CN103074488B - Oxidation leaching method and system - Google Patents
Oxidation leaching method and system Download PDFInfo
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Abstract
The invention provides an oxidation leaching method which comprises the steps of 1) smashing a raw material, and mixing with sodium chlorate, potassium chlorate or potassium permanganate, 2) adding water and filling oxygen-bearing gas into a sealed system, and igniting with a combustible, 3) stopping filling the oxygen-bearing gas, spraying water mist into a reaction mixture and filling chlorine or oxygen for 20-600min, 4) stopping spraying the water mist till the reaction mixture does not generate steam any longer, adding an inorganic acid dissolution reaction mixture, and controlling a pH (Potential of Hydrogen) value of a solution to be 1-3.5, and 5) conducting solid-liquid separation on the reaction mixture and taking a liquid phase. According to the method, harmful gas such as the chlorine is leached without a tail gas absorption facility any longer, mixed gas with lower percent by volume of the chlorine can be made full use of, oxidizing gas is effectively utilized while the operating cost of tail gas absorption is lowered, the utilization ratio of a reagent and a material is increased, the process control point is simplified, the operation is simple, and the process is easier to control.
Description
Technical field
The invention belongs to raw-material preprocessing technical field, be specifically related to the raw-material method of a kinds of oxidation reaction pre-treatment and system thereof.
Background technology
In the fields such as metallurgy, materials processing, need insoluble raw material to leach dissolution process.For insoluble raw material, existing dissolving leaching-out technique mainly contains: chlorine leaching, sulfuric acid oxidation leaching, pressure leaching etc.These dissolve leaching method is all directly in solution, raw material to be carried out to redox reaction and dissolution process, has the shortcomings such as equipment investment cost is high, production technology and device systems complexity, production efficiency is low, processing speed is slow, easy contaminate environment, material use efficiency is low, running cost is high, economic and technical norms are low.
In leaching process, reach specific physics and chemistry condition by controlling handled solid material and raw material environment of living in, under this condition, can there is the controlled chemical reaction of speed in the reagent material of particulate solid raw material and interpolation, generates the Matter Composition that is easier to leaching and dissolves.Wherein, physical condition: the volume by volume concentration of solid particles surface temperature, environmental stress, gas ingredients; Electrochemical conditions: the energy barrier of the oxidisability of reactant and reductibility, redox reaction.
The variation that the combination (inductive condition) of physical condition and electrochemical conditions can break through energy barrier, the oxidation-reduction quality of reactant and the Gibbs free energy of chemical reaction that redox reaction need to overcome can be carried out reaction smoothly, and chemical reaction process to be redox reaction continue to provide favourable condition.The startup of inductive condition has two kinds of modes, does not use the starting method treatment condition toggle speed of other chemical reagent material slow, the speed that adds of oxidative reaction thing changes at any time, and operation is controlled more complicated; Use sodium chlorate etc. to play the starting method of chemical reagent of same oxidisability effect simple, inductive condition toggle speed is fast.
Summary of the invention
The object of this invention is to provide a kind of method of Oxidation Leaching.
Another object of the present invention is to propose a kind of system for Oxidation Leaching.
A method for Oxidation Leaching, comprises step:
1) raw material pulverizing, mixes with the one in sodium chlorate, Potcrate or potassium permanganate;
2) in airtight system, add water, pass into the gas that contains oxygen, with inflammable substance igniting, firing point is positioned at step 1) gained mixture inside;
3) passing into of the gas that stops containing oxygen, sprays into water smoke to reaction mixture, passes into chlorine or oxygen 20-260min, and to keep the pressure in airtight system be normal pressure;
4) to reaction mixture no longer include steam produce time stop spraying into water smoke, add inorganic acid solution reaction mixture, and control solution pH value be 1-3.5;
5) solid-liquid separation reaction mixture, gets liquid phase.
Wherein, raw material in described step 1) is raw mineral materials and/or the waste that contains metal or metallic compound, described metal is one or more in copper, iron, Ruthenium, rhodium, palladium, cobalt, manganese, nickel, lead, zinc, gold and silver, osmium, iridium, rare earth element, and described raw material is crushed to below 10mm.Described raw material can be salt, simple substance, oxide compound, sulfide and the alloy form of metal.Inflammable substance are selected from the one in carbon dust, timber, cotton, withered grass, dead leaf, fiber.
The mass ratio of the raw material in described step 1) and sodium chlorate, Potcrate or potassium permanganate is 10:1-5; The water-soaked that described raw material is 10-50% with mass ratio.
