CN104294040A - Method for synchronously extracting vanadium and chrome in electrochemical reinforced vanadium slag decomposition of sodium hydroxide solution - Google Patents
Method for synchronously extracting vanadium and chrome in electrochemical reinforced vanadium slag decomposition of sodium hydroxide solution Download PDFInfo
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Abstract
The invention relates to a method for synchronously extracting vanadium and chrome in electrochemical reinforced vanadium slag decomposition of sodium hydroxide solution. The method comprises the following steps: (1) ingredient preheating: vanadium slag and sodium hydroxide water solution are mixed and heated to prepare mixed slurry; (2) electrolysis: the preheated slurry is added in an electrolytic bath; and oxide gas is fed in the solution for electrolyzing to obtain reactive slurry; and (3) solid-liquid separation: the reactive slurry in the step (2) is filtered and separated to obtain tailings and vanadium and chrome-contained aqueous alkali. The method is low in operation temperature, low in energy consumption and simple in operation, and can realize efficient coextraction of the vanadium and the chrome; the extraction rate of the vanadium can reach 85-99%; and the extraction rate of the chrome can reach 80-95%.
Description
Technical field
The present invention relates to a kind of method of simultaneous extraction vanadium chromium, particularly relate to electrochemically strengthening vanadium slag in a kind of sodium hydroxide solution and decompose the method for simultaneous extraction vanadium chromium.
Background technology
Vanadium slag is the general designation containing the bits of vanadium oxide that is that obtain through oxidation blowing in vanadium extracting process vanadium-bearing hot metal or that obtain through wet method vanadium extraction containing vanadium iron concentrate.The vanadium slag produced by vanadium titano-magnetite in 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 composition, each factory vanadium slag composition difference is also very large, but its phase structure is substantially identical, by compositions such as spinel, peridotites, quartz.
Current is that the enterprise of raw material production vanadium product all adopts traditional vanadium slag sodium roasting technique vanadium extraction from vanadium slag with vanadium titano-magnetite, climbing steel, hold steel, sea, South Africa Wilder, New Zealand Steel Ltd. etc. as China.The technique ultimate principle of sodium roasting is with Na
2cO
3, NaCl, Na
2sO
4be additive Deng sodium salt, by high temperature sodium roasting (750-850 DEG C), the water-insoluble vanadium of lower valency is converted into the sodium salt of water-soluble pentavalent vanadium, again to the direct water logging of sodium roasting product, obtain the leaching liquid containing vanadium, after add ammonium salt obtain ammonium poly-vanadate precipitation, after reducing roasting, obtain the oxide product of vanadium.Sodium roasting technique vanadium recovery is low, and single roasting vanadium recovery is about 70%, and after repeatedly roasting, the rate of recovery of vanadium is also only 80%, and chromium can not extract; Maturing temperature high (750-850 DEG C), energy consumption is higher; In addition, harmful HCl, Cl can be produced in roasting process
2deng aggressive gas, contaminate environment.Therefore, there is correlative study, by improving deficiency to the improvement of above-mentioned technique.
As CN101215005A proposes a kind of method of vanadium slag and sodium salt (sodium carbonate, sodium-chlor) or sylvite (salt of wormwood, Repone K) roasting, this invention is applicable to the low vanadium vanadium slag of high silicon, maturing temperature is 700 ~ 820 DEG C, multiple temperature sections roasting, by control temperature system and salt proportioning, can prevent furnace charge from sintering, make technique direct motion, also roasting soaking time is reduced, V in 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 is all the additive (Na by using different ratio
2cO
3, NaCl, Na
2sO
4, Na
2sO
3deng) and the different index such as extraction yield, roasting time, furnace charge sintering of temperature schedule to vanadium improve, but above technique and traditional sodium roasting principle, operating process, service temperature are substantially identical, maturing temperature cannot be avoided to cross the problem of high traditional technology.
CN101161831A proposes a kind of method of calcification vanadium slag sintering, without the progressively temperature-rise period from low temperature to high temperature after vanadium slag and lime or Wingdale mix, the stoving oven directly entering more than 600 DEG C carries out calcification baking, the vanadium in vanadium slag is made to change calcium vanadate into, in roasting grog, vanadium enters solution through vitriol lixiviation, and then prepares barium oxide product.Compared with sodium roasting technique, the process of this method without the need to progressively heating up to high temperature through low temperature, but directly high-temperature roasting, the temperature of stoving oven is more easily controlled, and shortens roasting time, the production capacity of equipment also increases.But the maturing temperature of calcification baking is very high (600 ~ 950 DEG C) still, and in vanadium slag, chromium is not recovered.
