CN103060843A - Method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in potassium hydroxide solution - Google Patents
Method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in potassium hydroxide solution Download PDFInfo
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Abstract
The invention relates to a method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in a potassium hydroxide solution. The method comprises the steps as follows: introducing oxidizing gas into mixed slurry containing the vanadium slag, potassium hydroxide and water; carrying out electrochemical oxidization reaction; and after the reaction, carrying out solid-liquid separation on the mixed slurry to obtain tailings and a vanadium and chromium alkali solution. The method is low in cost, high in extraction efficiency, pollution-free and moderate in process conditions, and can be used for efficiently and synchronously extracting vanadium and chromium; the vanadium extraction rate can reach 85-99%; and the chromium extraction rate can reach 80-95%.
Description
Technical field
The present invention relates to a kind of method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium, particularly the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium in a kind of potassium hydroxide solution.
Background technology
Vanadium slag is a kind of vanadium enrichment material of being produced in oxygen-containing gas existence condition blowing down by vanadium-bearing hot metal, and the vanadium slag by vanadium titano-magnetite production in the Iron And Steel Industry is the main raw material of vanadium extraction.The composition of vanadium slag is relevant with vanadium titano-magnetite composition and production method, and in general, vanadium slag is by V
2O
5, SiO
2, Al
2O
3, MgO, Cr
2O
3, TiO
2, the component such as CaO forms, each factory's vanadium slag composition difference is also very large, but its phase structure is basic identical, by compositions such as spinel, peridotites, quartz.
Current enterprise take vanadium titano-magnetite as raw material production vanadium product all adopts traditional vanadium slag sodium roasting technique vanadium extraction from vanadium slag, climbing steel, hold steel, sea, South Africa Wilder, New Zealand Steel Ltd. etc. such as China.The technique ultimate principle of sodium roasting is with Na
2CO
3, NaCl, Na
2SO
4Be additive Deng sodium salt, the water-insoluble vanadium of lower valency is converted into the sodium salt of water-soluble pentavalent vanadium by high temperature sodium roasting (750-850 ℃), again to the direct water logging of sodium roasting product, obtain containing the leaching liquid of vanadium, rear adding ammonium salt makes the ammonium poly-vanadate precipitation, obtains the oxide product of vanadium after reducing roasting.Sodium roasting technique vanadium recovery is low, and single roasting vanadium recovery is about 70%, and the rate of recovery of vanadium also only is 80% after roasting repeatedly, and chromium can not extract; Maturing temperature high (750-850 ℃), energy consumption is higher; In addition, in roasting process, can produce harmful HCl, Cl
2Deng aggressive gas, contaminate environment.
CN101215005A has proposed the method for a kind of vanadium slag and sodium salt (yellow soda ash, sodium-chlor) or sylvite (salt of wormwood, Repone K) roasting, this patent is applicable to the low vanadium vanadium slag of high silicon, maturing temperature is 700 ~ 820 ℃, the multiple temperature sections roasting, by control temperature schedule and salt proportioning, can prevent the furnace charge sintering, make the technique direct motion, also reduced the roasting soaking time, V in the tailings
2O
5Content can reach 0.5 ~ 1%.
CN1884597A, CN86108218A, CN102477491A, CN102242274A etc. have carried out different improvement to factors such as the additive of sodium roasting technique and temperature controls, and ultimate principle all is by using the additive (Na of different proportionings
2CO
3, NaCl, Na
2SO
4, Na
2SO
3Deng) and different temperature schedule the indexs such as the extraction yield of vanadium, roasting time, furnace charge sintering improved and improved, but above technique and traditional sodium roasting principle, operating process, service temperature are basic identical, can't avoid maturing temperature to cross the problem of high traditional technology.
CN101161831A has proposed a kind of method of calcification vanadium slag sintering, behind vanadium slag and lime or the Wingdale mixing without the progressively temperature-rise period from low temperature to high temperature, the stoving oven that directly enters more than 600 ℃ carries out calcification baking, makes the vanadium in the vanadium slag change vanadic acid calcium into; In the roasting grog, vanadium enters solution through vitriol lixiviation, and then preparation barium oxide product.Compare with sodium roasting technique, this method need not the process that progressively heats up to high temperature through low temperature, but directly high-temperature roasting makes the easier control of temperature of stoving oven, and shortened roasting time, and the production capacity of equipment also increases.But the maturing temperature of calcification baking is very high (600 ~ 950 ℃) still, and chromium is not recovered in the vanadium slag.
