CN101717858B - Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals - Google Patents
Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals Download PDFInfo
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Abstract
The invention discloses a method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals, comprising the following steps of: ball-milling the polymetallic black-shale paragentic minerals, and then adding into a pressure kettle for oxygen pressure leaching to obtain leach liquor containing ferrous sulphate, molybdenum trisulfate acyl, vanadic acid and nickel sulfate and leach residues containing molybdic acid sediments; adding ammonia water into the leach liquor to extract the vanadium; then carrying out reextraction to obtain ammonium vanadate; generating sediments containing the molybdenum and the ferrum and a solution containing the nickel; filtering to obtain nickel carbonate; carrying out warming alkaline leach on the leach residues containing the molybdic acid sediments and the sediments containing the molybdenum and the ferrum; filtering to obtain an alkaline leach solution containing the molybdenum and filter residues containing the ferrum; after resin absorbs the molybdenum, eluting, acid-precipitating, filtering, drying and calcining to obtain molybdenum trioxide; and acid-dissolving, reducing and filtering the filter residues containing the ferrum to obtain green vitriol. The invention prevents the pollution of smoke gases, such as sulfur dioxide and the like in environment and has low production cost and high recovery rate of molybdenum, nickel and by-products of the vanadium and the ferrum.
Description
Technical field
The present invention relates to a kind of method of from many metals black shale mineral intergrowth, extracting molybdenum nickel vanadium iron, belong to the chemical metallurgy technical field.
Background technology
At present, profuse many metals black shale type mineral deposit is contained in China Hunan, Chongqing, three provinces and cities junctions, Guizhou Province, its resource compose deposit stable, grow better, bury more shallow, be easy to exploitation.More than 140 square kilometre black shale polymetallic ore district is only just arranged in area, Zun Yi; The estimation of resource amount of metal reaches about 1,000,000 tons, and wherein molybdenum reaches 3.5-9%, nickel 2-6%; Phosphorus 8-20%, sulphur 10-18%, iron 12-15%, carbon 10-12%, vanadium 0.05-1%, uranium 0.05%; Also have noble metals such as tungsten, platinum, rhodium, lead, possess commercial exploitation mostly and be worth, micro-characteristic shows the obvious enrichment of molybdenum, nickel, vanadium, cadmium, iron, zinc, copper of polymetallic ore layer in the black shale system.The black shale polymetallic ore is mainly composed a cover that is stored in Lower Cambrian Series and is rich in the siliceous black series of rocks of organic carbon, and the carbonaceous mudstone that comprise yeath, silicite, contains phosphorite nodule is formed, and contact surface has the thick waste mantle of 5～10cm.Apart from the about 2m of waste mantle place is the polymetallic ore layer, and ore body is stratiform, like stratiform and lensing output.
Find that after deliberation black shale is organic in close relations with various metalliferous minerals in the multiple metallic element ore bed, the symbiotic relationship between them mainly contains three kinds: one, organic matter and nickel molybdenum sulphide, pyrite are along a layer symbiosis; Two, organic parcel pyrite or nickel molybdenum sulphide: three, organic, pyrite is embedded in the nickel molybdenum sulphide, also finds in ore bed, to exist the cystocarp of red algae in addition, and the nickel molybdenum sulphide mainly accumulates in the encapsulating of cystocarp periphery.Through X-ray powder diffraction analysis and scanning electron microscope analysis; Its mineral composition is except the sulfide of main nickel molybdenum; Also have pyrite, zink sulphide, mispickel, yellow copper ore, lead glance etc.; Nickel-containing mineral has vaesite, bravoite, sulphur nickel minerals, millerite, nickel glance NiAsS, violarite, iron nickel glance NiAsS etc., and molybdenum mainly exists with the form of carbon sulphur molybdenum ore.
Because the singularity of mineral form, the comprehensive recovery ore dressing effect of many metals black shale mineral association resource is all undesirable, because the technique of preparing horizontal constraints; Process for extracting mainly adopts traditional electrosmelting molybdenum-iron; Roasting is leached, and high temperature oxygen is pressed and leached, on the process methodes such as normal temperature wet method leaching; What at present, do not have also that plant-scale technology and technology can be effective extracts molybdenum, nickel and other metals from many metals black shale mineral intergrowth.