CN102127655A proposes a kind of method of NaOH solution decomposing vanadium slag under normal pressure, temperature of reaction 180 ~ 260 DEG C, and compared with sinter process, vanadium extracting process temperature reduces greatly, and energy consumption reduces, and vanadium extraction efficiency significantly improves, but cannot realize the extraction of chromium; CN102127654A proposes a kind of sodium hydroxide fused salt that uses and decomposes the method containing vanadium chromium slag, temperature of reaction 500 ~ 600 DEG C, and this technique can realize vanadium chromium and carry altogether, but molten salt react ion process temperature is higher; CN102127656A proposes 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 comparatively sodium hydroxide fused-salt medium temperature of reaction reduces, but introduce SODIUMNITRATE medium, subsequent separation process step increases; CN102531056A proposes a kind of method of vanadium slag pressure leaching cleaner production vanadic acid sodium Sodium chromate, temperature of reaction 100-400 DEG C, pressure 0.1-5.0MPa, and this method can realize vanadium chromium and carry altogether, but temperature of reaction is higher, and needs pressurized operation; CN101812588A proposes a kind of method of decomposing vanadium slag with solution of potassium hydroxide under normal pressure, and 180 ~ 260 DEG C of reactions, temperature reduces greatly, and can realize vanadium chromium and carry altogether, and shortcoming is that potassium hydroxide medium cost is higher; CN102534232A proposes a kind of method that decomposing vanadium slag under normal pressure by adding carbon-containing substance into sodium hydroxide solution extracts vanadium chromium, and this method can realize vanadium chromium and carry altogether, but chromium extraction yield still lower (less than 20%).
CN102134640A proposes the method for a kind of catalytic oxidation leaching From Converter Vanadium-bearing Slag, by From Converter Vanadium-bearing Slag and MnSO
2, H
2sO
4furnishing pulp slurry carries out, without the leaching of barrier film catalytic oxidation, utilizing the Mn of the strong oxidizing property of anodic formation
3+realize the Oxidation Leaching of Vanadium in Vanadium Residue, leaching liquid extracts vanadium wherein by conventional ammonia method of sinking, and then prepares Vanadium Pentoxide in FLAKES product.This method avoids the high energy consumption, the high pollution problem that exist in traditional leaching method, and it is widely applicable, and selectivity is good, and processing condition are gentle simultaneously, pollution-free, but this method leaching efficiency is lower; CN102534299A proposes a kind of method of Selectively leaching vanadium from From Converter Vanadium-bearing Slag, 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 diaphragm-free electrolysis leaching vat, leaching reaction is carried out under electric field action, but this method adopts with the DSA anode of iridium tantalum pentoxide coating and Ti cathode, and cost is higher.
CN103060843A proposes the method for electrochemical decomposition vanadium slag simultaneous extraction vanadium chromium in a kind of potassium hydroxide solution, add in normal pressure electrolyzer by after vanadium slag and potassium hydroxide aqueous solution Hybrid Heating, ventilation oxidizing gas, carries out electrochemical oxidation reactions under 120-200 DEG C of condition.This method can realize Vanadium in Vanadium Residue chromium and synchronously reclaim under lower temperature conditions, and vanadium chromium solubility rate can reach 85-99% and 80-95% respectively.But this method is with stainless steel or iron for anode, and there is comparatively serious anodic corrosion problem, and this method take potassium hydroxide as reaction medium, cost is relatively high.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide electrochemically strengthening vanadium slag in a kind of sodium hydroxide solution to decompose the method for simultaneous extraction vanadium chromium.The method of the invention adopts sodium hydroxide solution, realizes Vanadium in Vanadium Residue chromium high efficiency synchronous and extract under electrochemical field effect under lesser temps and alkali concn.Method operational condition of the present invention is gentle, easy handling.
In sodium hydroxide solution provided by the invention, electrochemically strengthening vanadium slag decomposes the method for simultaneous extraction vanadium chromium, comprises the following steps:
(1) vanadium slag is mixed obtained mixture slip with aqueous sodium hydroxide solution;
(2) the mixture slip that step (1) obtains is placed in electrolyzer, passes into oxidizing gas, carry out electrolysis;
(3) by the reaction slurry solid-liquid separation that step (2) obtains, rich iron tailings and the alkaline solution containing vanadium, chromium is obtained.
