutual roasting according to a certain ratio and obtains calcining product; Then, product of roasting is carried out to neutrality and leach, reclaim(ed) sulfuric acid manganese from neutral leach liquor; Then use the above-mentioned neutral leaching residue of mineral acid acidleach, the heavy metals such as the recyclable gold and silver of gained acid leaching slag, the rich bismuth solution that acidleach obtains is produced bismuth chemical for next step, or directly extracts bismuth after purifying.Concrete steps are as follows:
1) bismuth sulfide ore and pyrolusite grind respectively, are evenly mixed to get the ore deposit of mixing of bismuth sulfide ore and pyrolusite after grinding;
2) mixing ore deposit is placed in to roasting apparatus, maturing temperature 400-900 ℃, roasting time 1-7h, obtains product of roasting;
3) product of roasting water being carried out to neutrality leaches, controlling temperature in neutral leaching process is 20-70 ℃, extraction time is 10min-360min, and with sulfuric acid, controlling neutral leaching endpoint pH is 4.0-7.0, obtains the leach liquor I of sulfur acid manganese and the leached mud I of bismuth-containing species;
Manganese in raw material enters in leach liquor I with the form of manganous sulfate.By leach liquor I is processed and can be obtained manganous sulfate crystalline solid.
4) with mineral acid, leached mud I is carried out to Ore Leaching processing, controlling Ore Leaching temperature in acidleach process is 25-90 ℃, the Ore Leaching time is 10min-360min, the initial hydrogen ion concentration of Ore Leaching is 1mol/L-8mol/, the liquid-solid 2-6 that compares of Ore Leaching, Ore Leaching process stirring velocity 300～1000 turn/min, obtain leach liquor II and the leached mud II of rich bismuth.
Wherein, leached mud II can be extracted valuable metal and precious metal in slag by this area ordinary method.
Wherein, described bismuth sulfide ore is bismuth sulfide concentrate, chats, raw ore, and the grain graininess that described grinding obtains is 100 order-250 orders.
Wherein, described pyrolusite is concentrate, raw ore or chats, and the grain graininess that described grinding obtains is 100 order-250 orders.
Wherein, the bismuth sulfide ore after described grinding and pyrolusite blending ratio are for being n according to mixing in ore deposit the molar ratio of manganese content in total sulfur content and pyrolusite mn: n s=1.0-10.0:1.Preferably, in mixing ore deposit, in total sulfur content and pyrolusite, the molar ratio of manganese content is n mn: n s=1.5-5.0:1.
Preferably, the maturing temperature described step 2) is 500 ℃-700 ℃.Described step 2) roasting apparatus in is tube type resistance furnace, retort furnace, reverberatory furnace, rotary kiln, multiple hearth furnace or the vulcanization bed roasting apparatus in existing industrial production, and its mode of production can be continuous production, also can batch production.
Wherein, described step 2) calcination atmosphere in is oxidizing atmosphere, can be one or more in air, oxygen-rich air or oxygen.
Preferably, the roasting time described step 2) is 2-6h.
Wherein, in described step 3), controlling liquid-solid ratio is 2-8(liquid volume: solid masses, unit is mL/g or L/kg).
Preferably, endpoint pH 4.5-5.5 in described step 3).By add sulfuric acid in neutral leaching process, can control endpoint pH.According to practical experience, sulfuric acid can be used the sulphuric acid soln of low concentration, for example sulphuric acid soln of 0.2-2% (volume ratio) or 0.1-2mol/L.
Wherein, in described step 4), Ore Leaching is a kind of Ore Leaching that carries out using in sulfuric acid, hydrochloric acid, nitric acid.
Wherein, in described step 3) and step 4), Ore Leaching process need stirs, and stirring velocity is turn/min of 300-1000.
Through step 1) to 4) bismuth enters into leach liquor II in raw material, and available existing metallurgical technology carries out purification and impurity removal to leach liquor II, extracts bismuth metal or prepares the Chemicals of bismuth.For example, leach liquor II is carried out to bismuth meal reduction ferric iron, once hydrolysis, secondary hydrolysis, can obtain chlorine oxygen bismuth, and further dechlorination, finally obtains bismuthous oxide bismuth trioxide.The method of extracting bismuth also comprises extraction process, iron-deoxidize etc.
