CN104152687B - Aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale - Google Patents

Aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale Download PDF

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CN104152687B
CN104152687B CN201410343878.5A CN201410343878A CN104152687B CN 104152687 B CN104152687 B CN 104152687B CN 201410343878 A CN201410343878 A CN 201410343878A CN 104152687 B CN104152687 B CN 104152687B
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molybdenum
vanadium
nickel
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sulfate
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罗侣旦
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罗侣旦
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
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    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/234Recovering metals from waste by hydro metallurgy

Abstract

The invention discloses a kind of production technology that the elements such as aluminium, molybdenum, vanadium, nickel are reclaimed from black shale, comprise the following steps:Ore reduction fine grinding, adds additive, water and the concentrated sulfuric acid to mix thoroughly, then seals curing up for safekeeping;Curing material is blunged leaching, aluminum sulfate, nickel sulfate, molybdenum trisulfate acyl and vanadium sulfate acyl solution, solid-liquor separation is obtained;Filtrate adds ammonium salt or sylvite generation alum crystal, is separated by filtration;Aoxidized after filtrate regulation pH value, then adsorbed with resin anion (R.A.), desorbed with alkali lye;Regulation desorbed solution pH value, adds ammonium salt generation vanadic acid root, is separated by filtration;Filtrate adjusts pH value again, generates molybdic acid crystal, is separated by filtration;Liquid phosphoramidic-resin adsorbs nickel after ion exchange, and sulfuric acid wash-out is concentrated by evaporation generation nickel sulfate Crystallization Separation;Filtrate returns and uses.

Description

Aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale

Technical field

The present invention relates to a kind of non-ferrous metal low cost extraction scheme, comprehensively extracted particularly from black shale aluminium, vanadium, The elements such as molybdenum, nickel, the production technology without " three wastes " discharge, belong to hydrometallurgy chemical technology field.

Background technology

The main preservation of black shale in the ancient stratum such as Sinian system, Cambrian system and Silurian, because outward appearance containing charcoal be in black Or black gray expandable, some places are referred to as bone coal, have ash high, high-sulfur and the big feature of hardness mostly.Black shale often contains one Kind or several metallic elements, both individually into ore deposit can form navajoite, molybdenum ore, nickel minerals or uranium ore etc., also can association into ore deposit, formation vanadium Various mineral reserve such as molybdenum ore, molybdenum nickel minerals, molybdenum nickel navajoite, uvanite.This black shale ore deposit spreads all over province more than China, especially in China Guizhou Province, Hunan, Yu San province junctions contain very abundant many metal shales, only zunyi, guizhou just has more than 100 square kilometres Black shale Polymetallic Ore Deposit, in ore contain molybdenum 0.03 ~ 8.5%, nickel 0.1 ~ 5%, vanadium 0.1 ~ 2.5%, uranium 0.01 ~ 0.05%, aluminium 1.0 ~ 15%, iron 5 ~ 25%, sulphur 2 ~ 25%, charcoal 6 ~ 20%, metals resources amount exceed millions of tons.Black shale mineral intergrowth is China one Very advantageous mineral are planted, this black shale ore deposit is the multi-metal sulfide that a kind of difficulty selects amorphous state colloid state, and inside contains There are the organic compositions such as pitch, composition is complicated.Individual event metal element content is not high, it is difficult to carry out richness by the method for ore dressing Most of collection, traditional technique are that the technique of separating-purifying is leached using pyrogenic process roast wet, but can produce a large amount of titanium dioxides Sulphur gaseous contamination environment, and consume a large amount of chemical agents etc..Thereafter the new technology of many hydrometallurgys is occurred in that again, it is big to reduce Gas pollutes, and improves the rate of recovery.

Patent CN101338365 is, at 90 ~ 120 degree, to be presoaked miberal powder under 0 ~ 2 atmospheric pressure, and whole leaching is then will be pre- Immersion liquid at 85 ~ 150 degree, 0 ~ 5 atmospheric pressure, and be passed through under conditions of chlorine and carry out, whole phase analysis then wash molybdenum with ammoniacal liquor;

Patent CN101899569A is to insert in reactor miberal powder and NaOH, pressurizes and lead to oxygen, controls temperature 110 ~ 150 degree, molybdenum is dissolved, and nickel is retained in slag, realizes separation;

