CN101049968A - Method for associated producing ammonium molybdate and manganese sulfate by roasting molybdenite and pyrolusite - Google Patents
Method for associated producing ammonium molybdate and manganese sulfate by roasting molybdenite and pyrolusite Download PDFInfo
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- CN101049968A CN101049968A CN 200710034928 CN200710034928A CN101049968A CN 101049968 A CN101049968 A CN 101049968A CN 200710034928 CN200710034928 CN 200710034928 CN 200710034928 A CN200710034928 A CN 200710034928A CN 101049968 A CN101049968 A CN 101049968A
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Abstract
This invention discloses a method for combined production of ammonium molybdate and manganese sulfate by co-torrefication of molybdenite and pyrolusite. The method comprises: (1) mixing molybdenite and pyrolusite at a ratio of nMnO2:nMoS2 = 1.0-10.0; (2) co-torrefying the mixture at 350-950 deg.C for 60-360 min; (3) acidolyzing with an inorganic acid at 5-95 deg.C and a liquid/solid ratio of 1.0-50.0 for 5-300 min until the pH value is below 5.5; (4) extracting the leaching solution with solvent, separating to obtain an organic phase containing Mo and an aqueous phase containing Mn, and back-extracting the organic phase with ammonia to obtain ammonium molybdate; (5) processing into ammonium molybdate and manganese sulfate products by using the present metallurgical technique. The method has such advantages as short process, simple apparatus, low energy consumption, little pollution, high metal recovery rate, and high product quality.
Description
Technical field
The present invention relates to a kind of method with molybdenum glance and pyrolusite direct production ammonium molybdate and manganous sulfate.
Background technology
Molybdenum is a kind of crucial yttrium, is widely used in fields such as metallurgy, chemical industry, machinery, space flight and aviation and biology, becomes increasingly important metallic substance.The molybdenum in China resource reserve is big, distribution is wide, type is many, complex ore is many, and explored reserves have 4.15Mt, occupy the second in the world, are one of countries of molybdenum products export amount maximum in the world, and concentrated molybdenum ore throughput rapidly increases, and has reached 70kt/a at present.
During 60～seventies of 20th century, almost roasting-ammonia soaking technology is all adopted in the production of 90% pure molybdenum compound in the world.Roasting-the ammonia soaking technology is that concentrated molybdenum ore is carried out oxidizing roasting under 600～700 ℃ to tradition, and common equipment has shaft furnace, reverberatory furnace, mechanical kiln (raking), multiple hearth furnace, fluidizing furnace etc., and (principal constituent is MoO to the molybdenum calcining that roasting is come out
3) through ammonia soak, steps such as purification and impurity removal, acid are heavy, filtration, crystallization obtain ammonium molybdate product (I.Sasaki, US6559085; C.J.Mahesh, US6190625), MoO
3795 ℃ of down significantly distillations, this technology is because the roasting process temperature is too high, and the ult rec that causes Mo is only about 90%, and energy consumption is higher.
Common sinter process of lime-concentrated molybdenum ore and NaCO have been developed both at home and abroad in succession
3The common sinter process of-concentrated molybdenum ore.The common sinter process of lime-concentrated molybdenum ore that the later stage eighties 20th century grows up is at molybdenum glance SO in roasting process
2The recovery problem of pollution and association rhenium element, the main effect of lime is solid sulphur (CaSO
4) and solid rhenium (Ca (ReO
4)
2), although molybdenum, the rhenium rate of recovery can be brought up to 95% and 74% respectively, SO
2Pollution problem is not still better solved, and raw material consumption, waste residue and waste liquid amount obviously increase in the production process, so be difficult to apply (Liu Yinghan. from the rhenium-containing concentrated molybdenum ore, extract the research [J] of molybdenum and rhenium. Jiangxi Univ.'s journal (natural science edition), 1989,13 (1): 88～95.).NaCO
3The common sinter process of-concentrated molybdenum ore is mainly used to handle and contains the higher molybdenum calcining ammonia leaching residue of molybdenum amount, and its principle is to make the molybdate of metals such as Fe in the slag, Cu, Pb transform into the more carbonate of indissoluble, and molybdenum then transforms into sodium salt soluble in water.