What vanadium slag of the present invention was preferably produced through blast furnace or direct-reduction flow process by vanadium titano-magnetite contains vanadium (chromium) pig iron (water) more under the high temperature conditions with the vanadium slag that oxygen or air adopt the production processes such as shaking ladle vanadium extraction, hot metal ladle vanadium extraction and the vanadium extraction of various top blast combined blown converter to be formed for oxidizing medium.
Preferably, step (1) described vanadium slag is through pre-treatment, and described pre-treatment comprises mechanical activation or roasting; Described pre-treatment is affiliated field known technology, does not repeat them here.
Preferably, described sodium hydroxide is more than 1:1 with the ratio of vanadium slag quality, such as, be 3:1,4:1,5:1,7:1,9:1,11:1 etc., is preferably 2:1-8:1, more preferably 2:1-6:1.
Preferably, in described aqueous sodium hydroxide solution, the mass concentration of sodium hydroxide is more than 20wt%, be such as 22wt%, 26wt%, 31wt%, 35wt%, 39wt%, 44wt%, 49wt%, 55wt%, 60wt%, 66wt%, 73wt%, 79wt%, 82wt%, 88wt%, 90wt% etc., be preferably 20wt%-80wt%.
Preferably, after the described mixture slurry preparation of step (1) completes, first carry out preheating, and then carry out step (2).
Preferably, described preheating temperature is more than 80 DEG C, such as, be 90 DEG C, 95 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 135 DEG C, 145 DEG C, 155 DEG C, 160 DEG C, 170 DEG C etc., is preferably 80-150 DEG C.
Preferably, step (2) described electrolyzer is normal pressure electrolyzer.
Preferably, described oxidizing gas is the one kind or two or more mixing in oxygen, air, oxygen-rich air or ozone, the typical but non-limiting example of described combination has: the combination of oxygen and air, the combination of oxygen and ozone, the combination etc. of oxygen, oxygen-rich air, ozone, is preferably oxygen and/or air.The volume fraction that described oxygen-rich air refers to oxygen is greater than the air of the average oxygen purity in air.
Preferably, step (2) described electrolysis is under agitation carried out.
Preferably, the anodic current density of described electrolysis is 250A/m
2above, be such as 260A/m
2, 270A/m
2, 300A/m
2, 350A/m
2, 390A/m
2, 450A/m
2, 550A/m
2, 600A/m
2, 700A/m
2, 800A/m
2, 900A/m
2, 1100A/m
2deng, be preferably 500-1000A/m
2.
Preferably, the time of described electrolysis is more than 1h, such as, be 1.5h, 2h, 2.5h, 3h, 3.5h, 4.2h, 4.9h, 5.5h, 6h, 7h, 9h, 10h etc., is preferably 4-8h.
Preferably, the anode material of electrolysis described in step (2) is the one kind or two or more combination in nickel, stainless steel, pure iron or cast iron, is preferably nickel and/or stainless steel, more preferably nickel; Preferred anodes form is tabular or bar-shaped.
Preferably, the anode of described electrolysis is nickel plate or nickel rod.
Preferably, the negative electrode material of described electrolysis is the one kind or two or more combination in stainless steel bar, iron staff or cast iron bar.
Preferably, step (3) described reaction slurry first dilutes with thinner, obtains the reaction slurry after diluting, and then carries out solid-liquid separation.
Preferably, described thinner be water or concentration at below 300g/L, be such as the aqueous sodium hydroxide solution of 10g/L, 50g/L, 90g/L, 110g/L, 140g/L, 180g/L, 22g/L, 260g/L, 290g/L etc., be preferably water.
Preferably, after described reaction slurry thinner dilution, the content of sodium hydroxide is wherein 100-500g/L, such as, be 120g/L, 150g/L, 180g/L, 205g/L, 240g/L, 280g/L, 330g/L, 370g/L, 440g/L, 490g/L etc.
Preferably, reaction slurry temperature during filtering separation described in step (3) is 60-100 DEG C, such as, be 64 DEG C, 69 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 84 DEG C, 88 DEG C, 92 DEG C, 96 DEG C, 99 DEG C etc.