Patent CN10267680A is that miberal powder and nitrate, acid and water are configured in leaching solution addition reactor in proportion Reaction, filtrate is realized separating through UF membrane or ion-exchange process, and regulation pH value respectively obtains the compound of nickel and molybdenum;

Patent CN103014331A be will miberal powder, catalyst and acid solution add pressure reaction still in, lead to oxygen Leaching Molybdenum and Nickel.Catalyst used is the soluble compound of variable valency metal;

Patent CN101323915 is that molybdenum ore is carried out into pressurised oxygen leaching, then by extract and separate, generates nickel salt and oxidation Molybdenum;

Patent CN101289702 is that, by miberal powder diluted acid and oxidant pressure leaching, leachate passes through to extract and different Back washing agent respectively obtains ammonium molybdate and nickel sulfate;

Patent CN101177735 is that miberal powder is led into oxygen ammonification high pressure Leaching Molybdenum and nickel, is then produced by extract and separate Product;

Patent CN101717858A, is to carry out oxygen leaching during miberal powder is added into autoclave pressure, obtains sulfur acid ferrous iron, molybdenum trisulfate Acyl, the leachate of sulfuric acid vanadic acid and nickel sulfate and the leached mud containing precipitate molybdic acid;Then extracting vanadium, is stripped vanadium and obtains ammonium vanadate, Generation contains molybdenum, the sediment of iron and nickeliferous solution, filters to obtain nickelous carbonate;To contain the leached mud of precipitate molybdic acid with containing molybdenum, iron Sediment carries out heating alkali leaching, filters the alkali immersion liquid and the filter residue of iron content that must contain molybdenum;Eluted again after resin adsorption molybdenum, acid is heavy, mistake Filter;To contain that scum acid is molten, reduce, filter to obtain ferrous sulfate heptahydrate.

There is problems with above-mentioned technique:

First, reacted using autoclave pressure mostly, it is necessary to logical oxygen insulation of being pressurizeed, equipment manufacturing cost is high, unit source consumption Height, monomer production material is few, overall low production efficiency;

2nd, the consumption of acid is larger in whole flow process, and additive amount of medicament is more, and last part technology needs a large amount of alkali to neutralize, cost It is higher;

3rd, because content is too low, such as some vanadium molybdenum ores contain vanadium 1.5% to the low-grade element in ore, but only have containing molybdenum 0.1%, some molybdenum nickel minerals, containing molybdenum 5%, nickeliferous but there was only 0.15%, these low-grade first procatarxis extraction costs are higher in ore, Abandoned with slag after essential element is extracted mostly, cause the waste of resource;

4th, need to add a large amount of additives such as ammonium nitrate, sodium chlorate Strengthen education, so as to generate nitric acid in leachate Root, chlorate anions plasma, these ions can constantly remain accumulation in production is circulated, and not only influence the separation of next step to carry It is pure, and make industrial water be difficult to recycle.These waste water pollute the environment without being arranged outside purified treatment, if carried out net Then cost is very high for change treatment.

The black shale paragenetic mineral resource of China is enriched, and reserves are big, and accompanying element is more, if can comprehensively utilize, can be significantly Increase economic benefit and social benefit.Therefore, a kind of low production cost is found, environmental protection can to greatest extent extract ore In beneficial element production technology be hydrometallurgy industry from now on vital task.

The content of the invention

The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of technological process is simple, energy-conservation Consumption reduction, easy to operate, environmental protection, sour consumption is low, comprehensive recovery is high extraction aluminium, vanadium, molybdenum, nickel etc. from black shale The production technology of element.

To solve the above problems, technical scheme proposed by the present invention is realized by following step:

(1)Black shale is carried out into broken fine grinding, adds additive, water and the concentrated sulfuric acid to stir in proportion, Ran Hou Being stacked in digester carries out high-temperature maturing for 1-7 days, and temperature, humidity and the time of reaction are controlled in maturing process;

(2)By step(1)The leaching at normal temperatures and pressures of resulting Curing material, obtains sulfuric acid after solid-liquor separation Aluminium, nickel sulfate, molybdenum trisulfate acyl, vanadium sulfate acyl leachate and filter residue, filter residue send factory to make fuel;

(3)By step(2)Resulting leachate adds ammonium salt, aluminum sulfate and ammonium salt to combine to form alum crystallisation, filters Separate;