CN102127655A has proposed a kind of method of NaOH solution decomposing vanadium slag under normal pressure, and temperature of reaction is 180 ~ 260 ℃; Compare with sinter process, the vanadium extracting process temperature reduces greatly, Energy Intensity Reduction, and vanadium extraction efficient obviously improves, but can't realize the extraction of chromium; CN102127654A has proposed a kind of method of using the sodium hydroxide fused salt to decompose to contain vanadium chromium slag, and 500 ~ 600 ℃ of temperature of reaction, this technique can realize that vanadium chromium carries altogether, but the molten salt react ion process temperature is higher; CN102127656A has proposed a kind of method of decomposing vanadium slag by liquid phase oxidation, by using sodium hydroxide, SODIUMNITRATE medium, oxygenolysis vanadium slag process is strengthened, and reduces than sodium hydroxide fused-salt medium temperature of reaction, but introduced the SODIUMNITRATE medium, the subsequent separation process step increases; CN102531056A proposes a kind of method of vanadium slag pressure leaching cleaner production vanadic acid sodium Sodium chromate, and temperature of reaction 100-400 ℃, pressure 0.1-5.0MPa, this method can realize that vanadium chromium carries altogether, but temperature of reaction is higher, and need pressurized operation; CN101812588A has proposed a kind of method of decomposing vanadium slag with solution of potassium hydroxide under normal pressure, and 180 ~ 260 ℃ of reactions, temperature reduces greatly, and can realize that vanadium chromium carries altogether, yet the method requires very high take high-temperature high concentration KOH solution as reaction medium to equipment material; CN102534232A proposes the method that a kind of decomposing vanadium slag under normal pressure by adding carbon-containing substance into sodium hydroxide solution extracts vanadium chromium, and this method can realize that vanadium chromium carries altogether, but chromium extraction yield still lower (less than 20%).
CN102134640A proposes a kind of method of catalytic oxidation leaching From Converter Vanadium-bearing Slag, with From Converter Vanadium-bearing Slag and MnSO
4, H
2SO
4The furnishing pulp slurry carries out utilizing the Mn of the strong oxidizing property of anodic formation without the leaching of barrier film catalytic oxidation
3+Realize the Oxidation Leaching of Vanadium in Vanadium Residue, leaching liquid is by the heavy method extraction of conventional ammonia vanadium wherein, and then preparation Vanadium Pentoxide in FLAKES product.The problem includes: high energy consumption, the high pollution problem that this method has avoided problem in traditional leaching method, and it is widely applicable, selectivity is good, and processing condition are gentle simultaneously, and are pollution-free, but this method leaching efficiency is lower.
CN102534229A propose a kind of from From Converter Vanadium-bearing Slag selectivity leach the method for vanadium, Powdered From Converter Vanadium-bearing Slag and sulfuric acid, tributyl phosphate and sulfonated kerosene are mixedly configured into pulp slurry, pulp slurry is placed in the diaphragm-free electrolysis leaching vat, under electric field action, leach reaction, but this method adopts DSA anode and titanium negative electrode with iridium tantalum pentoxide coating, and cost is higher.
Therefore, it is lower that a kind of cost need to be developed in this area, and extraction efficiency is high, pollution-free, processing condition are gentle, and can realize the method for the electrochemical decomposition vanadium slag that vanadium chromium is put forward altogether.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium in a kind of potassium hydroxide solution, described method cost is lower, and extraction efficiency is high, and is pollution-free, processing condition are gentle, and can realize that vanadium chromium carries altogether.
The present invention is achieved through the following technical solutions:
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium in a kind of potassium hydroxide solution, described method is in the slurry that contains vanadium slag, potassium hydroxide, pass into oxidizing gas, carry out electrochemical oxidation reactions, obtain tailings and the solution that contains vanadium chromium alkali through solid-liquid separation.
The present invention selects electrochemical oxidation reactions, by the direct or indirect oxygenizement of electrochemistry, reduced the concentration of temperature of reaction and reaction medium alkaline solution, the efficient oxidation of Vanadium in Vanadium Residue picotite decomposes under having realized at lesser temps, than the low alkaline concentration condition, has realized that the high efficiency synchronous of vanadium chromium is extracted.
Preferably, electrochemical oxidation reactions of the present invention carries out in electrolyzer, preferably carries out in the normal pressure electrolyzer, and further preferred described electrochemical oxidation reactions stirs in the normal pressure electrolyzer and carries out.