Step 2) in the gas that contains oxygen be the gas that contains volume ratio 20-80% oxygen; Add water and make liquid level arrive mixture bottom.Add water the device that loads raw material is immersed in the water, play the effect of protection.The described gas that contains oxygen can be used air.
Wherein, in described step 3), by passing into air, to keep the pressure in airtight system be normal pressure; In described step 4), mineral acid is the one in sulfuric acid, nitric acid, hydrochloric acid; While adding mineral acid, reaction mixture is stirred.
Wherein, also comprise that the solid phase that solid-liquid separation is obtained carries out the step of Oxidation Leaching processing again after described step 5).The inorganic acid solution adding by control, the water smoke spraying into, added water, the volume (L) that finally obtains liquid phase is 7.2-16.3:1 with raw materials quality (kg) ratio.
For a system for Oxidation Leaching, it comprises airtight tank body, carrying apparatus, heating unit, spraying plant and whipping appts;
Described carrying apparatus, heating unit, spraying plant and whipping appts are all positioned at the inside of described tank body, and described spraying plant is positioned at the top of carrying apparatus, and described heating unit is positioned at the below of carrying apparatus and contacts with carrying apparatus;
Described tank body is also provided with the pipeline of ventilation, import and the outlet of solution.
Wherein, on described tank body, be also provided with liquid level emasuring device, stress measuring device; Described heating unit is electric heater unit.
Wherein, described system is also provided with the device that makes gas circulation in tank body; The device of described gas circulation comprises gas circulation pipeline, on gas circulation pipeline, is provided with blower fan; Described gas circulation pipeline is connected with the pipeline of described ventilation.
Wherein, described carrying apparatus is plate-like, and there is projection centre.The top of projection is firing point, places inflammable substance above, can heat below.
The method that the present invention proposes, the scope of its oxidation reaction condition parameter is:
Solid particles surface temperature: >=300 ℃
Environmental stress: normal pressure;
Oxidisability reagent is in the situation of gas, when oxidizing gas is oxygen or chlorine, and oxidizing gas volume by volume concentration: >=40%.
The temperature of Oxidation Leaching reaction process comprises two aspects: the temperature at oxidizing reaction center; The temperature that mixture surface embodies.
The temperature of reactive center is mainly determined by the speed of exothermic heat of reaction speed and heat release, adds speed control chemical reaction velocity by controlling oxidisability reagent, reaches the object of controlling heat release speed.The speed of heat release, by changing to adding water in the mixture that starts to react or the method for solution is controlled, the water adding or solution are in the time approaching reactive center high-temperature zone, and liquid water vaporization absorbs heat, accelerates heat release speed.
In mixture reaction process, the reaction heat at chemical reaction center, to external diffusion, shows certain temperature on mixture surface.The temperature on mixture surface can be by controlling at the vaporific water of mixture surface spraying or the method for solution.
According to the feature of Oxidation Leaching reaction, guaranteeing that, under the condition of certain economic and technical norms, the material quantity of primary treatment is larger, the speed of reaction can be faster, this be because:
(1) impact of the core temperature surface temperature of raw material generation chemical reaction is little, and in surface temperature one timing, raw material total amount is larger, adds the speed of oxidisability reagent faster, and Oxidation Leaching speed of response is faster.
(2) material quantity is larger, can in raw material, increase adding a little of oxidisability reagent, realizes multiple spot reaction, improves speed of response.
(3) accelerate extraneous cooling rate, for example, increase injection flow rate or increase hot gas circulation speed.
The feature of Oxidation Leaching (induction process) technology can also can compare completely and react with raw material in the situation that oxidizing gas concentration (partial pressure in other words) is lower, and this feature has determined also can be applied to when oxidizing gas purity is lower Oxidation Leaching technology.The condition that low concentration chlorine is applied to leaching-out technique is:
(1) gas mixing with oxidizing gas is air or nontoxic gas;
(2) in mixed gas, the shared volume ratio of oxidizing gas is not less than 30%;
(3) in mixed gas, oxidizing gas composition is lower, and the utilization ratio of oxidizing gas is lower.
In redox reaction, oxidisability reagent is a class consumable material.In the time that induction processing Leaching reaction has started to carry out, can effectively utilize airborne oxygen by the control of reaction process, concrete grammar has:
(1) pass into air to forming in the raw material of reaction conditions, when oxygen content in air is not enough to maintain reaction while carrying out with certain speed, stop passing into air, be adjusted into and add the material higher containing oxidisability composition, speed of response is improved again, in the time reaching certain condition, be adjusted into again and pass into air, be so used alternatingly with the high material of oxidisability composition and air, effectively utilize airborne oxygen, reduce the consumption ratio of oxidisability reagent.