(4)By step(3)Resulting filtrate regulation pH value, adds oxidant, molybdenum trisulfate acyl and vanadium sulfate acyl to be oxidized Into molybdate and vanadic acid root;

(5)By step(4)Resulting oxidation solution passes through acrylic acid or styrenic anion exchanger resin, molybdate and vanadium Acid group is attracted on resin, is then parsed with alkali lye, the resin regeneration of sulfuric acid after parsing;

(6)The desorbed solution regulation pH value that will be obtained, adds ammonium salt, generates ammonium metavanadate precipitate, is separated by filtration;

(7)By step(6)The filtrate regulation pH value for obtaining, heating stirring generates precipitate molybdic acid, is separated by filtration, and filtrate is returned Return to step(1)For mixing and stirring material;

(8)By step(5)Again by phosphoramidic-resin, nickel ion is adsorbed liquid, uses sulfuric acid after the ion exchange for obtaining Parsing, the resin alkali liquid regeneration after parsing;

(9)Step(8)Liquid is back to step after resulting ion exchange(2), for leaching;

Realize that specific process parameter of the invention and flow are as follows

In above-mentioned steps(1)In, it is described to be characterized as:Fineness after black shale ball milling be accounting for less than 0.25mm 80% with On.

In above-mentioned steps(1)In, it is described to be characterized as:Additive refers to sodium sulphate, potassium sulfate, ferric sulfate, ferrous sulfate etc. One or more in sulfate.If internal chemical reaction during curing can be balanced, without addition.

In above-mentioned steps(1)In, it is described to be characterized as:Oxidant refers to oxygen, hydrogen peroxide, excessively sodium peroxide, carbon in air One kind in sour sodium, potassium permanganate, ammonium persulfate, manganese dioxide, the preferential oxygen using in air.In this step, in principle Chemical oxidizing agent need not be added, if necessary to control reaction speed, then above-mentioned chemical oxidizing agent can be properly added, but it is unsuitable The oxidants such as ammonium nitrate, sodium chlorate are imported, because a large amount of nitrate anions and chlorate anions can be generated, the recycling to leachate brings It is difficult.

In above-mentioned steps(1)In, it is described to be characterized as:Additive, water, the concentrated sulfuric acid proportioning be respectively ore weight 0.1 ~ 3%:5~15%:5~25%.The material mixed is inserted in digester and gives free rein to curing, it is not necessary to temperature-pressure, and the time is 1 ~ 7 day;It is ripe It is 60 ~ 200 degrees Celsius to change temperature, and no more than 250 degrees Celsius, otherwise moisture evaporation may cause very much spontaneous combustion to curing temperature soon. The control of curing temperature is proportioning by adjusting water and control evaporation capacity to be realized.

In above-mentioned steps(2)In, it is described to be characterized as:The leaching of Curing material is leaching at normal temperatures and pressures, liquid-solid ratio 1:1.The leachate and filter residue of aluminum sulfate, nickel sulfate, molybdenum trisulfate acyl and vanadium sulfate acyl are obtained after separation of solid and liquid.Filter residue contains More than 10% carbon can be sent to thermal power plant, cement plant and brick field as fuel.

In above-mentioned steps(3)In, it is described to be characterized as:The method that the method for extracting aluminium is plus ammonium salt or sylvite generate alum, Solubility is relatively low at normal temperatures for alum, and speed of separating out is very fast.Crystallization is finished, and can carry out separation of solid and liquid.The salt refers to sulfuric acid One kind in ammonium, ammonium carbonate, ammonium hydrogen carbonate, potassium sulfate, potassium carbonate.This step should not add ammonium chloride, potassium chloride, ammonium nitrate, The salts such as potassium nitrate, can otherwise influence the recycling of leachate.

In above-mentioned steps(4)In, it is described to be characterized as:By step(3)Resulting filtrate regulation pH value is 2 ~ 3.5, is added Oxidant, molybdenum trisulfate acyl and vanadium sulfate acyl in solution are oxidized to molybdate and vanadic acid root respectively.Described oxidant refers to One kind in hydrogen peroxide, sodium peroxide, SODIUM PERCARBONATE, potassium permanganate, ammonium persulfate.In this step, should not import ammonium nitrate, The oxidants such as sodium chlorate, otherwise can bring difficulty to the recycling of leachate.