Preferably, described anode electrolytic cell current density is controlled at 300A/m
2More than, 305A/m for example
2, 312A/m
2, 354A/m
2, 398A/m
2, 407A/m
2, 482A/m
2, 507A/m
2, 548A/m
2, 587A/m
2, 634A/m
2, 682A/m
2, 747A/m
2, 852A/m
2, 975A/m
2, 1032A/m
2, 1285A/m
2Deng, preferred 500-1000A/m
2
Preferably, the time 〉=1h of described electrochemical oxidation, such as 1.2h, 3.4h, 5.9h, 6.8h, 7.4h, 9.5h, 12h etc., preferred 4-8h;
Preferably, the electrode material of described electrolyzer is the combination of any a kind or at least 2 kinds in the iron, preferably the combination of any a kind or at least 2 kinds in stainless steel, pure iron or cast iron; Electrode shape is preferably tabular or bar-shaped.
The anode of described electrolyzer can be in any 1 in stainless steel plate, stainless steel bar, pure iron plate, pure iron rod, cast iron plate or the cast iron bar; The negative electrode of described electrolyzer can be in any 1 in stainless steel plate, stainless steel bar, pure iron plate, pure iron rod, cast iron plate or the cast iron bar.
As optimal technical scheme, the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution of the present invention
(1) preparation contains the raw material slurry of vanadium slag, potassium hydroxide aqueous solution;
(2) the raw material slurry that step (1) is obtained places electrolyzer, passes into oxidizing gas, carries out electrochemical oxidation reactions, makes reaction paste;
(3) the reaction paste solid-liquid separation that step (2) is obtained obtains rich iron tailings and the solution that contains vanadium, chromium, alkali.
In the present invention, the described vanadium slag of step (1) is for the process pre-treatment or do not pass through pretreated vanadium slag, and described pre-treatment comprises any a kind in mechanical activation or the roasting; Described mechanical activation comprises any a kind in roller ball mill, planetary ball mill or the stirring ball-milling.
Mechanical activation is that solid material produces lattice distortion and local failure under mechanical force, form various defectives, cause interior can the increase, a kind of method of reactive behavior enhancing, comprise fragmentation, powder, ball milling etc., such as roller ball mill, planetary ball mill or stirring ball-milling etc.
Preferably, in the described raw material slurry of step (1), the mass ratio 〉=3:1 of potassium hydroxide and vanadium slag, such as 3.2:1,3.6:1,4.3:1,4.8:1,5.1:1,5.8:1,6.3:1,6.8:1,7.2:1,7.8:1,8.4:1 etc., preferred 3:1 ~ 8:1, further preferred 4:1 ~ 6:1.Preferably, in the described raw material slurry, the mass concentration of potassium hydroxide aqueous solution is 50-70%, such as 50%, 55%, 60%, 65%, 70% etc.
Preferably, after the described raw material slurry preparation of step (1) is finished, carry out first preheating, and then carry out step (2).
Preferably, the temperature of described preheating is preferably 120-200 ℃, such as 120 ℃, 125 ℃, 130 ℃, 145 ℃, 150 ℃, 160 ℃, 165 ℃, 175 ℃, 180 ℃, 190 ℃, 200 ℃ etc., and further preferred 150-200 ℃, particularly preferably 150-180 ℃.
In the present invention, the described oxidizing gas of step (2) is selected from the combination of any a kind or at least 2 kinds in air, oxygen, oxygen-rich air or the ozone gas, preferred oxygen or air.
The combination of described oxidizing gas can be air ozone gas, oxygen ozone gas etc.
Preferably, the described electrolyzer of step (2) is the normal pressure electrolyzer.
Preferably, the described electrochemical oxidation reactions of step (2) carries out under agitation condition; Stir speed (S.S.) is preferably stir speed (S.S.) and is preferably 600-1200rpm, such as 600rpm, 650rpm, 700rpm, 750rpm, 850rpm, 900rpm, 950rpm, 1000rpm etc.; Preferred 700-1000rpm.
Preferably, the described anode electrolytic cell current density of step (2) is controlled at 300A/m
2More than, 300A/m for example
2, 350A/m
2, 400A/m
2, 450A/m
2, 500A/m
2,, 550A/m
2, 600A/m
2, 650A/m
2, 700A/m
2, 750A/m
2, 800A/m
2, 900A/m
2, 1000A/m
2, 1200A/m
2Deng, preferred 500-1000A/m
2
Preferably, the time 〉=1h of the described electrochemical oxidation of step (2), such as 1h, 2h, 4h, 6h, 8h, 10h, 12h etc., preferred 4-8h.
