CN101717858A - 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, 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-feature 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 to exist in ore bed the cystocarp of red algae in addition, and the nickel molybdenum sulphide mainly accumulates in the bag quilt 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, chalcopyrite, 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 technique of preparing horizontal constraints, extracting method mainly adopts traditional electrosmelting molybdenum-iron, roasting is leached, and high temperature oxygen is pressed and leached, on the processing 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, molten soaking, purifying treatment and getting, 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% molten soaking again, with clear water wash immersion liquid, the immersion liquid tailings gets nickel ore concentrate, again the immersion liquid dephosphorization is purified, filter, 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 processing 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, filtrate extraction and reextraction then, raffinate solution obtains single nickel salt through extraction and reextraction again, and raffinate obtains the byproduct 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 byproducts with value in the ore are not separated such as vanadium, iron, fail to reach to fully and effectively the utilizing of many metals black shale mineral intergrowth, have also simultaneously that technological operation complexity, reagent consumption are big, cost is than problems such as height.
At the treatment process of above-mentioned many metals black shale mineral intergrowth, its weak point is the technical matters complexity, and metal recovery rate is low and single, valuable metal disperses, the separation difficulty of molybdenum, Ni-V-Fe in the mineral, reagent consumption is big, cost height, 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, produce a large amount of flue gases, serious environment pollution in the roasting process.
Summary of the invention
At above-mentioned the deficiencies in the prior art part, the 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, tooling cost is low, 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 solution used in the present invention is: a kind of method of extracting molybdenum, Ni-V-Fe from many metals black shale mineral intergrowth is provided, and it comprises 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, carry out oxidizing reaction filter ferrous, the molybdenum trisulfate acyl of sulfur acid, vanadic acid and the leach liquor of single nickel salt and the leached mud that contains precipitate molybdic acid;
(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;
(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;
(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, and filters to such an extent that contain the alkali immersion liquid and the ferruginous filter residue of molybdenum;
(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, to get molybdic oxide after ammonium molybdate filtration, drying, the calcining, will make oxygen in the ammonium molybdate filtrate filtered returning pressure still and press leaching;
(f), with the molten generation ferric sulphate solution of ferruginous filter residue acid that step (d) obtains, reduction sulfuric acid high iron solution is a ferrous sulfate, filters and dry iron vitriol.
Realize that concrete processing parameter of the present invention is:
In step (a), 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;
In step (b), adjust pH value of solution=1.5～2.5 in the leach liquor, extraction is in a ratio of 1～3: 1, adjust strip liquor pH=8～10 in the strip liquor, logically 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 ℃;
In step (c), 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;
In step (d), the alkali of 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.
In step (e), used ammonia concn is 10%, adds silicon, phosphorus, arsenic in the magnesium chloride removal solution in the elutriant, and the condition that generates ammonium molybdate is pH=1.5～2.5;
In step (f), with 10%～30% industrial sulphuric acid, it is molten that temperature is carried out acid at 100 ℃, 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 be 91% 1
#Diesel oil, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol, the organic phase that contains vanadium is with 15% sulfuric acid back extraction.
Mass percent in many metals mineral intergrowth is: molybdenum 2.5%～8%, nickel 1%～5%, vanadium 0.5%～1.0%, iron 5%～20%, sulphur 7%～25%.
Compared with prior art, the beneficial effect that this invention brings is: the high-temperature oxidation process that carries out under pressurized state, 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 by high rotating speed, thereby realize the molybdenum in the ore, nickel, vanadium, the oxidation conversion reaction of compositions such as iron, generation is dissolved in the metal polyion of WATER AS FLOW MEDIUM and realizes molybdenum, nickel, vanadium, the leaching of iron, the oxidation that original oxidizing roasting leaching method changes in WATER AS FLOW MEDIUM is leached, smoke pollutions such as sulfurous gas have been avoided, make the metallurgical technology process environmentally friendly, metallurgical process is strengthened, and has realized the molybdenum in many metals black shale mineral intergrowth, nickel, vanadium, iron is oxidized to the metal ion compound of Yi Rong.Therefore, the present invention is a kind of pollution-free metallurgical technology of strengthening oxidizing reaction, whole technological process is simple, and the high and recyclable various metal of metal recovery rate effectively separates wherein valuable metal molybdenum, Ni-V-Fe, 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
The present invention is described in further detail below in conjunction with drawings and the specific embodiments.
As shown in Figure 1, each composition quality per-cent of described 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 is, 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, carries out counter-current extraction, the organic phase composition of extracting vanadium be 91% 1
#Diesel oil, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol, 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, with the ammonium vanadate drying, calcine Vanadium Pentoxide in FLAKES.Raffinate after the extracting vanadium adds oxygenant oxidation ferrous ion wherein makes it to become ferric ion, adjusts pH value of solution and separates, and makes the molybdenum in iron and the leach liquor generate precipitation simultaneously, and nickel is separated with molybdenum, iron.Nickeliferous solution obtains nickelous carbonate with the yellow soda ash precipitation, precipitation in molybdic acid in the leached mud and oxidation Separation of Molybdenum, the iron process is heated respectively after alkali soaks recovery molybdenum wherein, adjust alkali and soak 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 precipitation of oxidation Separation of Molybdenum, iron after alkali soaks, add industrial sulphuric acid and carry out sour molten reaction generation 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.