(2) in the raw material of reaction conditions, pass into material that oxidisability composition is high and the mixture of air to forming, oxidizing substance composition is reached and guarantee that redox reaction continues the concentration of carrying out, the consumption of oxidisability reagent is reduced.
Oxidation Leaching technology can directly be processed macrobead raw material under certain condition, processing macrobead raw material need to have the raw material after a certain proportion of fragmentation to start Oxidation Leaching condition, after condition starts, the size particles raw material mixing is participated in chemical reaction together, and now the feature of reaction has:
(1) size of macrobead raw material does not have specific requirement, can be the object that bulk or volume are very large, but the larger speed of response of volume is slower.
(2) reaction needed of macrobead raw material starts stronger induction processing leaching condition.
Method of the present invention is used specially designed equipment, and running cost is low, simple to operate, speed is fast:
(1) leaching plant increases sealing function: by measuring the pressure variation in sealing equipment, the speed that passes into of corresponding control reagent or gas; Prevent that available gas composition runs off; Be sealed in the gas in equipment, continue to utilize by gas circulating; Prevent the obnoxious flavour contaminate environment such as chlorine; Newly-generated gas, gas discharging or the recycling if responded.
(2) induction is processed in leaching plant and is established pallet, deposit pending raw material, pallet and pallet below are solution, pallet is immersed in certain depth in solution, above pallet, fix one or more reagent outlets, be used for adding reagent or gas, supporting portfire simultaneously, for the startup of Oxidation Leaching condition.
(3) temperature regulating device of configuration spray solution or water in equipment; Be equipped with necessary solution line entrance and exit; Be equipped with the required whipping appts of dissolution process process; Be equipped with the raw material storage of not dissolved and reclaim chute; Be equipped with solution filter facility adjustable and that change.
(4) induction is processed in leaching plant, and liquid level can regulate, control.
(5) the cooling Oxidation Leaching equipment of recirculating cooling water system (spraying), makes the inner vapor condenses Cheng Shui forming, and mixes with the solution in equipment, induces the bulk temperature of processing Leaching reaction in operating device simultaneously.
Leaching method provided by the invention has the following advantages:
(1) Leaching way of the obnoxious flavour such as chlorine no longer needs tail gas to absorb facility, has simplified Production Flow Chart, has reduced processing cost;
No longer needing tail gas to absorb facility is embodied in: after oxidation reaction condition has started, the raw material that reaches inductive condition in system occupies certain space, while passing into the obnoxious flavoures such as chlorine, from gas passes into, chlorine starts and raw material reaction, spreading towards periphery in process chlorine gas concentration can fast reducing, inductive condition can make chlorine fully react with raw material, the speed that passes into of controlling chlorine makes chlorine complete reaction in the space that possesses inductive condition, just completely consumed while also not arriving the outermost border of inductive condition raw material, no longer need tail gas to absorb facility.
(2) Oxidation Leaching technology can make full use of the mixed gas that chlorine volume percent is lower, or other mixed gas that contains certain proportion oxidizing gas, has reduced the running cost that tail gas absorbs when effectively utilizing oxidizing gas;
(3) improved the utilization ratio of reagent, material;
(4) process control point is simplified, and operates simplyr, and process is more easily controlled;
(5) can control more simply and effectively the technical qualification that leach terminal solution, for example control of infusion solution terminal pH, ionic concn;
(6) Application Areas is extensive, can simplify chlorine leaching, pressure leaching, sulfuric acid oxidation leaching etc., significantly reduces processing cost.
Accompanying drawing explanation
Fig. 1 is the system of embodiment 1 for Oxidation Leaching,
Fig. 2 is that embodiment 1 adds the system diagram after raw material.
In figure: 1 is tank body, 2 is pallet, and 3 is electric heater unit, and 4 is firing point, and 5 is shower nozzle, 6 is agitator, and 7 is the pipeline of charging, 8 imports that are solution, and 9 outlets that are solution, 10 is blower fan, 11 is gas circulation pipeline, 12 pipelines for ventilation, and 13 is projection, 14 is raw material.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
For the system (referring to Fig. 1) of Oxidation Leaching: comprise the pallet 2, electric heater unit 3 of airtight tank body 1, loading, shower nozzle 5 and the agitator 6 of four atomized water sprays;
The shower nozzle 5 of pallet 2, electric heater unit 3, four atomized water sprays and agitator 6 are all positioned at the inside of tank body 1, and shower nozzle 5 is positioned at the top of pallet 2, and described heating unit is positioned at pallet 2 belows and contacts with pallet 2; Pallet 2 is stainless steel.In tank body 1, be provided with the tensimeter of liquidometer and measurement tank internal gas pressure.Tank body 1 is also provided with the pipeline 7 of charging, import 8 and the outlet 9 of solution.In the middle of pallet, there is projection 13.