The patent No. is that 97107568.9 patent of invention " technology of yellow soda ash conversion processing separation molybdenum and nickel from black shale " provides a kind of technology with yellow soda ash conversion processing separation molybdenum and nickel from black shale, it is through desulphurizing roasting, size mixing, transform, dissolve soak, purifying treatment and get, earlier with black shale desulphurizing roasting and pulverizing; The yellow soda ash of adding 50% and 30% water are sized mixing; Then through pyrolytic conversion, add water 100% again and dissolve and soak, with clear water wash immersion liquid; The immersion liquid tailings gets nickel ore concentrate; Again the immersion liquid dephosphorization is purified, filters, get clean liquid, handle promptly getting molybdenum nickel calcium salt product through heavy molybdenum.Though this invention can realize molybdenum nickel and separate that nickel wherein still rests in the slag, fails to obtain further concentration and separation, and whole sepn process do not isolate the metal of other tool value addeds, and the desulphurizing roasting process is to severe environmental pollution.
The patent No. be 99114737.5 patent of invention " extract the method for molybdenum and nickel salt from the molybdenum-nickel paragenetic ore deposit with diluted acid " and described a kind of hydrometallurgy field molybdenum-nickel paragenetic raw ore is directly leached the process method of nickel molybdenum salt with diluted acid and oxygenant; With the broken ball milling of molybdenum nickel minerals raw ore process; Obtain ammonium molybdate with diluted acid and oxygenant leaching, filtration, filtrating extraction and reextraction then; The surplus solution that comes together obtains single nickel salt through extraction and reextraction again, and raffinate obtains the sub product ferric ammonium sulfate through evaporation concentration.The taste 4.0～8.0% of raw ore molybdenum, the taste of nickel are 2.5～4.0%, and sulphur is 23%.Though the molybdenum of this inventive method, the total yield of nickel are higher; But the composition that obtains after separating is few; And other sub products with value in the ore are not separated such as vanadium, iron; Fail to reach to fully with effectively the utilizing of many metals black shale mineral intergrowth, have also simultaneously that technological operation is complicated, reagent consumption is big, cost is than problems such as height.
To the treatment process of above-mentioned many metals black shale mineral intergrowth, its weak point is that technical matters is complicated, and metal recovery rate is low and single, and valuable metal disperses; The separation difficulty of molybdenum, Ni-V-Fe in the mineral, reagent consumption is big, and cost is high, of poor benefits; Be difficult to overcome the complicacy of mineral, slag can't be handled, and has oxidizing roasting or with the salt roasting process; The environmental pollution of sulfurous gas is serious, produces a large amount of flue gases, serious environment pollution in the roasting process.
Summary of the invention
Weak point to above-mentioned prior art; The present invention provides a kind of Wet-process metallurgy method that from many metals black shale mineral intergrowth, extracts molybdenum, Ni-V-Fe; Its technical matters is simple, and tooling cost is low, and metal recovery rate is high and reclaim numerous in variety; Pollute environment is low, can effectively solve the problem that above-mentioned prior art exists.
To achieve these goals, the technical scheme of the present invention's employing is: a kind of method of from many metals black shale mineral intergrowth, extracting molybdenum, Ni-V-Fe is provided, and it comprises the steps:
(a), just mass percent is: add behind many metals black shale mineral intergrowth ball milling of molybdenum 2.5%～8%, nickel 1%～5%, vanadium 0.5%～1.0%, iron 5%～20%, sulphur 7%～25% and carry out the leaching of oxygen pressure in the autoclave pressure; Time is 3～6 hours; Add entry in the autoclave pressure; Heating back bubbling air; The Heating temperature temperature is greater than or equal to 200 ℃, carry out oxidizing reaction cross filter that sulfur acid is ferrous, molybdenum trisulfate acyl, vanadic acid and the leach liquor of single nickel salt and the leached mud that contains precipitate molybdic acid, liquid-solid ratio is 2～5: 1;