As optimal technical scheme, described method comprises the steps:
(1) vanadium slag is mixed obtained mixture slip with aqueous sodium hydroxide solution: vanadium slag and aqueous sodium hydroxide solution Hybrid Heating are obtained mixture slip, and is preheated to more than 80 DEG C;
Wherein, sodium hydroxide is more than 1:1 with the ratio of vanadium slag quality, and in aqueous sodium hydroxide solution, the mass concentration of sodium hydroxide is more than 20wt%;
(2) the mixture slip that step (1) obtains is placed in normal pressure electrolyzer, passes into oxidizing gas and apply mechanical stirring, anodic current density is 250A/m
2above, carry out more than electrolysis 1h, obtained reaction slurry;
Wherein, electrolytic anode is a kind in nickel plate, stainless steel plate, pure iron plate, cast iron plate, nickel rod, stainless steel bar, pure iron rod or cast iron bar, and electrolysis cathode is a kind in stainless steel bar, iron staff or cast iron bar;
(3) reaction slurry that step (2) obtains is diluted at the aqueous sodium hydroxide solution of below 300g/L by water or concentration, the content making the sodium hydroxide diluted in rear slip is 100-500g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings; Then under 60-100 DEG C of condition, the mixed slurry obtained is carried out filtering separation, obtain rich iron tailings and the alkaline solution containing vanadium, chromium respectively.
Compared with prior art, the invention has the advantages that:
(1) from reaction system, leach liquor composition is simple, does not introduce new material in system;
(2) vanadium slag electrochemically strengthening provided by the invention decomposes the method for simultaneous extraction vanadium chromium, and adopt atmospheric operation, control temperature of reaction is 80-150 DEG C, compared with traditional technology, greatly reduce temperature of reaction, thus reduce energy consumption, be conducive to industrialization promotion;
(3) low containing vanadium chromium amount in the tailings that the method obtains, vanadium chromium single-trial extraction rate all can reach 80-95%, achieves the efficient of Vanadium in Vanadium Residue chromium and carries altogether;
(4) the present invention does not add any auxiliary material, and bed drain purge greatly reduces, and can not produce the harmful dust of human and environment and waste gas.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
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, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.Fig. 1 is process flow diagram of the present invention.
Embodiment 1
(1) to prepare burden preheating: be that the vanadium slag of below 200 orders and aqueous sodium hydroxide solution Hybrid Heating obtain mixture slip by screening, wherein sodium hydroxide and vanadium slag quality are than being 2:1, and aqueous sodium hydroxide solution mass concentration is 40%, namely takes vanadium slag 35g, NaOH70g, pure water 105g;
(2) electrolysis: the mixed slurry being preheated to 100 DEG C in step (1) is added in normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, control gas flow is 1.0L/min, stir speed (S.S.) is 1100rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 1200A/m
2, electrolysis 10h;
(3) dilute: with pure water, step (2) gained reaction slurry is diluted, being diluted to slip naoh concentration is about 200g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings;
(4) solid-liquid separation: under 80 DEG C of conditions, the mixed slurry that step (3) obtains is carried out filtering separation, obtain rich iron tailings respectively and contain vanadium chromium alkaline solution, utilize ICP to measure wherein vanadium, chromium content by after tailings washing, drying, calculate vanadium, chromium solubility rate is respectively 92.15% and 82.36%.
Embodiment 2
(1) to prepare burden preheating: be that the vanadium slag of below 200 orders and aqueous sodium hydroxide solution Hybrid Heating obtain mixture slip by screening, wherein sodium hydroxide and vanadium slag quality are than being 4:1, and aqueous sodium hydroxide solution mass concentration is 40%, namely takes vanadium slag 20g, NaOH80g, pure water 120g;
(2) electrolysis: the mixed slurry being preheated to 110 DEG C in step (1) is added in normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, control gas flow is 1.0L/min, stir speed (S.S.) is 1000rpm, take iron plate as anode, take stainless steel bar as negative electrode, control anodic current density 1000A/m
2, electrolysis 6h;
(3) dilute: with pure water, step (2) gained reaction slurry is diluted, being diluted to slip naoh concentration is about 200g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings;
(4) solid-liquid separation: under 70 DEG C of conditions, the mixed slurry that step (3) obtains is carried out filtering separation, obtain rich iron tailings respectively and contain vanadium chromium alkaline solution, utilize ICP to measure wherein vanadium, chromium content by after tailings washing, drying, calculate vanadium, chromium solubility rate is respectively 88.31% and 84.26%.