In above-mentioned steps(5)In, it is described to be characterized as:By step(4)In the oxidation solution that obtains adjust pH value to 1 ~ 5, pass through Acrylic acid or styrenic anion exchanger resin, vanadic acid root and molybdate in solution are adsorbed, then with the hydroxide of 3mol Sodium solution parses resin, obtains the eluent of sodium metavanadate and sodium molybdate.

In above-mentioned steps(6)In, it is described to be characterized as:By step(5)The eluent for obtaining adjusts pH value to 7 ~ 10, adds sulphur Sour ammonium, generates ammonium metavanadate precipitate, then separation of solid and liquid.This step should not add ammonium chloride, in order to avoid influence following for industrial water Ring is used.

In above-mentioned steps(7)In, it is described to be characterized as:By step(6)The filtrate for obtaining adjusts pH value to 1 ~ 2, and stirring stands, Precipitate molybdic acid is generated, then separation of solid and liquid.Filtrate cycle is used, and send step(1)Curing is mixed and stirred with sulfuric acid, raw material.In filtrate SO42-, Na+, NH4+ plasma will be in generation chemical reaction be cured in slag in maturing process.

In above-mentioned steps(8)In, it is described to be characterized as:By step(5)The filtrate for obtaining passes through nickel ion chelating resin special, Nickel is adsorbed, and is parsed with the sulfuric acid of 1mol, and nickel sulfate crystallization, separation of solid and liquid are generated after eluent concentration.

In above-mentioned steps(9)In, it is described to be characterized as:Step(8)Ion exchange after liquid recycle, send step(2)Stir Leaching is mixed, realizes that waste water circulation is used.

Technology principle

Present invention mainly solves four technical problems of aspect:

One is the leaching rate that aluminium, vanadium, molybdenum, nickel are improved by slaking reaction;Two is to chemically react to reduce sulfuric acid by itself Consumption;Three is the closed cycle for realizing industrial water;Four is that low-grade element is utilized effectively.

Curing principle

At normal temperatures and pressures, be put into digester after miberal powder and the uniform mixing by a certain percentage of sulfuric acid, additive, sulfuric acid with The metallic compounds such as aluminium, potassium, sodium, iron, molybdenum, vanadium, nickel in miberal powder and silicate chemically react and release heat, and generation is big Amount sulfate and water, consume substantial amounts of sulfuric acid, and the concentration of sulfuric acid is decreased, and the heat that simultaneous reactions are produced makes Curing material temperature More than 90 degree are increased to, make the moisture evaporation of the moisture of itself institute's band and reaction generation, sulfuric acid remains higher concentration, at this Plant high temperature, concentrated acid and in air under the continuous effect of oxygen, the metal oxide in ore reacts, and generates sulfate from ore In cement out.This course of reaction, similar to brewing industry in " fermentation ", without the heating logical oxygen of pressurization, without costliness High temperature high voltage resistant corrosion protection equipment, only the raw material that will need to mix and stir be deposited in be sealed up for safekeeping in cement digester and give free rein to fermentation i.e. Can.Therefore, either construction cost or manufacturing cost are all substantially reduced, and are also generated without flue gas, are a kind of extremely promising Hydrometallurgical processes.

Reduce acid consumption principle

In ore maturing process, the chemical reaction of a series of complex is there occurs, a series of this reaction of itself is produced New sulfuric acid has been given birth to, the consumption of sulfuric acid is substantially reduced.The contained sulphur in ore of self-produced sulfuric acid, such as molybdenum sulfide and vulcanization The sulphur that nickel is carried, in the presence of iron in ore, generates sulfuric acid.Principle is as follows:

Iron is a kind of variable valency metal of high oxidation state.In high-temperature acidic aerobic environment, iron and sulfuric acid reaction in ore Generation ferric sulfate, the iron of trivalent has strong oxidizing property, the sulphur carried in ore can be direct oxidation into+6 valencys from-divalent, so as to generate Sulfuric acid, reaction equation is:

2FeO+3 H2SO4=Fe2( SO4)3+3H2O

MeS+4H2O+4 Fe2( SO4)3=MeSO4+4 H2SO4+8Fe SO4

So also having another reaction simultaneously can generate sulfuric acid, the ihleite reaction for seeing below.Reacted at both The sulfuric acid generation of significant proportion is had under effect, during slaking reaction, thus the actual consumption of sulfuric acid can be substantially reduced.