Specific embodiment 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, high rotating speed (being not less than 200r/min) through airborne oxygen and reactor stirring carries out oxidizing reaction, the controlled oxidation time generated ferrous sulfate, molybdenum trisulfate acyl, vanadic acid and single nickel salt and enters solution at 3～6 hour under the condition of High Temperature High Pressure; Part molybdenum generates molybdic acid and enters 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 that ammoniacal liquor is adjusted solution, pour in the mixer-settler, with composition be 91% 1
#The organic phase of diesel oil, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol is carried out the Pyatyi counter-current extraction, extraction phase was than 0/A=1～3: 1, 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, add yellow soda ash, ammoniacal liquor adjustment strip liquor pH=8～10, logical be steam heated to 45 ℃～65 ℃, stir insulation 1～3 hour, precipitation gets ammonium vanadate, at last with the ammonium vanadate drying, 400 ℃ calcine Vanadium Pentoxide in FLAKES.Raffinate is added in the container for storing liquid, after oxygenant oxidation ferrous ions wherein such as adding clorox, hydrogen peroxide, 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 precipitation that makes ferric ion, molybdenum trisulfate acyl and other most of metal ion generations in the solution contain molybdenum 6%～15%, iron content 18%～30% is separated with nickel ion, filter the back and add yellow soda ash, generate basic nickel carbonate.With leached mud and contain molybdenum, the iron precipitate alkali of heating respectively and soak recovery molybdenum wherein, condition is as follows: 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, filter contain molybdenum alkali immersion liquid and ferruginous alkali soak slag.The alkali immersion liquid is adjusted pH value of solution and is become acid, the wherein polymerization of molybdenum ion, help 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 of back adjustment solution, make the very little ammonium molybdate precipitation of molybdenum generation solubleness, get molybdic oxide after filtration, drying, the calcining.Filtrate 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, industrial sulphuric acid with 10%～30% is heated in reactor and can be generated ferric sulphate solution by complete solubilizing reaction to 100 ℃ of acid is molten, with iron filings the ferric sulphate in the solution is reduced to ferrous sulfate, keep solution temperature to carry out reduction reaction at 60 ℃～80 ℃, filter out superfluous iron filings, after being placed to room temperature, 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 reactor, add 2T levigated polymetallic ore (300 orders 〉=90%) and 7T water, many metals black shale mineral intergrowth is heated to 200 ℃, feed 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 finishes after-filtration, get filtrate and washings 8.5T altogether, 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; Main component after the leached mud 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 enter leach liquor in the pressure oxidation leaching process, all the other molybdenums enter leached mud with the form of molybdic acid, and the molybdenum in the leached mud soaks by the alkali of heating after macroreticular weakly base resin reclaims.
Vanadium in the leach liquor adds the pH=2 that ammoniacal liquor is adjusted solution earlier, again with composition be 91% 1
#The organic phase of diesel oil, 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, and 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, and the yellow soda ash, the ammoniacal liquor mixing solutions that added 1: 1 are adjusted strip liquor pH=9, leads to be steam heated to 50 ℃, stir insulation 3 hours, precipitation gets ammonium vanadate, after the filtration with the ammonium vanadate drying, 400 ℃ calcine Vanadium Pentoxide in FLAKES, the filtrate after the precipitation is sent wastewater treatment.
Molybdenum in the raffinate, nickel, iron is after oxidation, adjust the pH value of raffinate, make molybdenum, iron separates with nickel with sedimentary form, the molybdenum deposition rate is 98%, the iron deposition rate is 93%, nickel recovery is 96%, reclaim molybdenum more respectively, nickel, iron, operating process is: add clorox and make that concentration reaches 10g/L in the solution, oxidation metal ion wherein treats in the solution that it is the oxidation terminal point that ferrous ion is oxidized into ferric ion entirely, add industrial sodium hydroxide and adjust the pH=4.5 of solution, heat to 90 ℃ of insulations 3 hours, temperature raises and helps molybdenum, the precipitation of iron, filter nickeliferous solution and contain molybdenum, the precipitation of iron.Nickeliferous solution is adjusted pH=9 through industrial sodium carbonate, stir filtered in 3.5 hours nickelous carbonate, the precipitation that contains molybdenum can be soaked and reclaimed with the molybdenum of the leached mud alkali of heating respectively, the precipitation 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.It is acid that the alkali immersion liquid is adjusted pH with sulfuric acid, allows 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 precipitation, solution is separated out ammonium molybdate precipitation by 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, keep 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 rate of recovery of molybdenum is 92%, and the omnidistance rate of recovery of nickel is 93%, and vanadium, the iron byproduct rate of recovery reach 86%.