Preferably, the electrode material of the described electrolyzer of step (2) is the combination of any a kind or at least 2 kinds in the iron, preferably the combination of any a kind or at least 2 kinds in stainless steel, pure iron or cast iron; Electrode shape is preferably tabular or bar-shaped.
Preferably, the anode of the described electrolyzer of step (2) is iron-based positive plate or iron-based anode bar; Preferred cast iron plate or cast iron bar;
Preferably, the negative electrode of the described electrolyzer of step (2) is the iron-based rod; Preferred stainless steel bar.
In the present invention, the described reaction paste of step (3) dilutes with thinner first, the reaction paste after obtaining diluting, and then carry out solid-liquid separation.Reaction paste is diluted, reduced the viscosity of reaction, be beneficial to further solid-liquid separation.
Preferably, after described reaction paste dilutes with thinner, the content of potassium hydroxide wherein is 100-500g/L, such as 105g/L, 113g/L, 128g/L, 141g/L, 170g/L, 205g/L, 247g/L, 288g/L, 320g/L, 365g/L, 406g/L, 448g/L, 475g/L, 496g/L, 498g/L etc.
Preferably, described thinner is the aqueous solution of water or the potassium hydroxide of mass concentration below 300g/L, preferred pure water.
It is the potassium hydroxide aqueous solution of 285g/L, the potassium hydroxide aqueous solution of 260g/L etc. that the typical but non-limiting example of described thinner has concentration.
As the preferred technical solution of the present invention, the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in described a kind of potassium hydroxide solution
(1) preparation contains the raw material slurry of vanadium slag, potassium hydroxide aqueous solution: vanadium slag and potassium hydroxide aqueous solution Hybrid Heating are made to be mixed obtain the raw material slurry, and be preheated to 120-200 ℃;
Wherein, potassium hydroxide is that the potassium hydroxide aqueous solution mass concentration is 50-70% more than the 3:1 with the vanadium slag quality ratio;
(2) electrochemical oxidation reactions: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, passes into oxidizing gas in solution, and applies mechanical stirring, control anodic current density 300A/m
2More than, carry out at least 1h of electrochemical oxidation reactions, react the complete reaction paste that obtains;
Wherein, anode is any a kind in stainless steel plate, stainless steel bar, iron plate or the iron staff, and negative electrode is stainless steel bar or iron staff;
(3) solid-liquid separation: step (2) gained reaction paste is diluted with thinner, the concentration of potassium hydroxide that is diluted in the slurry is 100-500g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings; Then under 60-130 ℃ of condition, resulting solid-liquid mixed slurry is carried out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution.
Compared with prior art, the present invention has following beneficial effect:
(1) from reaction system, do not introduce new material (such as oxygenant etc.) in the system, later separation is easy;
(2) vanadium slag electrochemical oxidation reactions provided by the invention adopts atmospheric operation, and the control temperature of reaction is 120 ~ 200 ℃, compares with traditional technology, greatly reduces temperature of reaction, thereby has reduced energy consumption, is conducive to industrialization promotion;
(3) it is low to contain vanadium chromium amount in the tailings that the method obtains, and vanadium chromium single extraction yield all can reach more than 80%, has realized efficiently carrying altogether of Vanadium in Vanadium Residue chromium;
(4) the present invention does not add any auxiliary material, and bed drain purge greatly reduces, and can not produce dust and the waste gas harmful to human and environment.
Description of drawings
Fig. 1 is the process flow sheet of the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium in the described potassium hydroxide solution of one embodiment of the present invention.
Embodiment
As one embodiment of the present invention, the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution of the present invention
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating make the raw material slurry, and be preheated to 120-200 ℃, the mass ratio 〉=3:1 of potassium hydroxide and vanadium slag wherein, the potassium hydroxide aqueous solution mass concentration is 50-70%;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 0.6-1.5L/min, stir speed (S.S.) is 600-1200rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 〉=300A/m
2, more than the electrolysis 1h, react the complete reaction paste that gets;
(3) dilution: step (2) gained reaction paste is diluted with thinner, the concentration of potassium hydroxide that is diluted in the slip is about 100-500g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 60-130 ℃ of condition step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, with utilizing ICP to measure wherein vanadium, chromium content after tailings washing, the drying, calculate vanadium, chromium solubility rate.Fig. 1 is the process flow sheet of the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium in the described potassium hydroxide solution of present embodiment.