(b), the leach liquor of ferrous, the molybdenum trisulfate acyl of sulfur acid that step (a) is obtained, vanadic acid and single nickel salt adds the ammoniacal liquor extracting vanadium, strip again ammonium vanadate, with calcine after the ammonium vanadate drying Vanadium Pentoxide in FLAKES; Wherein adjust pH value of solution=1.5～2.5 in the leach liquor, extraction is in a ratio of 1～3: 1, adjustment strip liquor pH=8～10 in the strip liquor; Lead to and be steam heated to 45 ℃～65 ℃; Stir insulation 1～3 hour, back extraction is in a ratio of 1～3: 1, and the temperature during calcining is 400 ℃;
(c), in the raffinate of step (b), add oxidizer oxygen Separation of Molybdenum, iron and nickel, generate the throw out and the nickeliferous solution that contain molybdenum, iron, add yellow soda ash generation basic nickel carbonate in the filtrate filtered; Wherein Heating temperature is 90 ℃ in raffinate, and the reaction times is 3～5 hours, adds pH=3.5～5 of ammoniacal liquor, sodium hydroxide, sodium carbonate regulating solution;
(d), the throw out that contains molybdenum, iron that obtains of the leached mud that contains precipitate molybdic acid that step (a) is obtained and step (c) alkali of heating soaks, cross and filter alkali immersion liquid and the ferruginous filter residue that contains molybdenum; The alkali of wherein heating soaks that concentration of sodium carbonate is 60～100g/L in the process, and extraction temperature is 90 ℃, and extraction time is 2～6 hours;
(e), the pH of the alkali immersion liquid that obtains of set-up procedure (d) becomes acid; The ammoniacal liquor wash-out must contain the elutriant of molybdenum again after resin is inhaled molybdenum; Filter behind the elutriant acid heavy ammonium molybdate; With getting molybdic oxide after ammonium molybdate filtration, drying, the calcining, press leaching with making oxygen in the ammonium molybdate filtrate filtered returning pressure still; Wherein used ammonia concn is 10%, adds magnesium chloride in the elutriant and removes silicon, phosphorus, arsenic in the solution, and the condition that generates ammonium molybdate is pH=1.5～2.5;
(f), ferruginous filter residue acid that step (d) is obtained dissolves and generates ferric sulphate solution, reduction sulfuric acid high iron solution is a ferrous sulfate, filters and dry iron vitriol; With 10%～30% industrial sulphuric acid, temperature is carried out acid at 100 ℃ and is dissolved, and ferric sulphate solution reduces at 60 ℃～80 ℃ with iron filings, 10 ℃～30 ℃ following crystallizations, in vacuum tightness be under the vacuum of 13Kpa iron vitriol.The organic phase composition of extracting vanadium is 91% Numberl diesel fuel, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol, and the organic phase that contains vanadium is with 15% sulfuric acid back extraction.
Compared with prior art, the beneficial effect that this invention brings is: the high-temperature oxidation process that under pressurized state, carries out, and can be with more than the temperature increase to 200 ℃; Water is as leaching medium; Under the oxygenizement of oxygen in water, increase the contact probability of mineralogical composition and dissolved oxygen through high rotating speed, thereby realize oxidation conversion reaction compositions such as the molybdenum in the ore, Ni-V-Fes; Generation is dissolved in the metal polyion of WATER AS FLOW MEDIUM and realizes the leaching to molybdenum, Ni-V-Fe; The oxidation that original oxidizing roasting leaching method changes in WATER AS FLOW MEDIUM is leached, avoided smoke pollutions such as sulfurous gas, make the metallurgical technology process environmentally friendly; Metallurgical process is strengthened, and has realized molybdenum, Ni-V-Fe in many metals black shale mineral intergrowth are oxidized to the easy metal ion compound that dissolves.Therefore, the present invention is a kind of pollution-free metallurgical technology of strengthening oxidizing reaction, and whole technological process is simple; High and the recyclable various metal of metal recovery rate effectively separates wherein valuable metal molybdenum, Ni-V-Fe, and reagent consumption is little; Cost is low, and is profitable, can effectively overcome the complicacy of mineral; Slag is effectively handled recovery, and whole process has reduced the pollution to environment.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done further detailed description.