The object of Oxidation Leaching: the leaching of the core component that contains noble metal catalyst composition is dissolved.
Raw material: the core component that contains valuable metal catalyst composition in spent catalyst equipment.The feature of raw material is the surface that metal catalyst composition sticks to the metallic substance such as iron, copper, after need to being dissolved, purifies.Raw material composition (mass ratio): metallic copper accounts for 78%, and metallic iron accounts for 12%, metal Ru, rhodium, palladium catalyst composition account for 6%, and oxygen and element silicon account for 4%.
Treatment process:
1) this raw material is carried out to mechanical disintegration, get solid particulate and evenly mix with sodium chlorate 300g for bearing 80 orders (0.18mm is following) powder 2000g, fully wetting with 450g water; Be placed on pallet 2;
2) firing point is placed 3g wood chip, and firing point is positioned in pallet protrusions 13;
3) referring to Fig. 2, wetting raw material 14 is put into pallet firing point and oxidizing gas entrance is surrounded, water filling in system, to liquid level to pallet height be 15mm, now tray edge is under water;
4) energising heating wood chip also slowly passes into 60% oxygen, wood chip takes fire, after approximately 5 seconds, there is steam in mixture top, in mixture, sodium chlorate is decomposed, and the oxygen of emitting reacts with catalystic material metal-powder, emitting a large amount of heat outwards spreads reaction, after 1 minute, mixture entirety red heat, mixture temperature >=800 ℃;
5) stop passing into oxygen, open spraying plant, uninterruptedly spray into continuously water smoke;
6) start to pass into chlorine, draft speed is 3L/min, open gas circulation simultaneously and establish in device (blower fan 10) twitch system the not gas of complete reaction and pass into from gas inlet again, gas is fully contacted with raw material again, make gas in equipment fully participate in oxidizing reaction; When gaseous tension reduces in equipment, suitably pass into air to maintain normal pressure;
7) reaction is carried out, after approximately 20 minutes, stopping passing into chlorine, continues spraying, treats that temperature reduces, and utilizes water smoke that temperature of reaction system is down to below 100 ℃;
8) contain the hydrionic sulphuric acid soln solubilizing reaction of 4 ± 0.5mol/L thing with the speed of 200 ± 50mL/min to injecting in equipment, and open and stir, the technical qualification such as terminal acidity, concentration of metal ions of the condition control leach liquors such as the add-on of while adjustment of acidity solution; Terminal pH2.
9) the terminal acidity of control solution, repeatedly add on a small quantity acidic solution, when reactant under agitation fully reacts 20min with acidic solution, and when solution acidity no longer changes, after dissolution process finishes, stop stirring, emit solution, finally take out unreacted raw material, by unreacted raw material circular treatment again.
Relevant chemical equation in treating processes:
Cl
2+ M=MCl
z+ Q(heat) (1)
Sodium chlorate decomposes chemical reaction: 2KCIO
3=2KCI+3O
2↑
In formula (1), M represents the one in copper, iron, ruthenium, rhodium, metallic palladium; Z is stoichiometric coefficient.
Result:
1, obtain the solution that contains ruthenium, rhodium, palladium precious metal ion as leading take copper and ferrous metal ion, the solution 14.5L of metal ion total concn 120.0g/L;
2, once induce processing leaching operation, the all operations were time is not more than in the situation of 1 hour, raw material leaching yield reaches 86.6%, 86.6% raw material enters in solution, in 4 hours, carry out 4 circulation-induced processing, leaching yield can reach chlorine leaching that 99.8%(is traditional under extraction time reaches the situation of 48 hours, and leaching yield is 96.7%);
3, use oxygen and air mixed oxidation raw material, in the oxygen of consumption, 40% oxygen, from air, and uses conventional chlorine leaching, and leaching required oxidizing gas be all chlorine, and approximately 10% of chlorine total amount consumed is absorbed by exhaust treatment system in addition;
4, circulation-induced is processed and is leached, leaching yield 100%.
5, leaching process is simply efficient, and reagent material utilization ratio is high, and equipment is simple, and operation steps is simple;
6, chlorine and oxygen are all oxidizing gas, and in industrial application process, it is can two kinds of gases general that leaching-out technique is processed in induction.