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand that described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating and make the slip that is mixed, and be preheated to 120-200 ℃, wherein potassium hydroxide is 4:1 with the vanadium slag quality ratio, the potassium hydroxide aqueous solution mass concentration is 50%, namely take by weighing vanadium slag 35g, KOH165g(contains 15% moisture), pure water 115g;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxygen and apply mechanical stirring, the control gas flow is 1.0L/min, stir speed (S.S.) is 700rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 725A/m
2, electrolysis 8h;
(3) dilution: step (2) gained reaction paste is diluted with pure water, being diluted to the slip concentration of potassium hydroxide is about 200g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 70 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, will tailings utilize ICP to measure wherein vanadium, chromium content after the washing, drying, calculate vanadium, the chromium solubility rate is respectively 95.10% and 85.05%.
Embodiment 2
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating and make the slip that is mixed, and be preheated to 150 ℃, wherein potassium hydroxide is 6:1 with the vanadium slag quality ratio, the potassium hydroxide aqueous solution mass concentration is 55%, namely take by weighing vanadium slag 20g, KOH141.20g(contains 15% moisture), pure water 77.00g;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 1.0L/min, stir speed (S.S.) is 850rpm, take iron plate as anode, take stainless steel bar as negative electrode, control anodic current density 1000A/m
2, electrolysis 4h;
(3) dilution: step (2) gained reaction paste is diluted with pure water, being diluted to the slip concentration of potassium hydroxide is about 200g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 70 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, will tailings utilize ICP to measure wherein vanadium, chromium content after the washing, drying, calculate vanadium, the chromium solubility rate is respectively 91.78% and 88.56%.
Embodiment 3
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating and make the slip that is mixed, and be preheated to 150 ℃, wherein potassium hydroxide is 6:1 with the vanadium slag quality ratio, the potassium hydroxide aqueous solution mass concentration is 60%, namely take by weighing vanadium slag 25g, KOH176.5g(contains 15% water), pure water 73.5g;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 0.8L/min, stir speed (S.S.) is 800rpm, take stainless steel plate as anode, take iron staff as negative electrode, control anodic current density 1000A/m
2, electrolysis 4h;
(3) dilution: with pure water step (2) gained reaction paste is diluted, being diluted to the slip concentration of potassium hydroxide is 250g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 80 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, with utilizing ICP to measure wherein vanadium chromium content after tailings washing, the drying, calculate vanadium chromium solubility rate and be respectively 94.15% and 90.47%.
Embodiment 4
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating and make the slip that is mixed, and be preheated to 150 ℃, wherein potassium hydroxide is 5:1 with the vanadium slag quality ratio, the potassium hydroxide aqueous solution mass concentration is 60%, namely take by weighing vanadium slag 30g, KOH176.5g(contains 15% moisture), pure water 73.5g;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 1.2L/min, stir speed (S.S.) is 750rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 900A/m
2, electrolysis 4h;
(3) dilution: step (2) gained reaction paste is diluted with pure water, being diluted to the slip concentration of potassium hydroxide is about 250g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 80 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, will tailings utilize ICP to measure wherein vanadium, chromium content after the washing, drying, calculate vanadium, the chromium solubility rate is respectively 92.15% and 87.85%.
Embodiment 5
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating and make the slip that is mixed, and be preheated to 180 ℃, wherein potassium hydroxide is 5:1 with the vanadium slag quality ratio, the potassium hydroxide aqueous solution mass concentration is 70%, namely take by weighing vanadium slag 40g, KOH235.30g(contains 15% moisture), pure water 50.42g;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 1.0L/min, stir speed (S.S.) is 750rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 725A/m
2, electrolysis 2h;
(3) dilution: step (2) gained reaction paste is diluted with pure water, being diluted to the slip concentration of potassium hydroxide is about 350g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 90 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, will tailings utilize ICP to measure wherein vanadium, chromium content after the washing, drying, calculate vanadium, the chromium solubility rate is respectively 90.15% and 89.05%.