As shown in Figure 1, each composition quality per-cent of said many metals black shale mineral intergrowth is: molybdenum 2.5%～8%, nickel 1%～5%, vanadium 0.5%～1.0%, iron 5%～20%, sulphur 7%～25%; Its technological process does, earlier with many metals mineral intergrowth ball mill crushing levigate after, in autoclave pressure, carry out oxygen and press and leach the leached mud that obtains containing the leach liquor of molybdenum, Ni-V-Fe and contain precipitate molybdic acid with oxygenant; Again leach liquor is adjusted pH value to 2 with ammoniacal liquor; In five mixer-settlers, carry out counter-current extraction; The organic phase composition of extracting vanadium is 91% Numberl diesel fuel, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol, and the organic phase that contains vanadium is with 15% sulfuric acid back extraction.Strip liquor send settling tank, and logical steam heating adds ammonium chloride, the ammoniacal liquor precipitation gets ammonium vanadate, and ammonium vanadate is dry, calcine Vanadium Pentoxide in FLAKES.Raffinate after the extracting vanadium adds oxygenant oxidation ferrous ion wherein makes it to become ferric ion, and the adjustment pH value of solution separates, and makes the molybdenum in iron and the leach liquor generate deposition simultaneously, and nickel is separated with molybdenum, iron.Nickeliferous solution obtains nickelous carbonate with the yellow soda ash deposition; Deposition in molybdic acid in the leached mud and oxidation Separation of Molybdenum, the iron process is heated respectively after alkali soaks recovery molybdenum wherein; Adjustment alkali soaks pH; Through macroreticular weakly base resin absorption, wash-out, the elutriant that contains molybdenum purifies, acid heavy ammonium molybdate, ammonium molybdate obtains molybdic oxide after through calcining.The iron content filter residue of the deposition of oxidation Separation of Molybdenum, iron after alkali soaks; Add industrial sulphuric acid and carry out the molten reaction generation of acid ferric sulphate solution; With iron filings the ferric sulphate in the solution is reduced to ferrous sulfate; Filter out after superfluous iron filings are placed to room temperature, make copperas solution separate out the iron vitriol crystallization at low temperatures, fractional crystallization and vacuum-drying obtain iron vitriol.
Concrete technological process of the present invention is: with many metals mineral intergrowth ball mill crushing and levigate to 300 orders more than or equal to 90%; Add in the autoclave pressure; Add liquid-solid ratio in the autoclave pressure in advance and be 2～5: 1 water; After being heated above or equaling 200 ℃, feeding pressure is the pressurized air of 2～3MPa, and the high rotating speed (being not less than 200r/min) that stirs through airborne oxygen and reaction kettle carries out oxidizing reaction; The controlled oxidation time generated ferrous sulfate, molybdenum trisulfate acyl, vanadic acid and single nickel salt and gets into solution at 3～6 hour under the condition of HTHP; Part molybdenum generates molybdic acid and gets in the leached mud; The solution that will be rich in molybdenum, Ni-V-Fe after the filtration adds in the container for storing liquid, adds pH=1.5～2.5 of ammoniacal liquor adjustment solution, pours in the mixer-settler; Using composition is that the organic phase of 91% Numberl diesel fuel, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol is carried out the Pyatyi counter-current extraction, and extraction phase is than 0/A=1～3: 1, and the organic phase that contains vanadium is with 10%～20% sulfuric acid back extraction; As best mode, adopt 15% sulfuric acid back extraction, 0/A=1～3: 1 is compared in its back extraction; Strip liquor send settling tank, adds yellow soda ash, ammoniacal liquor adjustment strip liquor pH=8～10, leads to be steam heated to 45 ℃～65 ℃; Stir insulation 1～3 hour; Precipitation gets ammonium vanadate, and is at last that ammonium vanadate is dry, 400 ℃ calcine Vanadium Pentoxide in FLAKES.Raffinate is added in the container for storing liquid; After oxygenant oxidation ferrous ions wherein such as adding Youxiaolin, ydrogen peroxide 50, potassium permanganate make it to become ferric ion; PH=3.5～5 of regulator solution behind adding ammoniacal liquor, sodium hydroxide, the yellow soda ash; Be heated to 90 ℃ of reactions 3～5 hours; The deposition that makes ferric ion, molybdenum trisulfate acyl and other most of metals ion generations in the solution contain molybdenum 6%～15%, iron content 18%～30% is separated with nickel ion, filters the back and adds yellow soda ash, generates basic nickel carbonate.With leached mud and contain molybdenum, the iron precipitate alkali of heating respectively and soak recovery molybdenum wherein; Condition is following: liquid-solid ratio is 2～5: 1, and concentration of sodium carbonate is 60～100g/L, and extraction temperature is 90 ℃; Extraction time is 2～6 hours, and filtering the alkali immersion liquid and the ferruginous alkali that contain molybdenum soaks slag excessively.Alkali immersion liquid adjustment pH value of solution becomes acid, and the wherein polymerization of molybdenum ion helps the absorption of macroreticular weakly base resin to molybdenum; Treat that the saturated back of resin absorption carries out wash-out with 10% ammoniacal liquor to the molybdenum of resin absorption; The elutriant that must contain molybdenum contains and adds magnesium chloride in the elutriant of molybdenum the ammonia magnesium salts of generations indissolubles such as wherein silicon, phosphorus, arsenic is removed, and filters pH=1.5～2.5 that solution is adjusted in the back; Make the very little ammonium molybdate deposition of molybdenum generation solubleness, get molybdic oxide after filtration, drying, the calcining.Filtrating after acid is heavy is returned to do to leach and is used; Reclaim wherein a spot of molybdenum, the iron that ferruginous alkali soaks in the slag exists with the form of ironic hydroxide, and the industrial sulphuric acid with 10%～30% is heated in reaction kettle and dissolved and can generate ferric sulphate solution by complete solubilizing reaction to 100 ℃ of acid; With iron filings the ferric sulphate in the solution is reduced to ferrous sulfate; Keep solution temperature to carry out reduction reaction, filter out superfluous iron filings at 60 ℃～80 ℃, be placed to room temperature after; Make copperas solution separate out the iron vitriol crystallization at low temperatures, fractional crystallization and vacuum-drying obtain iron vitriol.