Industrial application: white metal raw material from African import to China, leaches dissolving in China as a kind of cobalt raw metal, then carries out purification final production pure metal cobalt and the cobalt salt of cobalt metal.This method is exactly that dialogue alloy raw material carries out simply, efficiently leaches and dissolve for the application of white metal, obtains the solution that contains cobalt metal ion, then carries out subsequent purification.
Material characteristic: the raw material that the cobalt metal mine in Africa obtains through flotation carries out thick purification processes, obtain take copper, iron, cobalt metal as main white metal raw material, this type of raw material arrives China with the form import of cobalt raw material, because the crystalline form of its Metallic Solids has certain passivation, common leaching dissolving method is processed very difficult, equipment and material have high input, and leach dissolving result undesirable.Raw material composition: metallic copper accounts for 27.4%, metallic iron accounts for 33.7%, and cobalt metal accounts for 28.5%, and oxygen and element silicon account for 9.2%, and other is manganese etc.
Treatment process:
1) get these raw material-80 order particle 10000g, mix with 1000g sodium chlorate, 3000g water;
2) mixture is placed on to induction and processes in leaching plant pallet, liquid level position is 10mm above pallet, and firing point is put 10g wood chip;
3) leaching plant is processed in airtight induction, when starting electrically heated wood chip, pass into the oxygen of volume ratio 60% with the speed of 5L/min, electrically heated is during to approximately 400 ℃ of wood chips, wood chip takes fire, oxygen stops after passing into 20s, the oxygen that in mixture, sodium chlorate decomposes is emitted and the oxygen passing into and wood chip and raw material reaction, continue to emit a large amount of heat, impel sodium chlorate to continue to decompose and emit oxygen and raw material reaction, inductive condition sluggish is launched, when about 200s, inductive condition is in full swing in mixture;
4) in the time having steam to emerge in the mixture in pallet, stop logical oxygen, top starts atomized water spray, and maintains not red heat of spraying maintenance mixture skin;
5) now pass into chlorine with the speed of 10L/min, react after 260 minutes, stop logical chlorine;
6) top increases the speed of atomized water spray, to reacted material cooling, is cooled to when no longer including steam and emerging, stops spraying;
7) start stirring, and to start to add sulfuric acid concentration be the material after the solution solubilizing reaction of 2mol/L, to control the mode control solution terminal pH that adds amount of solution, solution terminal pH is 1.5;
8) open liquid exit, the filter plant of solution stream outside equipment.
9) unreacted material is placed on to induce in the pallet of processing leaching plant again and processes in order to continuing.
Result:
(1) obtain main grade cobalt concentration of metal ions 43.7g/L, terminal pH and be 1.5 solution 69.8L;
(2) because discharging without gas, so chlorine utilization reaches 100%;
(3) once induction is processed, and in the situation that the operating time is no more than 5 hours, leaching yield is 76.4%, and circulation-induced is processed and leached, and white metal raw material does not exist undissolvable slag, leaching yield 100%; Conventional chlorine leaching, leaching process is in 48 hours situations, leaching yield is 92.7%;
(4) leaching process is simply efficient, and reagent material utilization ratio is high, and equipment is simple, and operation steps is simple.
Embodiment 3
Industrial application: the cobalt-carrying solution purity requirement that battery production field is used is very high, a lot of solution needs directly to dissolve high pure metal cobalt powder by high purity acid.This method is for the dissolving of metal cobalt powder, the high and low cost of efficiency, and treating processes is simple, obtains required ideal solution.
Material characteristic: metal cobalt powder purity reaches more than 99.95%, is powdery, and maximum particle diameter is 0.2mm.Metal cobalt powder, density is large, hardness is high, is directly difficult to dissolve with acid, and other usual manner can increase again impurity composition.
Treatment process:
1) get this metal cobalt powder 10000g, mix with 300g water and 300g sodium chlorate;
2) mixture is placed on to induction and processes in leaching plant pallet, liquid level position is 5mm above pallet, and firing point is put the pure wooden carbon of 2g;
3) leaching plant is processed in airtight induction, when starting the pure wooden carbon of electrically heated, pass into the oxygen of volume ratio 60% with the speed of 0.5L/min, electrically heated is during to approximately 400 ℃, pure wooden carbon, pure wooden carbon takes fire, oxygen stops after passing into 10s, the oxygen that in mixture, sodium chlorate decomposes is emitted and the oxygen passing into and pure wooden carbon and raw material reaction, continue to emit a large amount of heat, impel sodium chlorate to continue to decompose and emit oxygen and raw material reaction, inductive condition sluggish is launched, when about 120s, inductive condition is in full swing in mixture;
4) in the time having steam to emerge in the mixture in pallet, stop logical oxygen, top starts atomized water spray, and maintains not red heat of spraying maintenance mixture skin;
5) now pass into oxygen (industrial oxygen) with the speed of 1L/min, react after 160 minutes, stop logical oxygen;
6) top increases the speed of atomized water spray, to reacted material cooling, is cooled to when no longer including steam and emerging, stops spraying;
7) start stirring, and to start to add sulfuric acid concentration be the material after the solution solubilizing reaction of 2mol/L, to control the mode control solution terminal pH that adds amount of solution, solution terminal pH is 3.5;
8) open liquid exit, the filter plant of solution stream outside equipment.