Domestic industry molybdenum oxide production producer has reached more than the various schools of thinkers at present, mostly adopt traditional roasting-ammonia soaking technology, but aggregate level is backward relatively, the mode of production adopts 8～12 layers of multiple hearth furnace except that indivedual larger enterprises, other medium and small producers account for ultimate production more than 1/3 all with reverberatory furnace or rotary kiln baking concentrated molybdenum ore, and most producers do not possess the recovering means of sulfurous gas, discharge a large amount of low concentration sulphur dioxide flue gas every year in atmosphere thus, this situation continues into the present over nearly 10 years always.
Pyrolusite is because 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), makes manganese sulfate product through operations such as sulfuric acid solution, removal of impurities then.At present domestic more than 30 the manufacturer's employing reducing roasting-sulfuric acid extract technology production manganous sulfate that surpasses, throughput reaches 30,000 t/a, the reducing roasting temperature requirement is up to 700～1000 ℃, also consume a large amount of fine coal simultaneously as reductive agent, production process energy consumption height, long flow path, and produce a large amount of CO
2With CO waste gas.The core procedure that extracts valuable metal in the sulfide mineral (as pyrite, zink sulphide, chalcopyrite) all is to come decomposing metal sulfide by oxygenizement, consider the comprehensive utilization of the strong oxidizing property and the resource of pyrolusite, begun the research (Mei Guanggui of the two ore deposit method extract technologies that flow process is short, equipment is simple, environmental pollution is little about eighties of last century the seventies, Zhong Zhuqian. zinc sulfide concentrates and pyrolusite leach and Zn-Mn electrolytic research [J] simultaneously simultaneously. and the journal .1982 of institute makes a study of subjects in Central-South ore deposit, (1): 18-25.), part is successfully shifted suitability for industrialized production onto.
Summary of the invention
The molybdenum glance that technical problem to be solved by this invention provides that a kind of flow process is short, equipment is simple, energy consumption is low, environmental pollution is little and metal comprehensive recovery height, quality product are high and the method for pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate.
In order to solve the problems of the technologies described above, the method for molybdenum glance provided by the invention and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate, it comprises the following step:
A, molybdenum glance and pyrolusite are pressed n
MnO2: n
MoS2=1.0～10.0 ratio mixings;
B, be 350 ℃～950 ℃ condition under common roasting in temperature with both mixture in same equipment, the time is 60～360min;
C, utilize mineral acid acidolysis product of roasting, acidolysis temperature is 5 ℃～95 ℃, and liquid-solid ratio is 1.0～50.0, and the acidolysis time is 5～300min, and the pH value of solution should obtain molybdenum salt, manganese salt solution and other insoluble impurities slag less than 5.5 after the acidolysis;
D, leach liquor after solvent extraction and separation, the raffinate water that obtains respectively containing the Mo extracted organic phase He contain Mn; For containing the Mo extracted organic phase, adopt the ammoniacal liquor back extraction to get ammonium molybdate solution;
E, the ammonium molybdate solution that obtains, manganese salt solution are continued to use existing corresponding ammonium molybdate and the manganese sulfate product of making of metallurgical technology.
The ratio n of molybdenum glance and pyrolusite in the above-mentioned steps (a)
MnO2: n
MoS2The mixing of=2.0～5.0, two kinds of mineral is that simple mechanical stirring is mixed, or adds binding agent compression moulding.
Two kinds of mineral intermixture roastings in same equipment in the above-mentioned steps (b), roasting apparatus there is not particular requirement, its roasting apparatus is reverberatory furnace, rotary kiln, multiple hearth furnace or the sulfuration bed roasting apparatus in the existing industrial production, and its mode of production can be a continuous production, also can batch production.
Maturing temperature is 450 ℃～600 ℃ in the above-mentioned steps (b).
Calcination atmosphere is an air in the above-mentioned steps (b), or pure oxygen.
Used mineral acid is sulfuric acid, hydrochloric acid or nitric acid in the above-mentioned steps (c), and the acidolysis process need keep the certain acidity of system.
Used extraction agent is a secondary amine in the above-mentioned steps (d).Described extraction agent is N235, and other composition of extracted organic phase has sulfonated kerosene, secondary octanol.
Metallurgical technology from ammonium molybdate solution recovery Mo in the above-mentioned steps (e) is that purification, acid are heavy, dry, and impurity level Gao Shixu carries out operations such as multistep ammonia is molten, acid is sunk.