Embodiment 3
(1) to prepare burden preheating: by screening for being not more than 200 object vanadium slags and aqueous sodium hydroxide solution Hybrid Heating obtains mixture slip, wherein sodium hydroxide and vanadium slag quality are than being 6:1, and aqueous sodium hydroxide solution mass concentration is 60%, namely takes vanadium slag 25g, NaOH150g, pure water 100g;
(2) electrolysis: the mixed slurry being preheated to 120 DEG C in step (1) is added in normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, 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 750A/m
2, electrolysis 6h
(3) dilute: with pure water, step (2) gained reaction slurry is diluted, being diluted to slip naoh concentration is 250g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings;
(4) solid-liquid separation: under 80 DEG C of conditions, the mixed slurry that step (3) obtains is carried out filtering separation, obtain rich iron tailings respectively and contain vanadium chromium alkaline solution, utilize ICP to measure wherein vanadium chromium content by after tailings washing, drying, calculate vanadium chromium solubility rate and be respectively 89.96% and 86.45%.
Embodiment 4
(1) to prepare burden preheating: be that the vanadium slag of below 200 orders and aqueous sodium hydroxide solution Hybrid Heating obtain mixture slip by screening, wherein sodium hydroxide and vanadium slag quality are than being 5:1, and aqueous sodium hydroxide solution mass concentration is 40%, namely takes vanadium slag 20g, NaOH100g, pure water 150g;
(2) electrolysis: the mixed slurry being preheated to 120 DEG C in step (1) is added in normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, 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 1000A/m
2, electrolysis 10h;
(3) dilute: with pure water, step (2) gained reaction slurry is diluted, being diluted to slip naoh concentration is about 200g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings;
(4) solid-liquid separation: under 80 DEG C of conditions, the mixed slurry that step (3) obtains is carried out filtering separation, obtain rich iron tailings respectively and contain vanadium chromium alkaline solution, utilize ICP to measure wherein vanadium, chromium content by after tailings washing, drying, calculate vanadium, chromium solubility rate is respectively 98.89% and 92.56%.
Embodiment 5
(1) to prepare burden preheating: be that the vanadium slag of below 200 orders and aqueous sodium hydroxide solution Hybrid Heating obtain mixture slip by screening, wherein sodium hydroxide and vanadium slag quality are than being 5:1, and aqueous sodium hydroxide solution mass concentration is 50%, namely takes vanadium slag 20g, NaOH100g, pure water 100g;
(2) electrolysis: the mixed slurry being preheated to 130 DEG C in step (1) is added in normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, 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 750A/m
2, electrolysis 4h;
(3) dilute: with pure water, step (2) gained reaction slurry is diluted, being diluted to slip naoh concentration is about 250g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings;
(4) solid-liquid separation: under 90 DEG C of conditions, the mixed slurry that step (3) obtains is carried out filtering separation, obtain rich iron tailings respectively and contain vanadium chromium alkaline solution, utilize ICP to measure wherein vanadium, chromium content by after tailings washing, drying, calculate vanadium, chromium solubility rate is respectively 85.24% and 80.86%.
Embodiment 6
(1) to prepare burden preheating: be that the vanadium slag of below 200 orders and aqueous sodium hydroxide solution Hybrid Heating obtain mixture slip by screening, wherein sodium hydroxide and vanadium slag quality are than being 6:1, and aqueous sodium hydroxide solution mass concentration is 20%, namely takes vanadium slag 10g, NaOH60g, pure water 240g;
(2) electrolysis: the mixed slurry being preheated to 110 DEG C in step (1) is added in normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, 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 1500A/m
2, electrolysis 10h;
(3) dilute: with pure water, step (2) gained reaction slurry is diluted, being diluted to slip naoh concentration is about 150g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings;
(4) solid-liquid separation: under 60 DEG C of conditions, the mixed slurry that step (3) obtains is carried out filtering separation, obtain rich iron tailings respectively and contain vanadium chromium alkaline solution, utilize ICP to measure wherein vanadium, chromium content by after tailings washing, drying, calculate vanadium, chromium solubility rate is respectively 87.68% and 85.46%.