Realize the principle that industrial water is recycled

The main method for realizing industrial water circulation is the residual accumulation of harmful ion in anti-water-stop body, such as chlorine root, chloric acid Root, nitrate anion, fluoric acid root etc., the accumulation of these ions influence whether whole production technology, and the cost of purified treatment is also very high, So must control as far as possible.The approach for reducing ion accumulation is mainly carried out in terms of two, and one is to reduce harmful ion from outside Importing, institute's doping can not contain above-mentioned ion, and should based on sulfate because sulfate radical be easy to in raw material Calcium binding generates calcium sulfate precipitation, it is easy to process, and other ions are then difficult to process;Two is to suppress iron, potassium, sodium from inside Deng the dissolution of metal ion, method used is ihleite method.Ihleite is a kind of crystalline precipitate of indissoluble, it is easy to filters and washes Wash, highly stable, the solubility in water is very low.The molecular formula of ihleite is AFe3(SO4)2(OH)2, A refers to monovalent ion, Its formation condition is in addition to Fe3+, it is necessary to have the monovalent ions such as Na+, K+, NH+, and reaction equation is as follows:

Sodium jarosite:3Fe2( SO4)3+Na2 SO4+12 H2O = Na2 Fe6(SO4)4(OH)12+6 H2SO4

Autunezite:3Fe2( SO4)3+K2 SO4+12 H2O = K2 Fe6(SO4)4(OH)12+6 H2SO4

Ammonium jarosite:3Fe2( SO4)3+2NH4OH+10 H2O=(NH42 Fe6(SO4)4(OH)12+5 H2SO4

When ihleite is formed, the monovalent ion such as Na+, K+, NH+ in solution is cured in siderotil and is not dissolved, while There is sulfuric acid to produce, promote proceeding for subsequent reactions.

In the present invention, the element for forming ihleite reaction mostlys come from ore in itself, and outer doping is intended only as A kind of supplement of chemical reaction equilibrium.Under regular situation, the monovalent ion in ore is less, and iron ion is superfluous, therefore needs outer Carry out monovalent ion supplement to ensure reaction balance.Step(4)In oxidation reaction and step(7)In the heavy molybdenum of precipitation after filtrate In can generate a number of monovalent ion, preferentially above-mentioned ion is added in raw material carries out slaking reaction or leaching, Ihleite solidification is formed during curing or leaching, it is ensured that the reduction of harmful ion in solution.If by chemistry point Analysis is calculated, and these reactions still can not be balanced, then it is complete to ensure reaction to need addition foreign ion.As hypoferrism, then need Addition molysite;As potassium, sodium, ammonium are very few, then addition potassium, sodium, the sulfate of ammonium are needed., it is necessary to control temperature during reaction Degree and pH value, to accelerate the formation of ihleite.By ihleite method, the harmful ion in solution can be solidificated in slag, it is ensured that The recycling of industrial water.The principle that low-grade element is comprehensively extracted, in the present invention, the low-grade element in ore is by sulphur Ore Leaching, due to realizing closed cycle, does not have outer row, therefore low-grade element is progressively enriched with, when finite concentration is reached, then Can be extracted by ion-exchange, realize maximum resource utilization.

The present invention optimizes operation details by above-mentioned several principles, can preferably solve equipment investment greatly, and leaching rate is low, Sulfuric acid and reagent consumption are big, and industrial water can not be circulated, the problem such as environmental pollution is serious.

The present invention produced operation as a trial by the industrialization of 2 years, fact proved, without " three wastes " discharge, environment-friendly, flow Simply, the rate of recovery is high, low production cost, and comprehensive benefit is good, is worthy to be popularized.

Brief description of the drawings

Fig. 1 is process chart of the invention

Specific embodiment

Embodiment 1:

Hunan Zhangjiajie somewhere black shale molybdenum nickel vanadium mineral intergrowth, main component is:Aluminium 4.65%, vanadium 0.53%, molybdenum 3.36%th, nickel 1.65%, iron 13.2%, sulphur 17.1%, carbon 13%.It is broken to be finely ground to 100 mesh, compare additive according to quality:Water:Sulfuric acid: Ore=1.5:10:18:100 ratio uniform mixing, is put into digester and cures naturally 5 days, with 1:1 water is stirred 1 hour and soaked Go out, be separated by filtration.Filtrate adds ammonium sulfate, and generation ammonia-alum crystallization is separated by filtration, and pH value is adjusted with calcium carbonate, adds dioxygen Water oxygen, then by acrylic acid negative resin, is parsed with NaOH, and regulation desorbed solution to pH value to 7 ~ 10 adds ammonium sulfate Precipitation, generates ammonium metavanadate precipitate.It is separated by filtration, adjusts pH value to 1 ~ 2, heating stirring to generate precipitate molybdic acid with sulfuric acid.Filtering point From filtrate send step(1), and raw material carries out proportioning curing, solidifies potassium therein, sodium, ammonium plasma.Extract vanadium, after molybdenum from Liquid passes through phosphoramidic-resin after son is exchanged, and nickel is adsorbed, and is parsed with sulfuric acid, condensing crystallizing, and generation nickel sulfate hexahydrate crystal is separated.Carry Liquid send step after ion exchange after nickel(2)Leaching, recycles.Measuring metal comprehensive recovery is:Vanadium 82%, molybdenum 91%th, nickel 92%, aluminium 61%.Industrial water is circulated two months, and whole flow process is discharged without waste water and gas.Sulfur content reduction in waste residue 90%, phosphorus content is constant, send cement plant as fuel utilization.

Embodiment 2:

Hunan Jishou somewhere black shale bone coal navajoite, main component is:Aluminium 5.25%, vanadium 1.50%, molybdenum 0.16%, iron 9.5%th, sulphur 3.1%, carbon 11%.It is broken to be finely ground to 100 mesh, compare additive according to quality:Water:Sulfuric acid:Ore=2:8:20:100 Ratio uniform mixing, is put into digester and cures naturally 6 days, with 1:1 water is stirred 1 hour and leached, and is separated by filtration.Filtrate adds Ammonium sulfate, generation ammonia-alum crystallization, is separated by filtration, and pH value is adjusted with calcium carbonate, ammonium persulfate oxidation is added, then by propylene Sour negative resin, liquid send step after ion exchange(2)Leaching, is parsed with NaOH, adjusts desorbed solution to pH value to 7 ~ 10, Ammonium sulfate precipitation is added, ammonium metavanadate precipitate is generated.It is separated by filtration, adjusts pH value to 1 ~ 2, heating stirring to generate molybdic acid with sulfuric acid Precipitation.It is separated by filtration, filtrate is by sending step(1)Proportioning curing is carried out with raw material, solidifies potassium therein, sodium, ammonium plasma.Survey Obtaining metal comprehensive recovery is:Vanadium 87%, molybdenum 63%, aluminium 52%.Industrial water is circulated six months, and whole flow process is arranged without waste water and gas Put, sulfur content reduction by 85% in waste residue, phosphorus content is constant, send cement plant as fuel utilization.

Embodiment 3:

Zunyi, guizhou somewhere black shale molybdenum nickel minerals, main component is:Aluminium 7.1%, molybdenum 6.1%, nickel 3.85%, iron 13.5%, Sulphur 18.1%, carbon 16%.It is broken to be finely ground to 100 mesh, compare additive according to quality:Water:Sulfuric acid:Ore=0.5:11:25:100 ratio Example uniform mixing, is put into digester and cures naturally 7 days, with 1:1 water is stirred 1 hour and leached, and is separated by filtration, and filter residue send cement Factory.Filtrate adds ammonium sulfate, and generation ammonia-alum crystallization is separated by filtration, and pH value is adjusted with calcium carbonate, adds potassium permanganate oxidation, Then by acrylic anionic resin, molybdenum is adsorbed.Parsed with NaOH, regulation desorbed solution to pH value to 1 ~ 2, stir by heating Mix, generate precipitate molybdic acid, be separated by filtration, filtrate send step(1), and raw material proportioning curing, solidify potassium therein, sodium, ammonium etc. from Son.By phosphoramidic-resin, nickel is adsorbed liquid, is parsed with sulfuric acid, concentrates result, generates sulfuric acid after extracting the ion exchange of molybdenum Nickel crystal.Liquid send step after putting forward the ion exchange after nickel(2)Leaching, realizes recycling.Measure metal comprehensive recovery For:Molybdenum 90%, nickel 93%, aluminium 69%.Industrial water is circulated two months, and whole flow process is discharged without waste water and gas, sulfur content drop in waste residue Low by 86%, phosphorus content is constant, and waste residue is used as fuel utilization.