Be to adjust pH value, purification and impurity removal, evaporative crystallization, recrystallization from containing the metallurgical technology that Mn solution reclaims Mn in the above-mentioned steps (e).
Method of the present invention is suitable for the molybdenum glance of any grade, comprises molybdenum glance concentrate, chats or raw ore etc.; The pyrolusite that is adopted can be the concentrate after the enrichment, also can be than the raw ore of higher-grade or chats etc.
In the method for the present invention, the mineral acid that is adopted can be sulfuric acid, hydrochloric acid, nitric acid etc., and acid hydrolysate is MoO
2SO
4, MoO
2Cl
2, MoO
2(NO
3)
2Solution and manganese salt are as MnSO
4, MnCl
2, Mn (NO
3)
2Solution.
Method of the present invention is generally carried out under normal pressure.
Adopt the molybdenum glance of technique scheme and the method for pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate, by a certain percentage with molybdenum glance with after pyrolusite mixes, place the roasting apparatus thorough roasting, a word used in place name sand product adopts the analysis of X-crystalline diffraction, confirms based on manganese molybdate; Contain manganese a word used in place name sand and utilize acidolysis can obtain molybdenum salt, acidolysis can be sulfuric acid, hydrochloric acid, nitric acid etc. based on mineral acid, and acid hydrolysate then is MoO
2SO
4, MoO
2Cl
2, MoO
2(NO
3)
2Solution and manganese salt are as MnSO
4, MnCl
2, Mn (NO
3)
2Solution; According to Mo, Mn ionic occurrence status, adopt solvent extraction technology to separate and carry out the separation and purification enrichment of Mo and Mn, the solution that can obtain respectively containing Mo He contain Mn is continued to use existing technology then and is made ammonium molybdate and manganese sulfate product.The present invention is based on the strong oxidizing property of pyrolusite, the reductibility of molybdenum glance and the stability of manganous sulfate, utilize the common novel roasting process of molybdenum glance-pyrolusite partly to overcome sulfur-containing smoke gas serious environment pollution in traditional roasting-ammonia lixiviate molybdenum technology, improve metal comprehensive recovery and quality product (the Mo rate of recovery reaches more than 95%), and significantly reduce raw material consumption and energy consumption in the pyrolusite decomposition course (as high temperature reduction roasting-acid leaching process).Calcining process of the present invention does not have particular requirement to equipment, can carry out in general molybdenum smeltery.
In sum, the molybdenum glance that the present invention is that a kind of flow process is short, equipment is simple, energy consumption is low, environmental pollution is little and metal comprehensive recovery height, quality product are high and the method for pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate.
Embodiment
The present invention is further specified by the following example, but is not subjected to the restriction of these embodiment.All umbers and percentage ratio all refer to quality except as otherwise herein provided among the embodiment.
Embodiment 1:
5 parts of molybdenum glance concentrate (containing Mo 47.4%), 8 parts of pyrolusites (containing Mn 50.4%) are mixed (n
MnO2/ n
MoS2=3.0), breeze packed into is placed on the roasting that heats up in the tube type resistance furnace in the silica tube, and an end of silica tube connects gas blower, and the control air quantity is 25ml/min, utilizes temperature regulator temperature to be controlled at 500 ℃, roasting 180min.Product of roasting is carried out element sulphur analysis, Mo material phase analysis etc., and the result shows that sulfur-fixing rate is 94.8%, the oxidation ratio of Mo is 100%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).
The manganese Mo a word used in place name sand that contains that obtains utilizes the sulphuric acid soln of 100g/L to leach, and leaches to room temperature (25 ℃), soaks that liquid-solid ratio is 10, the acidolysis time is 90min, obtains containing Mo (MoO
2SO
4), Mn (MnSO
4) red solution and sour insoluble slag, the leaching yield of Mo is 99.8%, the leaching yield of Mn is 89.0%.Adopt N235 (extracted organic phase is the secondary octanol of 20%N235+10%+70% sulfonated kerosene) to extract from contain Mn molybdenum calcine pickle liquor as extraction agent and reclaim Mo, extraction temperature is room temperature (25 ℃), compare O/W and be 1/5, cross current solvent extraction progression is 5 grades, aqueous phase sulfuric acid concentration≤100g/L; With weak ammonia extracted organic phase is washed earlier during back extraction, reverse-extraction agent adopts 17% ammoniacal liquor, and the back extraction temperature be a room temperature also, and to compare O/W be 1/2, extract progression is 2, and the percentage extraction of Mo, back extraction ratio reach 99.6%, 99.1% respectively under this condition.