9) unreacted material is placed on to induce in the pallet of processing leaching plant again and processes in order to continuing.
Relevant chemical equation in treating processes:
Oxygen reacts with cobalt metal in raw material:
O
2+ 2Co=2Co O+Q(heat) (2)
Result:
(1) obtain cobalt metal ionic concn 116.2g/L, terminal pH and be 3.5 solution 7.5L;
(2) because discharging without gas, so oxygen utilization rate reaches 100%;
(3) once induction is processed, and in the situation that the operating time is no more than 3 hours, leaching yield is 87.15%, and circulation-induced is processed and leached, and cobalt metal does not exist undissolvable composition, leaching yield 100%;
(4) leaching process is simply efficient, and reagent material utilization ratio is high, and equipment is simple, and operation steps is simple.
Embodiment 4
Industrial application: the nickelous sulfide intermediate raw material that nickel sulfide ore mountain plateau material obtains through ore dressing, this raw material is induced and processed leaching operation, high doubly more a lot of than conventional pressure leaching efficiency, cost is low.This raw material is induced to the sulfur dioxide gas of processing output in leaching operation process, the gas absorption or the relieving haperacidity support equipment that when same connection pressure leaching, use, do not need to increase miscellaneous equipment, leach merely dissolution process and can reach the object of raising the efficiency, reducing costs.
Object: the leaching of nickel sulfide concentrate is dissolved.
Material characteristic: nickel sulfide concentrate raw material is difficult to dissolve, conventional pressure leaching method equipment investment is large, danger is high, processing efficiency is low, leaches dissolving result undesirable.Raw material composition: nickelous sulfide accounts for 65%, cobaltous sulfide accounts for 2%, and the metals such as lead, manganese, copper, iron account for 3.4%, and other is indissoluble silicates.
Treatment process:
1) this raw material powder 2000g is evenly mixed with sodium chlorate 400g, fully wetting with 450g water;
2) heating and firing point are placed 3g wood chip; Wetting mixture is put into pallet firing point and production well are covered, in system, water filling liquid level is to pallet top 15mm, and approximately 15% raw material is under water;
3) gas circulation pipeline connects the external receiving apparatus that flows back to of sulfur dioxide gas;
4) electrically heated wood chip slowly to pass into volumetric concentration be 80% oxygen, wood chip takes fire, after approximately 8 seconds, there is steam in mixture top, mixture starts heated evaporate to dryness, and sodium chlorate is decomposed, and the oxygen of emitting reacts with raw material powder, emit a large amount of heat and sulfur dioxide gas, the new sulfur dioxide gas producing is drawn induction through gas discharging retrieving arrangement and is processed Leaching Systems, and chemical reaction spreads to entirety, approximately 1 minute, mixture bulk temperature reaches 1200 ℃, and inductive condition starts complete;
5) spraying plant of opening device top, uninterrupted spraying continuously; Pass into oxygen (industrial oxygen), draft speed is 1L/min, opens gas circulation simultaneously, makes oxidizing gas Multiple through then out induced reaction system in equipment and efficiently utilization;
6) induction is processed in the situation that temperature of reaction system in leaching process is not less than 1000 ℃, increases and passes into air simultaneously, to utilize airborne oxygen; Pass into the ratio of air so that temperature of reaction system is not less than 1000 ℃, when temperature is during lower than 1000 ℃, reduce AIR Proportional, increase oxygen proportion, make to react severe degree and increase, temperature raises.
7) reaction is carried out, after approximately 30 minutes, stopping passing into oxygen and air, continues spraying, and question response thing temperature reduces;
8) the dissolve with hydrochloric acid solution raw material after treatment that implantation concentration is 4mol/L, opens and stirs, and regulates the conditions such as acid adding amount simultaneously, and control leach liquor concentration of metal ions is not more than 150g/L, pH value is 1.3～1.5;
9) after dissolution process finishes, stop stirring, emit after filtration solution; Unreacted raw material and the processing of new raw material mixed cycle.