Embodiment two:
Add 2T levigated polymetallic ore (300 orders 〉=90%) and 6T water in 10000L enclosed reactor, 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 ℃, feed 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 finishes after-filtration, gets filtrate and washings 7.6T altogether, 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; Main component after the leached mud 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 enter leach liquor in the pressure oxidation leaching process, all the other molybdenums enter leached mud with the form of molybdic acid, and the molybdenum in the leached mud soaks by the alkali of heating after macroreticular weakly base resin reclaims.
Vanadium in the leach liquor adds the pH=2 that ammoniacal liquor is adjusted solution earlier, again with composition be 91% 1
#The organic phase of diesel oil, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol is carried out the Pyatyi counter-current extraction, extraction phase is than 0/A=1: 1, the extraction time is 1 hour, percentage extraction is 96%, contain the vanadium organic phase with 15% sulfuric acid back extraction, 0/A=1 is compared in back extraction: 1, and the time is 3 hours, back extraction ratio is 95.6%.Strip liquor send settling tank, and the yellow soda ash, the ammoniacal liquor mixing solutions that added 1: 1 are adjusted strip liquor pH=8.5, leads to be steam heated to 45 ℃, stir insulation 2 hours, precipitation gets ammonium vanadate, after the filtration with the ammonium vanadate drying, 400 ℃ calcine Vanadium Pentoxide in FLAKES, the filtrate after the precipitation is sent wastewater treatment.
Molybdenum in the raffinate, nickel, iron is after oxidation, adjust the pH value of raffinate, make molybdenum, iron separates with nickel with sedimentary form, the molybdenum deposition rate is 97%, the iron deposition rate is 94%, nickel recovery is 95%, reclaim molybdenum more respectively, nickel, iron, operating process is: add clorox, make that concentration reaches 8g/L in the solution, oxidation metal 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 that industrial sodium carbonate is adjusted solution, heat to 90 ℃ of insulations 3 hours, temperature raises and helps molybdenum, the precipitation of iron, filter nickeliferous solution and contain molybdenum, the precipitation of iron.Nickeliferous solution is adjusted pH=9 through industrial sodium carbonate, stir filtered in 3.5 hours nickelous carbonate, the molybdenum that contains the precipitation of molybdenum and the leached mud alkali of heating respectively soaks and is reclaimed, the precipitation 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 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.It is acid that the alkali immersion liquid is adjusted pH with hydrochloric acid, allows 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: the adding magnesium chloride is removed silicon, phosphorus, the arsenic in the ammonium molybdate solution earlier, make it to separate with molybdenum with ammonia magnesium salts precipitation, solution is separated out ammonium molybdate precipitation by 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, keep solution temperature to carry out reduction reaction 2 hours at 60 ℃, 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 rate of recovery of molybdenum is 93%, and the omnidistance rate of recovery of nickel is 92%, and vanadium, the iron byproduct rate of recovery reach 85%.
Claims (4)
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, carry out oxidizing reaction filter ferrous, the molybdenum trisulfate acyl of sulfur acid, vanadic acid and the leach liquor of single nickel salt and the leached mud that contains precipitate molybdic acid;
(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;
(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;
(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, and filters to such an extent that contain the alkali immersion liquid and the ferruginous filter residue of molybdenum;
(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, to get molybdic oxide after ammonium molybdate filtration, drying, the calcining, will make oxygen in the ammonium molybdate filtrate filtered returning pressure still and press leaching;
(f), with the molten generation ferric sulphate solution of ferruginous filter residue acid that step (d) obtains, reduction sulfuric acid high iron solution is a ferrous sulfate, filters and dry iron vitriol.
2. the method for extracting molybdenum nickel vanadium iron from many metals black shale mineral intergrowth according to claim 1 is characterized in that,
In the step (a), 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;
In the step (b), adjust pH value of solution=1.5～2.5 in the leach liquor, extraction is in a ratio of 1～3: 1, adjust strip liquor pH=8～10 in the strip liquor, logically 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 ℃;
In the step (c), the Heating temperature in the raffinate is 90 ℃, and the reaction times is 3～5 hours, adds pH=3.5～5 of ammoniacal liquor, sodium hydroxide, sodium carbonate regulating solution;
In the step (d), the alkali of 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.
In the step (e), used ammonia concn is 10%, adds silicon, phosphorus, arsenic in the magnesium chloride removal solution in the elutriant, and the condition that generates ammonium molybdate is pH=1.5～2.5;
In the step (f), with 10%～30% industrial sulphuric acid, it is molten that temperature is carried out acid at 100 ℃, 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.
3. the method for extracting molybdenum nickel vanadium iron from many metals black shale mineral intergrowth according to claim 1 is characterized in that, the organic phase composition of extracting vanadium be 91% 1
#Diesel oil, two-2-ethyl-hexyl phosphoric acid of 6%, 3% isodecyl alcohol, the organic phase that contains vanadium is with 15% sulfuric acid back extraction.
4. the method for from many metals black shale mineral intergrowth, extracting molybdenum nickel vanadium iron according to claim 1, it is characterized in that the mass percent in many metals mineral intergrowth is: molybdenum 2.5%～8%, nickel 1%～5%, vanadium 0.5%～1.0%, iron 5%～20%, sulphur 7%～25%.
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