Embodiment 6
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating and make the slip that is mixed, and be preheated to 180 ℃, wherein potassium hydroxide is 6:1 with the vanadium slag quality ratio, the potassium hydroxide aqueous solution mass concentration is 70%, namely take by weighing vanadium slag 40g, KOH282.4g(contains 15% moisture), pure water 60.5g;
(2) electrolysis: the mixed slurry that is preheated to 180 ℃ in the step (1) is added in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 1.0L/min, stir speed (S.S.) is 1000rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 725A/m
2, electrolysis 1h;
(3) dilution: step (2) gained reaction paste is diluted with pure water, being diluted to the slip concentration of potassium hydroxide is about 300g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 90 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, will tailings utilize ICP to measure wherein vanadium, chromium content after the washing, drying, calculate vanadium, the chromium solubility rate is respectively 87.86% and 81.21%.
Embodiment 7
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating make the raw material slurry, and be preheated to 153 ℃, wherein the mass ratio of potassium hydroxide and vanadium slag is 3:1, and the potassium hydroxide aqueous solution mass concentration is 52%; Namely take by weighing vanadium slag 51g, KOH180g(contains 15% moisture), pure water 115g;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 0.6L/min, stir speed (S.S.) is 600rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 300A/m
2, more than the electrolysis 12h, react the complete reaction paste that gets;
(3) dilute: the potassium hydroxide aqueous solution that with concentration is 300g/L dilutes step (2) gained reaction paste, the concentration of potassium hydroxide that is diluted in the slip is about 500g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 130 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, will tailings utilize ICP to measure wherein vanadium, chromium content after the washing, drying, calculate vanadium, the chromium solubility rate is respectively 91.8% and 87.01%.
Embodiment 8
The method of electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium comprises the steps: in a kind of potassium hydroxide solution
(1) batching preheating: will sieve as-200 purpose vanadium slags and potassium hydroxide aqueous solution Hybrid Heating make the raw material slurry, and be preheated to 150 ℃, wherein the mass ratio of potassium hydroxide and vanadium slag is 5.5:1, and the potassium hydroxide aqueous solution mass concentration is 52%; Namely take by weighing vanadium slag 28g, KOH181.2g(contains 15% moisture), pure water 115g;
(2) electrolysis: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, the control gas flow is 1.5L/min, stir speed (S.S.) is 1200rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 500A/m
2, more than the electrolysis 1h, react the complete reaction paste that gets;
(3) dilute: the potassium hydroxide aqueous solution that with concentration is 20g/L dilutes step (2) gained reaction paste, the concentration that is diluted to potassium hydroxide in the slip is about 100g/L, obtains containing the solution of potassium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings;
(4) solid-liquid separation: the mixed slurry that under 130 ℃ of conditions step (3) is obtained carries out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution, will tailings utilize ICP to measure wherein vanadium, chromium content after the washing, drying, calculate vanadium, the chromium solubility rate is respectively 90.03% and 85.01%.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium in the potassium hydroxide solution, it is characterized in that, described method is in the mixed slurry that contains vanadium slag, potassium hydroxide and water, pass into oxidizing gas, carry out electrochemical oxidation reactions, mixed slurry obtains tailings and the alkaline solution that contains vanadium chromium through solid-liquid separation after the reaction.
2. the method for claim 1 is characterized in that, described electrochemical oxidation reactions carries out in electrolyzer, preferably carries out in the normal pressure electrolyzer, and further preferred described electrochemical oxidation reactions stirs in the normal pressure electrolyzer and carries out;
Preferably, described anode electrolytic cell current density is controlled at 300A/m
2More than, preferred 500-1000A/m
2
Preferably, the time 〉=1h of described electrochemical oxidation, preferred 4-8h;
Preferably, the anode material of described electrolyzer is the combination of any a kind or at least 2 kinds in the iron, preferably the combination of any a kind or at least 2 kinds in stainless steel, pure iron or cast iron; Electrode shape is preferably tabular or bar-shaped.
Preferably, the negative electrode material of described electrolyzer is metallic substance or carbon material, and electrode shape is preferably bar-shaped.
3. method as claimed in claim 1 or 2 is characterized in that, described method comprises the steps:
(1) preparation contains the raw material slurry of vanadium slag, potassium hydroxide aqueous solution;
(2) the raw material slurry that step (1) is obtained places electrolyzer, passes into oxidizing gas, carries out electrochemical oxidation reactions, makes reaction paste;
(3) the reaction paste solid-liquid separation that step (2) is obtained, obtain rich iron tailings and contain vanadium, chromium, alkaline solution.