Beneficial effect of the present invention is:
(1) bismuth sulfide ore that the present invention proposes and the method for pyrolusite mutual roasting high efficiency extraction bismuth and co-producing sulfuric acid manganese, after by a certain percentage bismuth sulfide ore being mixed with pyrolusite, be placed in roasting apparatus and fully carry out mutual roasting, product of roasting adopts x-ray diffractometer analysis, confirms to have Bi in mutual product of roasting 2o 3, Bi 28o 32(SO 4) 10and MnSO 4.Product of roasting has obtained through neutral leaching the leach liquor I and the leached mud I that contain manganous sulfate, and leached mud I obtains being rich in the solution of bismuth through acidleach, by further processing, can directly extract bismuth or obtain the Chemicals of bismuth.The present invention is based on the stability of the strong oxidizing property of pyrolusite, the reductibility of bismuth sulfide ore and manganous sulfate, utilize the technique of bismuth sulfide ore and pyrolusite mutual roasting high efficiency extraction bismuth and co-producing sulfuric acid manganese, both the high energy consumption that the existing pyrometallurgical smelting process of bismuth sulfide ore brings, expensive, low-concentration sulfur dioxide pollution problem had been overcome, also overcome the seriously corroded that in the existing wet processing of bismuth sulfide ore, strong oxidizer brings, the problems such as equipment requirements height are a kind of bismuth smelting technologyes of clean and effective.
(2) for manganese resource, technique of the present invention has overcome conventional softer manganese ore and has produced manganous sulfate high energy consumption, and with serious pollution problem is the novel process that a kind of high-efficiency cleaning extracts manganese.
(3) flow process of the present invention is short, equipment is simple, and energy consumption is low, and environmental pollution is little, and metal comprehensive recovery is high, can realize a technical process, the comprehensive utilization of two kinds of resources.
Accompanying drawing explanation
Fig. 1: the process flow sheet of bismuth and co-producing sulfuric acid manganese is extracted in the mutual roasting of bismuth sulfide ore and pyrolusite;
The XRD figure of Fig. 2: embodiment 1 bismuth sulfide ore and the mutual product of roasting of pyrolusite;
The XRD figure spectrum of Fig. 3: embodiment 1 bismuth sulfide ore and the mutual product of roasting of pyrolusite leached mud I after neutrality leaches;
The XRD figure spectrum of Fig. 4: embodiment 1 Leaching in Hydrochloric Acid slag II.
Embodiment
Now with following most preferred embodiment, the present invention is described, but is not used for limiting the scope of the invention.
Embodiment 1:
The composition of the bismuth sulfide ore that Chenzhou, Hunan Province produces is: Bi25.95%, Fe23.53%, Cu4.86%, Pb3.28%, Zn0.51%, S26.76%;
The chemical composition that pyrolusite is produced in Tongren district Guizhou Province area: MnO 238.92%, SiO 228.2%, Al 2o 39.27%, S0.013%.
Technical process is referring to Fig. 1.
(1) dried 35.3g bismuth sulfide ore and 164.7g pyrolusite are carried out respectively to ball milling, obtain granularity and be 200 object bismuth sulfide ore and pyrolusites, n is pressed in two kinds of ore deposits after levigate mn: n s=2.5 molar ratios evenly mix, and are placed in retort furnace and carry out mutual roasting, and controlling maturing temperature is 650 ℃, and roasting time is 2 hours, and calcination atmosphere is industrial general oxygen, and flow 16L/h, obtains product of roasting.Product of roasting is carried out to element and material phase analysis etc., and result shows Bi in bismuth sulfide ore 2s 3mainly be converted into Bi 2o 3, also having part is Bi 28o 32(SO 4) 10, most of sulphur is converted into SO 2- 4, with the Mn of divalence 2+form manganous sulfate, mix the S in ore deposit 2-be converted into SO 4 2-transformation efficiency be 98.2%, also have part to exist with the form of MnS, sulfur-fixing rate reaches 99.4%, the XRD figure spectrum of product of roasting is as shown in Figure 2.