Relevant chemical equation in treating processes:
Oxygen reacts with raw material medium sulphide content:
O
2+ MS=M
xo
y+ SO
2 ↑+ Q(heat) (3)
In formula (3), M represents the one in copper, iron, cobalt, manganese, nickel metal; X, y are stoichiometric coefficient.
Result:
(1) obtain the about 37g/L of main grade nickel concentration of metal ions, terminal pH and be 1.5 solution 19.8L;
(2) use oxygen and air mixture oxide treatment raw material, in the oxygen of consumption, 35% oxygen is from air, and conventional pressure leaching method oxygen 100% is from purity oxygen;
(3) once induction processing leaching yield is 94.2%, and circulation-induced is processed and leached, leaching yield 100%; Leaching yield of conventional pressure leaching method is 82.5%, circular treatment, and leaching yield is 100%.
(4) leaching process is simply efficient, and reagent material utilization ratio is high, and equipment is simple, and operation steps is simple.
Raw material is with embodiment 3.
Treatment process:
1) get these raw material-80 order particle 1000g, mix with 200g sodium chlorate, 200 water, then get not broken white metal raw material 1000g, maximum particle diameter is not more than 10mm, more fully mixes with the above-mentioned mixture mixing;
2) mixture is placed on to induction and processes in leaching plant pallet, liquid level position is 10mm above pallet, and firing point is put 3g wood chip;
3) leaching plant is processed in airtight induction, when starting electrically heated wood chip, pass into volume ratio with the speed of 0.8L/min and be not less than 60% oxygen, electrically heated is during to approximately 400 ℃ of wood chips, wood chip takes fire, when passing into 30s, oxygen stops, in mixture, sodium chlorate is decomposed the oxygen of emitting and is continued react with material and make inductive condition start sluggish expansion, and when about 80s, inductive condition is in full swing in mixture;
4) in the time having steam to emerge in the mixture in pallet, top starts atomized water spray, and maintains not red heat of spraying maintenance mixture skin;
5) now pass into and the mixed gas of the chlorine volume ratio 40% of air mixed with the speed of 5L/min, react after 30 minutes, stop logical mixed gas;
6) top increases the speed of atomized water spray, to reacted material cooling, is cooled to when no longer including steam and emerging, stops spraying;
7) start stirring, and to start to add sulfuric acid concentration be solution and the reacted material of water dissolution of 2mol/L, add the mode control GOLD FROM PLATING SOLUTION of amount of solution to belong to ionic concn and solution terminal pH to control, solution terminal pH is 1.5;
8) open tap hole, and start overanxious equipment, when solution flows out, unreacted raw material is trapped in induction processing leaching plant by overanxious device;
9) unreacted material is placed on to induce in the pallet of processing leaching plant again and processes in order to continuing.
In treating processes, relevant chemical equation is formula (1), and in formula, M represents the one in the metals such as copper, iron, cobalt, manganese, nickel.
Result:
(1) obtain the about 39g/L of main grade cobalt concentration of metal ions, terminal pH and be 1.5 solution 16.3L;
Because of have air participate in react and have gas discharging, when chlorine volume ratio is 40%, chlorine utilization 99.6%, other is by the processing of residual air absorption unit;
(3) in air, oxygen is fully used, and through reasoning and calculation, utilization is 8.7mol oxygen, has saved the use of a large amount of chlorine;
(4) once induction processing leaching yield is 87.9%, and circulation-induced is processed and leached, and white metal raw material does not exist undissolvable slag, and leaching yield is 100%;
(5) process after leaching through inducing without broken white metal raw material, particle is all broken for fine powder abundant participation induction processing Leaching reaction, and the slag forming does not affect circulation-induced and processes leaching operation;
(6) leaching process is simply efficient, and reagent material utilization ratio is high, and equipment is simple, and operation steps is simple.
Embodiment 6
Raw material is with embodiment 3.