Can obtain ammonium molybdate solution and manganese sulfate solution (raffinate water) respectively through extraction process, continue to use existing metallurgical technology condition then and produce ammonium molybdate and manganese sulfate product respectively, promptly to ammonium molybdate solution carry out ammonium sulfide removal of impurities-acid heavy-ammonia is molten-acid is heavy-operations such as drying, obtain meeting the ammonium molybdate product of state quality standard (GB GB3460-82), the yield of this process Mo is 96.9%, and the ult rec of Mo is 95.5%; Manganese sulfate solution equally through adjusting pH value-purification and impurity removal-operations such as evaporative crystallization-recrystallization, is equally also obtained meeting the manganese sulfate product of state quality standard, and the yield of this process Mn is 90.3%, and the ult rec of Mn is 80.4%.
Embodiment 2:
5 parts of molybdenum glance concentrate (containing Mo 47.4%), 16 parts of pyrolusites (containing Mn 50.4%) are mixed (n
MnO2/ n
MoS2=6.0), breeze packed into is placed on the roasting that heats up in the tube type resistance furnace in the silica tube, and an end of silica tube connects gas blower, and the control air quantity is 25ml/min, utilizes temperature regulator temperature to be controlled at 600 ℃, roasting 90min.Product of roasting is carried out element sulphur analysis, Mo material phase analysis etc., and the result shows that sulfur-fixing rate is 98.8%, the oxidation ratio of Mo is 100%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4) and manganous sulfate.
The manganese Mo a word used in place name sand that contains that obtains utilizes the sulphuric acid soln of 300g/L to leach, and leaches and be controlled at 65 ℃, soaks liquid-solid ratio and be 5, the acidolysis time is 300min, obtains containing Mo (MoO
2SO
4), Mn (MnSO
4) red solution and sour insoluble slag, the leaching yield of Mo is 99.8%, the leaching yield of Mn is 73.4%.Adopt N235 (extracted organic phase is the secondary octanol of 20%N235+10%+70% sulfonated kerosene) to extract from contain Mn molybdenum calcine pickle liquor as extraction agent and reclaim Mo, extraction temperature is room temperature (25 ℃), compare O/W and be 1/5, cross current solvent extraction progression is 5 grades, aqueous phase sulfuric acid concentration≤200g/L; With weak ammonia extracted organic phase is washed earlier during back extraction, reverse-extraction agent adopts 17% ammoniacal liquor, and the back extraction temperature be a room temperature also, and to compare O/W be 1/2, extract progression is 2, and the percentage extraction of Mo, back extraction ratio reach 99.6%, 98.2% respectively under this condition.
Can obtain ammonium molybdate solution and manganese sulfate solution (raffinate water) respectively through extraction process, continue to use existing metallurgical technology condition then and produce ammonium molybdate and manganese sulfate product respectively, promptly to ammonium molybdate solution carry out ammonium sulfide removal of impurities-acid heavy-ammonia is molten-acid is heavy-operations such as drying, obtain meeting the ammonium molybdate product of state quality standard (GB GB3460-82), the yield of this process Mo is 96.9%, and the ult rec of Mo is 94.6%; Manganese sulfate solution equally through adjusting pH value-purification and impurity removal-operations such as evaporative crystallization-recrystallization, is equally also obtained meeting the manganese sulfate product of state quality standard, and the yield of this process Mn is 90.9%, and the ult rec of Mn is 66.7%.
Embodiment 3:
15 parts of molybdenum glance concentrate (containing Mo 47.4%), 8 parts of pyrolusites (containing Mn 50.4%) are mixed (n
MnO2/ n
MoS2=2.0), breeze packed into is placed on the roasting that heats up in the tube type resistance furnace in the silica tube, and an end of silica tube connects gas blower, and the control air quantity is 45ml/min, utilizes temperature regulator temperature to be controlled at 550 ℃, roasting 120min.Product of roasting is carried out element sulphur analysis, Mo material phase analysis etc., and the result shows that sulfur-fixing rate is 91.8%, the oxidation ratio of Mo is 100%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).