(2) product of roasting step (1) being obtained carries out neutrality and leaches, controlling temperature in neutral leaching process is 40 ℃, extraction time is 180min, liquid-solid ratio is 5(water: product of roasting, Unit/mL/g), stirring velocity is 600 turn/min, uses 1%(volume ratio in leaching process) dilute sulphuric acid control that neutral to leach endpoint pH be 5.0, manganous sulfate in product of roasting enters leach liquor I, and bismuth is with Bi 2o 3and Bi 28o 32(SO 4) 10enter leached mud I, leached mud I is carried out to the known manganous sulfate of material phase analysis and almost all leached in leach liquor I, the leaching yield of manganous sulfate reaches 99.5%, by conventional means, can obtain manganous sulfate solid.Bismuth is all stayed in leached mud, and the XRD figure of leached mud I is composed as shown in Figure 3.
(3) adopt hydrochloric acid to carry out Ore Leaching processing to the resulting leached mud I of step (2), controlling Ore Leaching temperature in acidleach process is 50 ℃, the Ore Leaching time is 120min, the concentration of the initial hydrochloric acid soln of Ore Leaching is 5mol/L, Ore Leaching is liquid-solid than 5(hydrochloric acid soln: leached mud I, Unit/mL/g), Ore Leaching process stirring velocity 1000 turn/min, obtain leach liquor II and the leached mud II of rich bismuth, the leaching yield that analytical results shows bismuth is up to being that 98.2%, XRD material phase analysis shows Bi in leached mud II 2o 3, Bi 18o 24(SO 4) 10and the thing of other most of foreign metal oxide compounds all do not exist mutually, Fig. 4 is the XRD figure spectrum of Leaching in Hydrochloric Acid slag II.
(4) to the Fe in bismuth meal reducing solution for leach liquor II 3+, by controlling the pH value of once hydrolysis, secondary hydrolysis, can obtain chlorine oxygen bismuth, further dechlorination, dechlorination rate is 99.5%, has finally obtained bismuthous oxide bismuth trioxide.
Embodiment 2:
Raw material is with embodiment 1.
(1) dried 30.3g bismuth sulfide ore and 169.7g pyrolusite are carried out respectively to ball milling, obtain granularity and be 150 object bismuth sulfide ore and pyrolusites, n is pressed in two kinds of ore deposits after levigate mn: n s=3.0 molar ratios evenly mix, and are placed in retort furnace and carry out mutual roasting, and controlling maturing temperature is 600 ℃, and roasting time is 4 hours, and calcination atmosphere is air, and flow 20L/h, obtains product of roasting.Product of roasting is carried out to element and material phase analysis etc., and result shows Bi in bismuth sulfide ore 2s 3mainly be converted into Bi 2o 3, also having small part is Bi 28o 32(SO 4) 10, most of sulphur is converted into SO 2- 4, with the Mn of divalence 2+produce manganous sulfate, mix the S in ore deposit 2-be converted into SO 4 2-transformation efficiency be 98.9%, part exists with the form of MnS, sulfur-fixing rate reaches 99.8%.
(2) product of roasting step (1) being obtained carries out neutrality and leaches, controlling temperature in neutral leaching process is 25 ℃, extraction time is 120min, liquid-solid ratio is 3(water: product of roasting, Unit/mL/g), stirring velocity is 500 turn/min, by sulphuric acid soln (concentration 1%, volume ratio) controlling leaching endpoint pH is 6.0, and the manganous sulfate in product of roasting enters leach liquor I, and bismuth is with Bi 2o 3and Bi 28o 32(SO 4) 10enter leached mud I, manganous sulfate has almost all leached in leach liquor I, and the leaching yield of manganous sulfate reaches 99.7%;
(3) adopt sulfuric acid to carry out Ore Leaching processing to the resulting neutral leaching residue I of step (2), controlling Ore Leaching temperature in acidleach process is 40 ℃, the Ore Leaching time is 150min, the initial concentration of hydrochloric acid of Ore Leaching is 6mol/, the liquid-solid ratio 6 of Ore Leaching, Ore Leaching process stirring velocity 600 turn/min, obtain being rich in leach liquor II and the leached mud II of bismuth ion, and the leaching yield of bismuth is up to being 98.2%.