Embodiment one:
The composition of many metals black shale mineral intergrowth is: molybdenum 3.78%, nickel 1.92%, vanadium 0.83%, iron 11.8%, sulphur 21.3%.In 10000L enclosed reaction kettle, add 2T levigated polymetallic ore (300 orders >=90%) and 7T water; Many metals black shale mineral intergrowth is heated to 200 ℃, feeds pressurized air, pressure is 2MPa; 200 ℃ of controlled oxidation extraction temperatures under the stirring of high rotating speed (200r/min) in autoclave pressure; Reacted 5 hours, reaction end after-filtration must be filtrated and washings is total to 8.5T; Leach wet slag and amount to 4.5T (water ratio 69%), leach liquor composition: molybdenum: 4.63g/L, nickel 3.94g/L, vanadium 1.53g/L, iron 21.8g/L; Leached mud is staple after drying: molybdenum 2.79%, nickel 0.13%, vanadium 0.12%, iron 1.7%; There is the molybdenum of 95.4% nickel, about 91% vanadium, iron and about 50% to get into leach liquor in the pressure oxidation leaching process; All the other molybdenums get into leached mud with the form of molybdic acid, and the molybdenum in the leached mud soaks through the alkali of heating after macroreticular weakly base resin reclaims.
Vanadium in the leach liquor adds the pH=2 of ammoniacal liquor adjustment solution earlier, and using composition again is that the organic phase of 91% Numberl diesel fuel, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol is carried out the Pyatyi counter-current extraction, and extraction phase was than 2: 1; The extraction time is 1 hour; Percentage extraction is 95.3%, contains the vanadium organic phase with 15% sulfuric acid back extraction, and back extraction is compared 2: 1; Time is 2 hours, and back extraction ratio is 94.7%.Strip liquor send settling tank, adds 1: 1 yellow soda ash, ammoniacal liquor mixing solutions adjustment strip liquor pH=9, leads to be steam heated to 50 ℃; Stir insulation 3 hours, precipitation gets ammonium vanadate, and is after the filtration that ammonium vanadate is dry; 400 ℃ calcine Vanadium Pentoxide in FLAKES, the filtrating after the precipitation is sent wastewater treatment.
Molybdenum in the raffinate, nickel, iron are after oxidation, and the pH value of adjustment raffinate makes molybdenum, iron separate with nickel with sedimentary form; The molybdenum deposition rate is 98%, and the iron deposition rate is 93%, and nickel recovery is 96%; Reclaim molybdenum, nickel, iron more respectively, operating process is: add Youxiaolin and make that concentration reaches 10g/L in the solution, oxidation metals ion wherein; Treat in the solution that it is the oxidation terminal point that ferrous ion is oxidized into ferric ion entirely, add the pH=4.5 of industrial sodium hydroxide adjustment solution, heat to 90 ℃ of insulations 3 hours; Temperature raises and helps the deposition of molybdenum, iron, crosses to filter nickeliferous solution and the deposition that contains molybdenum, iron.Nickeliferous solution is adjusted pH=9 through industrial sodium carbonate, stirs to cross in 3.5 hours to filter nickelous carbonate, and the deposition that contains molybdenum can be soaked and reclaims with the molybdenum of the leached mud alkali of heating respectively, the deposition that contains molybdenum, iron through the alkali of heating soak reclaim molybdenum after, reclaim iron wherein again.