The manganese Mo a word used in place name sand that contains that obtains adopts 30% salpeter solution leaching, leach to room temperature (25 ℃), soak that liquid-solid ratio is 15, extraction time is 30min, obtain containing red solution and the sour insoluble slag of Mo, Mn, the leaching yield of Mo is 99.9%, and the leaching yield of Mn is 98.2%.Subsequent step is with embodiment 1, and the ult rec of Mo is 96.0%, and the ult rec of Mn is 91.6% (Mn (NO
3)
2).
Embodiment 4:
113 parts of molybdenum glance chats (containing Mo 26.4%), 100 parts of pyrolusites (containing Mn 50.4%) are mixed (n
MnO2/ n
MoS2=3.0), breeze packed into is placed on the roasting that heats up in the tube type resistance furnace in the silica tube, and an end of silica tube connects gas blower, and the control air quantity is 20ml/min, utilizes temperature regulator that temperature is controlled at 450, roasting 360min.Product of roasting is carried out element sulphur analysis, Mo material phase analysis etc., and the result shows that sulfur-fixing rate is 92.9%, the oxidation ratio of Mo is 98.7%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).
The manganese Mo a word used in place name sand that contains that obtains adopts 17% hydrochloric acid soln leaching, leach to room temperature (25 ℃), soak that liquid-solid ratio is 30, extraction time is 180min, obtain containing red solution and the sour insoluble slag of Mo, Mn, the leaching yield of Mo is 97.9%, and the leaching yield of Mn is 88.2%.Subsequent step is with embodiment 1, and the ult rec of Mo is 93.7%, and the ult rec of Mn is 80.5% (MnCl
2).
Embodiment 5:
5 parts of molybdenum glance concentrate (containing Mo 47.4%), 16 parts of pyrolusite raw ores (containing Mn 24.8%) are mixed (n
MnO2/ n
MoS2=3.0), breeze packed into is placed on the roasting that heats up in the tube type resistance furnace in the silica tube, and an end of silica tube connects gas blower, and the control air quantity is 30ml/min, utilizes temperature regulator temperature to be controlled at 550 ℃, roasting 180min.Product of roasting is carried out element sulphur analysis, Mo material phase analysis etc., and the result shows that sulfur-fixing rate is 95.9%, the oxidation ratio of Mo is 100%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).The subsequent processing steps of a word used in place name sand is with embodiment 1.The ult rec of Mo is 95.7%, and the ult rec of Mn is 91.2% (MnSO
4).
Embodiment 6:
5 parts of molybdenum glance concentrate (containing Mo 47.4%), 16 parts of pyrolusite raw ores (containing Mn 24.8%) are mixed (n
MnO2/ n
MoS2=3.0), breeze packed into is placed on the roasting that heats up in the tube type resistance furnace in the silica tube, and an end of silica tube connects oxygen cylinder, and the control oxygen flow is 10ml/min, utilizes temperature regulator temperature to be controlled at 450 ℃, roasting 150min.Product of roasting is carried out element sulphur analysis, Mo material phase analysis etc., and the result shows that sulfur-fixing rate is 93.5%, the oxidation ratio of Mo is 100%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).The subsequent processing steps of a word used in place name sand is with embodiment 1.The ult rec of Mo is 95.9%, and the ult rec of Mn is 90.1% (MnSO
4).
Embodiment 7:
5 parts of molybdenum glance concentrate (containing Mo 47.4%), 16 parts of pyrolusite raw ores (containing Mn 24.8%) are mixed (n
MnO2/ n
MoS2=3.0) be placed on the roasting that heats up in the retort furnace, utilize temperature regulator that temperature is controlled at 350 ℃ of following roasting 60min, be warmed up to 450 ℃ of following roasting 60min then.Product of roasting is carried out the Mo material phase analysis, and the result shows that the oxidation ratio of Mo is 99.8%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).The subsequent processing steps of a word used in place name sand is with embodiment 1.The ult rec of Mo is 95.0%, and the ult rec of Mn is 89.5% (MnSO
4).