Claims (5)

1. aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale, it is characterised in that:
Comprise the following steps:
(1)Black shale is carried out into broken fine grinding, adds additive, water and the concentrated sulfuric acid to stir in proportion, in digester Stacking carries out high-temperature maturing for 1-7 days, and temperature, humidity and the time of reaction are controlled in maturing process;It is described additive, water, dense The proportioning of sulfuric acid is respectively the 0.1 ~ 3% of ore weight:5~15%:5~25%;Described additive refers to sodium sulphate, potassium sulfate, sulphur One or more in sour iron, ferrous sulfate;
(2)By step(1)The leaching at normal temperatures and pressures of resulting Curing material, obtains aluminum sulfate, sulphur after solid-liquor separation Sour nickel, molybdenum trisulfate acyl, vanadium sulfate acyl leachate and filter residue, filter residue send factory to make fuel;
(3)By step(2)Resulting leachate adds ammonium salt, and aluminum sulfate and ammonium salt combine to form alum crystallisation, be separated by filtration; The ammonium salt refers to one or more in ammonium sulfate, ammonium hydrogen carbonate, ammonium carbonate;
(4)By step(3)Resulting filtrate regulation pH value, adds oxidant, and molybdenum trisulfate acyl and vanadium sulfate acyl are oxidized to molybdenum Acid group and vanadic acid root;The oxidant refers to the one kind in hydrogen peroxide, sodium peroxide, potassium permanganate, ammonium persulfate, manganese dioxide Or it is several;
(5)By step(4)Resulting oxidation solution regulation pH value, is adsorbed by anion exchange resin, molybdate and vanadium Acid group is attracted on resin, is then parsed with alkali lye, the resin regeneration of sulfuric acid after parsing;The anion exchange resin is Refer to acrylic acid or styrenic anion exchanger resin;The parsing of the resin is to use NaOH, and the regeneration of resin is to use sulfuric acid;
(6)By step(5)Resulting desorbed solution regulation pH value, adds ammonium sulfate, generates ammonium metavanadate precipitate, is separated by filtration;
(7)By step(6)The filtrate regulation pH value for obtaining, generates precipitate molybdic acid, is separated by filtration, and filtrate returns to step(1)With In mixing and stirring material;
(8)By step(5)Again by phosphoramidic-resin, nickel ion is adsorbed, is parsed with sulfuric acid liquid after the ion exchange for obtaining;
(9)Step(8)Liquid is back to step after resulting ion exchange(2), for leaching.
2. it is as claimed in claim 1 that aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale, its It is characterised by:
The approach for reducing sulphuric acid cost is to generate sulfuric acid under chemical reaction effect using the self-contained sulphur of ore.
3. it is as claimed in claim 1 that aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale, its It is characterised by:
The step(8)The method of extraction nickel be technique with ion exchange, ion exchange resin is phosphoramidic-resin, tree The parsing of fat is to use sulfuric acid, and regeneration is to use NaOH.
4. it is as claimed in claim 1 that aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale, its It is characterised by:
It is that the residual for controlling difficult element is accumulated to realize that industrial wastewater is circulated and reduces the approach of production cost:One is from outside Reduce or prevent chlorine root, chlorate anions, nitrate anion, the importing of fluoric acid root, the non-above-claimed cpd of institute's doping;Two is from inside Suppress iron, potassium, the dissolution of sodium metal ion, method used is ihleite method;Three be to be formed ihleite reaction element more Come from ore in itself, outer doping is intended only as a kind of supplement of chemical reaction equilibrium.
5. it is as claimed in claim 1 that aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale, its It is characterised by:
The method for extracting ore middle-low grade element is, by the iterative cycles of leachate, these Minor elements is constantly accumulated Enrichment, concentration is stepped up so as to reach the purpose of separating-purifying.
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CN105039746A (en) * 2015-08-28 2015-11-11 长沙矿冶研究院有限责任公司 Method for directly extracting high-purity vanadium pentoxide from stone coal vanadium ore
CN105714119B (en) * 2016-04-08 2018-06-29 金川集团股份有限公司 A kind of method for recycling nickel from nickeliferous calcium and magnesium slag with ion exchanged soln
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
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CN102260792A (en) * 2011-07-25 2011-11-30 张国茂 Method for extracting vanadium by heap leaching and adding concentrated sulfuric acid and additive in vanadium-containing stone coal

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