Leached mud and the leach liquor oxidation precipitation alkali of heating respectively soaks recovery molybdenum wherein; Operating process is: concentration of sodium carbonate 80g/L; Liquid-solid mass ratio 4: 1,90 ℃ of extraction temperatures leach 2 hours after-filtration; Molybdenum content is 0.15% in the leached mud, and the pH of alkali immersion liquid is more than or equal to 8.5 leachings fully with the assurance molybdenum.The alkali immersion liquid uses sulfuric acid adjustment pH to be acidity, lets molybdenum carry out polymerization, helps the absorption of macroreticular weakly base resin to molybdenum, treats that saturated back 10% ammonia soln with 1.5 times of resin volumes of resin absorption carries out wash-out, and must contain molybdenum is the 65g/L ammonium molybdate solution.
It is heavy that the ammonium molybdate solution that will contain molybdenum and be 65g/L carries out acid: add magnesium chloride earlier and remove silicon, phosphorus, arsenic in the ammonium molybdate solution; Make it to separate with molybdenum with ammonia magnesium salts deposition; Solution is separated out ammonium molybdate deposition through the stirring of fierceness with the pH to 2 of nitric acid adjustment solution behind silica removal, phosphorus, the arsenic under 50 ℃ of temperature.After the filtration ammonium molybdate crystal and the heavy liquid of acid, the heavy liquid of acid contains the molybdenum of 2.6g/L, can return to do pressurised oxygen and soak recovery molybdenum wherein, ammonium molybdate crystal becomes molybdic oxide through washing, oven dry, roasting.
The leach liquor oxidation precipitation is after the alkali of heating soaks the recovery molybdenum; The ironic hydroxide that ferruginous alkali soaks in the slag is heated molten to 100 ℃ of acid in enamel reaction still with 25% industrial sulphuric acid; Solubilizing reaction generates ferric sulphate solution fully, with iron filings the ferric sulphate in the solution is reduced to ferrous sulfate, keeps solution temperature at 70 ℃; Carried out reduction reaction 2 hours; Filter out after superfluous iron filings are placed to room temperature, make copperas solution separate out the iron vitriol crystallization at low temperatures, fractional crystallization and vacuum-drying obtain iron vitriol.The omnidistance recovery of molybdenum is 92%, and the omnidistance recovery of nickel is 93%, and vanadium, the iron sub product recovery reach 86%.
Embodiment two:
In 10000L enclosed reaction kettle, add 2T levigated polymetallic ore (300 orders >=90%) and 6T water, the composition of many metals black shale mineral intergrowth is: molybdenum 7.05%, nickel 3.93%, vanadium 0.73%, iron 13.8%, sulphur 18.7%.Many metals black shale mineral intergrowth is heated to 250 ℃, feeds pressurized air, pressure is 2.5MPa; 250 ℃ of controlled oxidation extraction temperatures under the stirring of high rotating speed (200r/min) in autoclave pressure; Reacted 4 hours, reaction end after-filtration must be filtrated and washings is total to 7.6T; Leach wet slag and amount to 3.5T (water ratio 59%), the leach liquor composition: molybdenum 11.13g/L, nickel 9.98g/L, vanadium 1.82g/L, iron 34.5g/L; Leached mud is staple after drying: molybdenum 3.93%, nickel 0.19%, vanadium 0.05%, iron 0.96%; There is the molybdenum of 95.4% nickel, about 95% vanadium, iron and about 50% to get into leach liquor in the pressure oxidation leaching process; All the other molybdenums get into leached mud with the form of molybdic acid, and the molybdenum in the leached mud soaks through the alkali of heating after macroreticular weakly base resin reclaims.
Vanadium in the leach liquor adds the pH=2 of ammoniacal liquor adjustment solution earlier, and using composition again is that the organic phase of 91% Numberl diesel fuel, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol is carried out the Pyatyi counter-current extraction, and extraction phase is than 0/A=1: 1; The extraction time is 1 hour; Percentage extraction is 96%, contains the vanadium organic phase with 15% sulfuric acid back extraction, and 0/A=1 is compared in back extraction: 1; Time is 3 hours, and back extraction ratio is 95.6%.Strip liquor send settling tank, adds 1: 1 yellow soda ash, ammoniacal liquor mixing solutions adjustment strip liquor pH=8.5, leads to be steam heated to 45 ℃; Stir insulation 2 hours, precipitation gets ammonium vanadate, and is after the filtration that ammonium vanadate is dry; 400 ℃ calcine Vanadium Pentoxide in FLAKES, the filtrating after the precipitation is sent wastewater treatment.