Embodiment 8:
5 parts of molybdenum glance concentrate chats (containing Mo 26.4%), 15 parts of pyrolusite raw ores (containing Mn 24.8%) are mixed (n
MnO2/ n
MoS2=5.0) be placed on the roasting that heats up in the retort furnace, utilize temperature regulator that temperature is controlled at temperature and be controlled at 550 ℃, roasting 100min.Product of roasting is carried out element sulphur analysis, Mo material phase analysis etc., and the result shows that sulfur-fixing rate is 96.9%, the oxidation ratio of Mo is 100%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).The subsequent processing steps of a word used in place name sand is with embodiment 1.The ult rec of Mo is 95.3%, and the ult rec of Mn is 74.9% (MnSO
4).
Embodiment 9:
5 parts of molybdenum glance concentrate chats (containing Mo 26.4%), 6 parts of pyrolusite raw ores (containing Mn 24.8%) are mixed (n
MnO2/ n
MoS2=2.0) after, utilize 0.1% CMC solution, breeze is pressed into cylindricality (diameter 5mm, high 8mm), place the retort furnace roasting that heats up, utilize temperature regulator that temperature is controlled at temperature and be controlled at 700 ℃, roasting 240min as binding agent.Product of roasting is carried out the Mo material phase analysis, and the result shows that the oxidation ratio of Mo is 99.4%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).The subsequent processing steps of a word used in place name sand is with embodiment 1.The ult rec of Mo is 94.7%, and the ult rec of Mn is 85.2% (MnSO
4).
Embodiment 10:
Molybdenum glance concentrate chats (containing Mo 26.4%), pyrolusite raw ore (containing Mn 24.8%) are mixed (n by 5: 3 mass ratioes
MnO2/ n
MoS2=1.0) after, join continuously in the small-sized rotary kiln, and discharging continuously; The temperature at rotary kiln middle part is controlled at 700～750 ℃, and the material roasting time is (residence time) 240min.Product of roasting is carried out the Mo material phase analysis, and the result shows that the oxidation ratio of Mo is 99.4%, the main component of a word used in place name sand is manganese molybdate (MnMoO
4).The subsequent processing steps of a word used in place name sand is with embodiment 1.The ult rec of Mo is 96.3%, and the ult rec of Mn is 87.1% (MnSO
4).
Claims (10)
1, the method for a kind of molybdenum glance and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate, it comprises the following step:
A, molybdenum glance and pyrolusite are pressed n
MnO2: n
MoS2=1.0～10.0 ratio mixings;
B, be 350 ℃～950 ℃ condition under common roasting in temperature with both mixture in same equipment, the time is 60～360min;
C, utilize mineral acid acidolysis product of roasting, acidolysis temperature is 5 ℃～95 ℃, and liquid-solid ratio is 1.0～50.0, and the acidolysis time is 5～300min, and the pH value of solution should obtain molybdenum salt, manganese salt solution and other insoluble impurities slag less than 5.5 after the acidolysis;
D, leach liquor after solvent extraction and separation, the raffinate water that obtains respectively containing the Mo extracted organic phase He contain Mn; For containing the Mo extracted organic phase, adopt the ammoniacal liquor back extraction to get ammonium molybdate solution;
E, the ammonium molybdate solution that obtains, manganese salt solution are continued to use existing corresponding ammonium molybdate and the manganese sulfate product of making of metallurgical technology.
2, the method for molybdenum glance according to claim 1 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate is characterized in that: the ratio n of molybdenum glance and pyrolusite in the above-mentioned steps (a)
MnO2: n
MoS2The mixing of=2.0～5.0, two kinds of mineral is that simple mechanical stirring is mixed, or adds binding agent compression moulding.
3, the method for molybdenum glance according to claim 1 and 2 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate, it is characterized in that: two kinds of mineral intermixture roastings in same equipment in the above-mentioned steps (b), its roasting apparatus is reverberatory furnace, rotary kiln, multiple hearth furnace or sulfuration bed roasting apparatus, its mode of production can be a continuous production, also can batch production.
4, the method for molybdenum glance according to claim 1 and 2 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate is characterized in that: maturing temperature is 450 ℃～600 ℃ in the above-mentioned steps (b).
5, the method for molybdenum glance according to claim 1 and 2 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate is characterized in that: calcination atmosphere is an air in the above-mentioned steps (b), or pure oxygen.
6, the method for molybdenum glance according to claim 1 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate is characterized in that: used mineral acid is sulfuric acid, hydrochloric acid or nitric acid in the above-mentioned steps (c), and the acidolysis process need keep the certain acidity of system.