Embodiment 3:
Raw material is with embodiment 1
(1) dried 52.6g bismuth sulfide ore and 147.4g pyrolusite are carried out respectively to ball milling, obtain granularity and be 200 object bismuth sulfide ore and pyrolusites, n is pressed in two kinds of ore deposits after levigate mn: n s=1.5 molar ratio evenly mixes, and is placed in retort furnace and carries out mutual roasting, and controlling maturing temperature is 700 ℃, and roasting time is 4 hours, and calcination atmosphere is oxygen-rich air, and flow 50L/h, obtains product of roasting.Product of roasting is carried out to element and material phase analysis etc., and result shows Bi in bismuth sulfide ore 2s 3mainly be converted into Bi 2o 3, small part is Bi 28o 32(SO 4) 10, most of sulphur is converted into SO 2- 4, with the Mn of divalence 2+form manganous sulfate, mix the S in ore deposit 2-be converted into SO 4 2-transformation efficiency be 97.8%, small part exists with the form of MnS, sulfur-fixing rate reaches 98.9%.
(2) product of roasting step (1) being obtained carries out neutrality and leaches, controlling extraction temperature in neutral leaching process is 50 ℃, extraction time is 180min, liquid-solid ratio is 3(water: product of roasting, Unit/mL/g), stirring velocity is 500 turn/min, and in leaching process, adding sulphuric acid soln (concentration is 1% volume ratio) control leaching endpoint pH is 4.5, manganous sulfate in product of roasting enters leach liquor I, and bismuth is with Bi 2o 3and Bi 28o 32(SO 4) 10enter leached mud I, leached mud I is carried out to the known manganous sulfate of material phase analysis and almost all leached in leach liquor I, the leaching yield of manganous sulfate reaches 99.1%, and bismuth is all stayed in leached mud;
(3) adopt nitric acid to carry out Ore Leaching processing to the resulting neutral leaching residue I of step (2), controlling Ore Leaching temperature in acidleach process is 60 ℃, the Ore Leaching time is 120min, the initial concentration of nitric acid of Ore Leaching is 3mol/L, Ore Leaching is liquid-solid than 4(salpeter solution: leached mud I, the L/kg of unit), Ore Leaching process stirring velocity 500 turn/min, obtain being rich in leach liquor II and the leached mud II of bismuth, the leaching yield of bismuth is up to being 98.8%.
Embodiment 4:
Raw material is with embodiment 1.
(1) dried 19.3g bismuth sulfide ore and 180.7g pyrolusite are carried out respectively to ball milling, obtain granularity and be 150 object bismuth sulfide ore and pyrolusites, n is pressed in two kinds of ore deposits after levigate mn: n s=5 molar ratios evenly mix, and are placed in retort furnace and carry out mutual roasting, and controlling maturing temperature is 500 ℃, and roasting time is 6 hours, and calcination atmosphere is industrial general oxygen, and flow 16L/h, obtains product of roasting.Product of roasting is carried out to element and material phase analysis etc., and result shows Bi in bismuth sulfide ore 2s 3mainly be converted into Bi 2o 3, also having small part is Bi 28o 32(SO 4) 10, most of sulphur is converted into SO 2- 4, with the Mn of divalence 2+form manganous sulfate, mix the S in ore deposit 2-be converted into SO 4 2-transformation efficiency be 99.8%, small part exists with the form of MnS, sulfur-fixing rate reaches 99.8%.