4. such as the described method of one of claim 1-3, it is characterized in that the described vanadium slag of step (1) is through pre-treatment, described pre-treatment comprises any a kind in mechanical activation or the roasting; Described mechanical activation comprises any a kind in roller ball mill, planetary ball mill or the stirring ball-milling;
Preferably, in the described raw material slurry of step (1), the mass ratio 〉=3:1 of potassium hydroxide and vanadium slag, preferred 3:1 ~ 8:1, further preferred 4:1 ~ 6:1;
Preferably, in the described raw material slurry, the mass concentration of potassium hydroxide aqueous solution is 50-70%.
5. such as the described method of one of claim 1-4, it is characterized in that, after the described raw material slurry preparation of step (1) is finished, carry out first preheating, and then carry out step (2);
Preferably, the temperature of described preheating is preferably 120-200 ℃, and further preferred 150-200 ℃, particularly preferably 150-180 ℃.
6. such as the described method of one of claim 1-5, it is characterized in that the described oxidizing gas of step (2) is selected from the combination of any a kind or at least 2 kinds in air, oxygen, oxygen-rich air or the ozone gas, preferred oxygen or air.
7. such as the described method of one of claim 1-6, it is characterized in that the described electrolyzer of step (2) is the normal pressure electrolyzer;
Preferably, the described electrochemical oxidation reactions of step (2) carries out under agitation condition; Stir speed (S.S.) is preferably 600-1200rpm, preferred 700-1000rpm;
Preferably, the described anode electrolytic cell current density of step (2) is controlled at 300A/m
2More than, preferred 500-1000A/m
2
Preferably, the time 〉=1h of the described electrochemical oxidation of step (2), preferred 4-8h.
8. such as the described method of one of claim 1-7, it is characterized in that the anode material of the described electrolyzer of step (2) is the combination of any a kind or at least 2 kinds in the iron, preferably the combination of any a kind or at least 2 kinds in stainless steel, pure iron or cast iron; Electrode shape is preferably tabular or bar-shaped;
Preferably, the anode of the described electrolyzer of step (2) is iron-based positive plate or iron-based anode bar; Preferred cast iron plate or cast iron bar;
Preferably, the negative electrode of the described electrolyzer of step (2) is iron-based rod or carbon back rod; Preferred stainless steel bar.
9. such as the described method of one of claim 1-8, it is characterized in that the described reaction paste of step (3) dilutes with thinner first, the reaction paste after obtaining diluting, and then carry out solid-liquid separation;
Preferably, after described reaction paste diluted with thinner, the content of potassium hydroxide wherein was 100-500g/L;
Preferably, described thinner is the aqueous solution of water or the potassium hydroxide of mass concentration below 300g/L, preferred pure water.
10. such as the described method of one of claim 1-9, it is characterized in that described method comprises the steps:
(1) preparation contains the raw material slurry of vanadium slag, potassium hydroxide aqueous solution: vanadium slag and potassium hydroxide aqueous solution Hybrid Heating are made to be mixed obtain the raw material slurry, and be preheated to 120-200 ℃;
Wherein, potassium hydroxide is that the potassium hydroxide aqueous solution mass concentration is 50-70% more than the 3:1 with the vanadium slag quality ratio;
(2) electrochemical oxidation reactions: the raw material slurry that step (1) is obtained adds in the normal pressure electrolyzer, passes into oxidizing gas in solution, and applies mechanical stirring, control anodic current density 300A/m
2More than, carry out at least 1h of electrochemical oxidation reactions, react the complete reaction paste that obtains;
Wherein, anode is any a kind in stainless steel plate, stainless steel bar, iron plate or the iron staff, and negative electrode is stainless steel bar or iron staff;
(3) solid-liquid separation: step (2) gained reaction paste is diluted with thinner, the concentration of potassium hydroxide that is diluted in the slurry is 100-500g/L, obtains containing the solution of potassium hydroxide, potassium vanadate, potassiumchromate and water-soluble impurity component and the solid-liquid mixed slurry of rich iron tailings; Then under 60-130 ℃ of condition, resulting solid-liquid mixed slurry is carried out filtering separation, obtain respectively rich iron tailings and contain vanadium chromium alkaline solution.
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| CN104294040A (en) * | 2013-07-15 | 2015-01-21 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chrome in electrochemical reinforced vanadium slag decomposition of sodium hydroxide solution |
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