Molybdenum in the raffinate, nickel, iron are after oxidation, and the pH value of adjustment raffinate makes molybdenum, iron separate with nickel with sedimentary form; The molybdenum deposition rate is 97%, and the iron deposition rate is 94%, and nickel recovery is 95%; Reclaim molybdenum, nickel, iron more respectively, operating process is: add Youxiaolin, make that concentration reaches 8g/L in the solution; Oxidation metals ion wherein treats in the solution that it is the oxidation terminal point that ferrous ion is oxidized into ferric ion entirely, adds the pH=4.5 of industrial sodium carbonate adjustment solution; Heat to 90 ℃ of insulations 3 hours, temperature raises and helps the deposition of molybdenum, iron, crosses and filters nickeliferous solution and the deposition that contains molybdenum, iron.Nickeliferous solution is adjusted pH=9 through industrial sodium carbonate, stirs to cross in 3.5 hours to filter nickelous carbonate, and the deposition that contains molybdenum and the molybdenum of the leached mud alkali of heating respectively soaks and reclaims, the deposition that contains molybdenum, iron through the alkali of heating soak reclaim molybdenum after, recovery iron wherein again.
Leached mud and the leach liquor oxidation precipitation alkali of heating respectively soaks recovery molybdenum wherein; Operating process is: concentration of sodium carbonate 100g/L; Liquid-solid mass ratio 3: 1,90 ℃ of extraction temperatures, 2.5 hours after-filtration of extraction time; Molybdenum content is 0.33% in the leached mud, and the pH of alkali immersion liquid is more than or equal to 8.5 leachings fully with the assurance molybdenum.The alkali immersion liquid uses hydrochloric acid adjustment pH to be acidity, lets molybdenum carry out polymerization, helps the absorption of macroreticular weakly base resin to molybdenum, treats that saturated back 10% ammonia soln with twice resin volume of resin absorption carries out wash-out, and must contain molybdenum is the 57g/L ammonium molybdate solution.
It is heavy for the 57g/L ammonium molybdate solution carries out acid to contain molybdenum: add magnesium chloride earlier and remove silicon, phosphorus, arsenic in the ammonium molybdate solution; Make it to separate with molybdenum with ammonia magnesium salts deposition; Solution is separated out ammonium molybdate deposition through the stirring of fierceness with the pH to 1.6 of hydrochloride adjusted solution behind silica removal, phosphorus, the arsenic under 45 ℃ of temperature.After the filtration ammonium molybdate crystal and the heavy liquid of acid, the heavy liquid of acid contains the molybdenum of 1.1g/L, can return to do pressurised oxygen and soak recovery molybdenum wherein, ammonium molybdate crystal becomes molybdic oxide through washing, oven dry, roasting.
The leach liquor oxidation precipitation is after the alkali of heating soaks the recovery molybdenum; The ironic hydroxide that ferruginous alkali soaks in the slag is heated molten to 100 ℃ of acid in enamel reaction still with 20% industrial sulphuric acid; Solubilizing reaction generates ferric sulphate solution fully; With iron filings the ferric sulphate in the solution is reduced to ferrous sulfate, keeps solution temperature to carry out reduction reaction 2 hours, filter out after superfluous iron filings are placed to room temperature at 60 ℃; Make copperas solution separate out the iron vitriol crystallization at low temperatures, fractional crystallization and vacuum-drying obtain iron vitriol.The omnidistance recovery of molybdenum is 93%, and the omnidistance recovery of nickel is 92%, and vanadium, the iron sub product recovery reach 85%.