(2) product of roasting step (1) being obtained carries out neutrality and leaches, controlling neutral extraction temperature in neutral leaching process is 40 ℃, extraction time is 180min, liquid-solid ratio is 5(water: product of roasting, Unit/mL/g), stirring velocity is 600 turn/min, according to the pH value of solution, change the value with dilute sulphuric acid (sulfuric acid concentration 1mol/L) regulator solution pH, controlling and leaching endpoint pH is 5.0, and the manganous sulfate in product of roasting enters leach liquor I, and bismuth is with Bi 2o 3and Bi 28o 32(SO 4) 10enter leached mud I, leached mud I is carried out to the known manganous sulfate of material phase analysis and almost all leached in leach liquor I, the leaching yield of manganous sulfate reaches 99.8%, and bismuth is all stayed in leached mud;
(3) adopt hydrochloric acid to carry out Ore Leaching processing to the resulting neutral leaching residue I of step (2), controlling Ore Leaching temperature in acidleach process is 50 ℃, the Ore Leaching time is 120min, the initial concentration of hydrochloric acid of Ore Leaching is 5mol/L, Ore Leaching is liquid-solid than 5(hydrochloric acid soln: leached mud I, Unit/mL/g), Ore Leaching process stirring velocity 1000 turn/min, obtain the leach liquor II and the leached mud II that contain bismuth ion, the leaching yield of bismuth is up to being 98.5%.
Above embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various modification and improvement that the common engineering technical personnel in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.

Claims (10)

1. a method for bismuth and co-producing sulfuric acid manganese is extracted in the mutual roasting of bismuth sulfide ore and pyrolusite, it is characterized in that, comprises step:
1) bismuth sulfide ore and pyrolusite grind respectively, are evenly mixed to get the ore deposit of mixing of bismuth sulfide ore and pyrolusite after grinding;
2) mixing ore deposit is placed in to roasting apparatus, maturing temperature 400-900 ℃, roasting time 1-7h, obtains product of roasting;
3) product of roasting water being carried out to neutrality leaches, controlling temperature in neutral leaching process is 20-70 ℃, extraction time is 10min-360min, and with sulfuric acid, controlling neutral leaching endpoint pH is 4.0-7.0, obtains the leach liquor I of sulfur acid manganese and the leached mud I of bismuth-containing;
4) with mineral acid, leached mud I is carried out to Ore Leaching processing, controlling temperature in acidleach process is 25-90 ℃, and the time is 10min-360min, the initial H of Ore Leaching +concentration is 1mol/L-8mol/L, and Ore Leaching is liquid-solid than 2-6, obtains leach liquor II and the leached mud II of bismuth-containing.
2. method according to claim 1, is characterized in that: described bismuth sulfide ore is bismuth sulfide concentrate, chats or raw ore; Described pyrolusite is concentrate, raw ore or chats; The grain graininess that described grinding obtains is 100 order-250 orders.
3. method according to claim 1, is characterized in that: the bismuth sulfide ore after described grinding and pyrolusite blending ratio are for being n according to mixing in ore deposit the molar ratio of manganese content in total sulfur content and pyrolusite mn: n s=1.0-10.0:1 mixes.
4. method according to claim 1, is characterized in that: the maturing temperature described step 2) is 500 ℃-700 ℃.
5. method according to claim 1, is characterized in that: the calcination atmosphere described step 2) is oxidizing atmosphere, can be one or more in air, oxygen-rich air or oxygen.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: the roasting time described step 2) is 2-6h.
7. according to the arbitrary described method of claim 1-5, it is characterized in that: in described step 3), controlling liquid-solid ratio is 2.0-8.0.
8. according to the arbitrary described method of claim 1-5, it is characterized in that: in described step 3), with sulfuric acid, control the neutral endpoint pH 4.5-5.5 that leaches.
9. according to the arbitrary described method of claim 1-5, it is characterized in that: in described step 4), Ore Leaching is a kind of Ore Leaching that carries out using in sulfuric acid, hydrochloric acid, nitric acid.
10. according to the arbitrary described method of claim 1-5, it is characterized in that: in described step 3) and step 4), Ore Leaching process need stirs, and stirring velocity is turn/min of 300-1000.
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