Treatment process:
1) get these raw material-80 order particle 10000g, mix with 1000g sodium chlorate, 3000g water;
2) mixture is placed on to induction and processes in leaching plant pallet, liquid level position is 10mm above pallet, and firing point is put 10g wood chip;
3) leaching plant is processed in airtight induction, when starting electrically heated wood chip, pass into volume in 60% oxygen with the speed of 5L/min, electrically heated is during to approximately 400 ℃ of wood chips, wood chip takes fire, oxygen stops after passing into 20s, the oxygen that in mixture, sodium chlorate decomposes is emitted and the oxygen passing into and wood chip and raw material reaction, continue to emit a large amount of heat, impel sodium chlorate to continue to decompose, emit oxygen and raw material reaction, inductive condition sluggish is launched, and when about 200s, inductive condition is in full swing in mixture;
4) in the time having steam to emerge in the mixture in pallet, stop passing into oxygen, top starts atomized water spray, and it is outer moist to maintain spraying maintenance mixture;
5) now pass into chlorine as 50% and mixture air take the speed of 15L/min, react after 30 minutes, stop passing into mixed gas;
6) top increases the speed of atomized water spray, to reacted material cooling, is cooled to when no longer including water vapor and emerging, stops spraying;
7) start stirring, and start to add the material after the solution solubilizing reaction that water and sulfuric acid concentration are 2mol/L, to control the mode control solution terminal pH that adds acid-containing solution amount, solution terminal pH is 1.5;
8) open tap hole, and start overanxious equipment, when solution flows out, unreacted raw material is trapped in induction processing leaching plant by overanxious device;
9) unreacted material is placed on to induce in the pallet of processing leaching plant again and processes in order to continuing.
Result:
(1) obtain the about 42.5g/L of main grade cobalt concentration of metal ions, terminal pH and be 1.5 solution 72.6L;
(2) because there being the gases such as unreacted nitrogen to discharge, so chlorine utilization does not reach 100%, practical efficiency is 98.4%;
(3) once induction processing leaching yield is 86.7%, and circulation-induced is processed and leached, and white metal raw material does not exist undissolvable slag, leaching yield 100%;
(4) leaching process is simply efficient, and reagent material utilization ratio is high, and equipment is simple, and operation steps is simple.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. a method for Oxidation Leaching, is characterized in that, comprises step:
1) raw material pulverizing, mixes with the one in sodium chlorate, Potcrate or potassium permanganate; Described raw material is raw mineral materials and/or the waste that contains metal or metallic compound, described metal is one or more in copper, iron, Ruthenium, rhodium, palladium, cobalt, manganese, nickel, lead, zinc, gold and silver, osmium, iridium, rare earth element, and described raw material is crushed to below 10mm;
2) in airtight system, add water, pass into the gas that contains oxygen, with inflammable substance igniting, firing point is positioned at step 1) gained mixture inside;
3) passing into of the gas that stops containing oxygen, sprays into water smoke to reaction mixture, passes into chlorine or oxygen 20-600min, and to keep the pressure in airtight system be normal pressure;
4) to reaction mixture no longer include steam produce time stop spraying into water smoke, add inorganic acid solution reaction mixture, and control solution pH value be 1-3.5;
5) solid-liquid separation reaction mixture, gets liquid phase.
2. the method for claim 1, is characterized in that, the mass ratio of the raw material in described step 1) and sodium chlorate, Potcrate or potassium permanganate is 10:1-5; The water-soaked that described raw material is 10-50% with mass ratio.
3. the method for claim 1, is characterized in that, described step 2) in the gas that contains oxygen be the gas that contains volume ratio 20-80% oxygen; Add water and make liquid level reach mixture bottom.
4. the method for claim 1, is characterized in that, in described step 3), by passing into air, to keep the pressure in airtight system be normal pressure; In described step 4), mineral acid is one or more in sulfuric acid, nitric acid, hydrochloric acid; While adding mineral acid, reaction mixture is stirred.
5. the method as described in as arbitrary in claim 1-4, is characterized in that, also comprises that the solid phase that solid-liquid separation is obtained carries out the step of Oxidation Leaching processing again after described step 5).
6. the method as described in as arbitrary in claim 1-4, is characterized in that, the system that described Oxidation Leaching method is used comprises airtight tank body, carrying apparatus, heating unit, spraying plant and whipping appts;
Described carrying apparatus, heating unit, spraying plant and whipping appts are all positioned at the inside of described tank body, and described spraying plant is positioned at the top of carrying apparatus, and described heating unit is positioned at the below of carrying apparatus and contacts with carrying apparatus;
Described tank body is also provided with the pipeline of ventilation, import and the outlet of solution.
7. method as claimed in claim 6, is characterized in that, is also provided with liquid level emasuring device, stress measuring device on described tank body; Described heating unit is electric heater unit.
8. method as claimed in claim 6, is characterized in that, described system is also provided with the device that makes gas circulation in tank body; The device of described gas circulation comprises gas circulation pipeline, on gas circulation pipeline, is provided with blower fan; Described gas circulation pipeline is connected with the pipeline of described ventilation.
9. method as claimed in claim 6, is characterized in that, described carrying apparatus is plate-like, and there is projection centre.
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