Claims (1)
1. from many metals black shale mineral intergrowth, extract the method for molybdenum nickel vanadium iron, it is characterized in that, comprise the steps:
(a), carry out the leaching of oxygen pressure in the autoclave pressure with adding behind many metals black shale mineral intergrowth ball milling; Add entry in the autoclave pressure; Heating back bubbling air carries out obtaining after oxidizing reaction is filtered that sulfur acid is ferrous, molybdenum trisulfate acyl, vanadic acid and the leach liquor of single nickel salt and the leached mud that contains precipitate molybdic acid; Wherein the extraction time in autoclave pressure is 3～6 hours, and temperature is greater than or equal to 200 ℃, and liquid-solid ratio is 2～5: 1;
(b), the leach liquor of ferrous, the molybdenum trisulfate acyl of sulfur acid that step (a) is obtained, vanadic acid and single nickel salt adds the ammoniacal liquor extracting vanadium, strip again ammonium vanadate, with calcine after the ammonium vanadate drying Vanadium Pentoxide in FLAKES; Wherein adjust pH value of solution=1.5～2.5 in the leach liquor, extraction is in a ratio of 1～3: 1, adjustment strip liquor pH=8～10 in the strip liquor; Lead to and be steam heated to 45 ℃～65 ℃; Stir insulation 1～3 hour, back extraction is in a ratio of 1～3: 1, and the temperature during calcining is 400 ℃;
(c), in the raffinate of step (b), add oxidizer oxygen Separation of Molybdenum, iron and nickel, generate the throw out and the nickeliferous solution that contain molybdenum, iron, add yellow soda ash generation basic nickel carbonate in the filtrate filtered; Wherein Heating temperature is 90 ℃ in raffinate, and the reaction times is 3～5 hours, adds pH=3.5～5 of ammoniacal liquor, sodium hydroxide, sodium carbonate regulating solution;
(d), the throw out that contains molybdenum, iron that obtains of the leached mud that contains precipitate molybdic acid that step (a) is obtained and step (c) alkali of heating soaks, cross and filter alkali immersion liquid and the ferruginous filter residue that contains molybdenum; The alkali of wherein heating soaks that concentration of sodium carbonate is 60～100g/L in the process, and extraction temperature is 90 ℃, and extraction time is 2～6 hours;
(e), the pH of the alkali immersion liquid that obtains of set-up procedure (d) becomes acid; The ammoniacal liquor wash-out must contain the elutriant of molybdenum again after resin is inhaled molybdenum; Filter behind the elutriant acid heavy ammonium molybdate; With getting molybdic oxide after ammonium molybdate filtration, drying, the calcining, press leaching with making oxygen in the ammonium molybdate filtrate filtered returning pressure still; Wherein used ammonia concn is 10%, adds magnesium chloride in the elutriant and removes silicon, phosphorus, arsenic in the solution, and the condition that generates ammonium molybdate is pH=1.5～2.5;
(f), ferruginous filter residue acid that step (d) is obtained dissolves and generates ferric sulphate solution, reduction sulfuric acid high iron solution is a ferrous sulfate, filters and dry iron vitriol; With 10%～30% industrial sulphuric acid, temperature is carried out acid at 100 ℃ and is dissolved, and ferric sulphate solution reduces at 60 ℃～80 ℃ with iron filings, 10 ℃～30 ℃ following crystallizations, in vacuum tightness be under the vacuum of 13Kpa iron vitriol.
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| CN102140576B (en) * | 2011-02-21 | 2013-03-06 | 中国科学院长春应用化学研究所 | Method for extracting nickel and molybdenum from nickel-molybdenum ore |
| CN102108440B (en) * | 2011-03-15 | 2012-08-08 | 中南大学 | Method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution |
| CN102312109B (en) * | 2011-09-16 | 2014-07-30 | 重庆大学 | Technology for extracting and separating nickel and molybdenum from bone coal ore by vacuum carbothermal reduction |
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| KR101466928B1 (en) * | 2014-03-05 | 2014-12-03 | 한국지질자원연구원 | Leaching method of valuable metal in spent catalyst of denitrification using high pressured leaching process |
| CN105925796A (en) * | 2016-04-29 | 2016-09-07 | 昆明理工大学 | Method for separating and recycling nickel-molybdenum iron from black rock series nickel-molybdenum iron sulfide ores |
| CN109411746B (en) * | 2018-11-05 | 2021-08-06 | 中南大学 | Method for preparing high-nickel ternary material precursor by using nickel-molybdenum ore |
| CN111392783B (en) * | 2020-03-26 | 2022-08-05 | 吉林吉恩镍业股份有限公司 | Method for removing vanadium ions from high-acid iron-and vanadium-containing nickel sulfate solution |
| CN113278797B (en) * | 2021-04-15 | 2022-05-17 | 有研工程技术研究院有限公司 | Process for extracting nickel and vanadium from black polymetallic shale based on microbial fluorination leaching |
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| CN101481754A (en) * | 2009-02-17 | 2009-07-15 | 昆明理工大学 | Method for separating molybdenum and nickel in molybdenum- and nickel-containing black shale |
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