7, the method for molybdenum glance according to claim 1 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate is characterized in that: used extraction agent is a secondary amine in the above-mentioned steps (d).
8, the method for molybdenum glance according to claim 7 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate, it is characterized in that: described extraction agent is N235, other composition of extracted organic phase has sulfonated kerosene, secondary octanol.
9, the method for molybdenum glance according to claim 1 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate, it is characterized in that: the metallurgical technology from ammonium molybdate solution recovery Mo in the above-mentioned steps (e) is that purification, acid are heavy, dry, and impurity level Gao Shixu carries out operations such as multistep ammonia is molten, acid is sunk.
10, the method for molybdenum glance according to claim 1 and pyrolusite common roasting coproduction ammonium molybdate and manganous sulfate is characterized in that: be to adjust pH value, purification and impurity removal, evaporative crystallization, recrystallization from containing the metallurgical technology that Mn solution reclaims Mn in the above-mentioned steps (e).
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320665A (en) * | 2011-07-27 | 2012-01-18 | 姚茂君 | Application of secondary air to process for reducing pyrolusite and producing sulfuric acid in fluidized bed furnace |
| CN101328540B (en) * | 2008-08-01 | 2012-05-23 | 自贡硬质合金有限责任公司 | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue |
| CN103343242A (en) * | 2013-07-01 | 2013-10-09 | 中南大学 | Method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate |
| CN104762474A (en) * | 2015-05-06 | 2015-07-08 | 中南大学 | Method for preparing ammonium molybdate through molybdenite |
| CN108396142A (en) * | 2018-05-03 | 2018-08-14 | 中南大学 | A kind of method of acid decomposed by phosphoric acid molybdenum calcining |
| CN109055727A (en) * | 2018-11-05 | 2018-12-21 | 中南大学 | A kind of method of nickel molybdenum in synthetical recovery nickel-molybdenum ore |
| CN109280764A (en) * | 2018-11-05 | 2019-01-29 | 中南大学 | A kind of cleaning smelting process using nickel-molybdenum ore |
| TWI779371B (en) * | 2019-10-21 | 2022-10-01 | 美商萬騰榮公司 | Molybdenum oxychloride with improved bulk density |
| CN116395744A (en) * | 2023-04-11 | 2023-07-07 | 辽宁天桥新材料科技股份有限公司 | Preparation method of ammonium molybdate |
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2007
- 2007-05-15 CN CN 200710034928 patent/CN101049968A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328540B (en) * | 2008-08-01 | 2012-05-23 | 自贡硬质合金有限责任公司 | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue |
| CN102320665A (en) * | 2011-07-27 | 2012-01-18 | 姚茂君 | Application of secondary air to process for reducing pyrolusite and producing sulfuric acid in fluidized bed furnace |
| CN103343242A (en) * | 2013-07-01 | 2013-10-09 | 中南大学 | Method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate |
| CN103343242B (en) * | 2013-07-01 | 2014-07-16 | 中南大学 | Method for interactively roasting bismuth sulfide ore and pyrolusite to extract bismuth and co-produce manganese sulfate |
| CN104762474A (en) * | 2015-05-06 | 2015-07-08 | 中南大学 | Method for preparing ammonium molybdate through molybdenite |
| CN108396142A (en) * | 2018-05-03 | 2018-08-14 | 中南大学 | A kind of method of acid decomposed by phosphoric acid molybdenum calcining |
| CN108396142B (en) * | 2018-05-03 | 2020-10-23 | 中南大学 | Method for decomposing molybdenum calcine by phosphoric acid |
| CN109055727A (en) * | 2018-11-05 | 2018-12-21 | 中南大学 | A kind of method of nickel molybdenum in synthetical recovery nickel-molybdenum ore |
| CN109280764A (en) * | 2018-11-05 | 2019-01-29 | 中南大学 | A kind of cleaning smelting process using nickel-molybdenum ore |
| TWI779371B (en) * | 2019-10-21 | 2022-10-01 | 美商萬騰榮公司 | Molybdenum oxychloride with improved bulk density |
| CN116395744A (en) * | 2023-04-11 | 2023-07-07 | 辽宁天桥新材料科技股份有限公司 | Preparation method of ammonium molybdate |
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