Embodiment 7
(1) to prepare burden preheating: be that the vanadium slag of below 200 orders and aqueous sodium hydroxide solution Hybrid Heating obtain mixture slip by screening, wherein sodium hydroxide and vanadium slag quality are than being 8:1, and aqueous sodium hydroxide solution mass concentration is 40%, namely takes vanadium slag 20g, NaOH160g, pure water 240g;
(2) electrolysis: the mixed slurry being preheated to 130 DEG C in step (1) is added in normal pressure electrolyzer, in solution, pass into oxidizing gas and apply mechanical stirring, control gas flow is 1.6L/min, stir speed (S.S.) is 1200rpm, take stainless steel plate as anode, take stainless steel bar as negative electrode, control anodic current density 250A/m
2, electrolysis 12h;
(3) dilute: with pure water, step (2) gained reaction slurry is diluted, being diluted to slip naoh concentration is about 100g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings;
(4) solid-liquid separation: under 60 DEG C of conditions, the mixed slurry that step (3) obtains is carried out filtering separation, obtain rich iron tailings respectively and contain vanadium chromium alkaline solution, utilize ICP to measure wherein vanadium, chromium content by after tailings washing, drying, calculate vanadium, chromium solubility rate is respectively 86.69% and 82.56%.
Applicant states, 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, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. in sodium hydroxide solution, electrochemically strengthening vanadium slag decomposes a method for simultaneous extraction vanadium chromium, comprises the following steps:
(1) vanadium slag is mixed obtained mixture slip with aqueous sodium hydroxide solution;
(2) the mixture slip that step (1) obtains is placed in electrolyzer, passes into oxidizing gas, carry out electrolysis;
(3) reaction slurry that step (2) obtains is carried out solid-liquid separation, obtain rich iron tailings and the alkaline solution containing vanadium, chromium.
2. the method for claim 1, is characterized in that, step (1) described vanadium slag is through pre-treatment, and described pre-treatment comprises mechanical activation or roasting;
Preferably, described sodium hydroxide is more than 1:1 with the ratio of vanadium slag quality, is preferably 2:1-8:1, more preferably 2:1-6:1;
Preferably, in described aqueous sodium hydroxide solution, the mass concentration of sodium hydroxide is more than 20wt%, is preferably 20wt%-80wt%.
3. method as claimed in claim 1 or 2, is characterized in that, after the described mixture slurry preparation of step (1) completes, first carry out preheating, and then carry out step (2);
Preferably, described preheating temperature is more than 80 DEG C, is preferably 80-150 DEG C.
4. the method as described in any one of claim 1-3, is characterized in that, step (2) described electrolyzer is normal pressure electrolyzer;
Preferably, described oxidizing gas is the one kind or two or more mixing in oxygen, air, oxygen-rich air or ozone, is preferably oxygen and/or air.
5. the method as described in any one of claim 1-4, is characterized in that, step (2) described electrolysis is under agitation carried out;
Preferably, the anodic current density of described electrolysis is 250A/m
2above, 500-1000A/m is preferably
2;
Preferably, the time of described electrolysis is more than 1h, is preferably 4-8h.
6. the method as described in any one of claim 1-5, it is characterized in that, the anode material of electrolysis described in step (2) is the one kind or two or more combination in nickel, stainless steel, pure iron or cast iron, is preferably nickel and/or stainless steel, more preferably nickel; Preferred anodes form is tabular or bar-shaped;
Preferably, the anode of described electrolysis is nickel plate or nickel rod;
Preferably, the negative electrode material of described electrolysis is the one kind or two or more combination in stainless steel bar, iron staff or cast iron bar.
7. the method as described in any one of claim 1-6, is characterized in that, step (3) described reaction slurry first dilutes with thinner, obtains the reaction slurry after diluting, and then carries out solid-liquid separation;
Preferably, described thinner is water or the concentration aqueous sodium hydroxide solution at below 300g/L, is preferably water;
Preferably, after described reaction slurry thinner dilution, the content of sodium hydroxide is wherein 100-500g/L.
8. the method as described in any one of claim 1-7, is characterized in that, reaction slurry temperature during filtering separation described in step (3) is 60-100 DEG C.
9. the method as described in any one of claim 1-8, is characterized in that, described method comprises the steps:
(1) vanadium slag is mixed obtained mixture slip with aqueous sodium hydroxide solution: vanadium slag and aqueous sodium hydroxide solution Hybrid Heating are obtained mixture slip, and is preheated to more than 80 DEG C;
Wherein, sodium hydroxide is more than 1:1 with the ratio of vanadium slag quality, and in aqueous sodium hydroxide solution, the mass concentration of sodium hydroxide is more than 20wt%;
(2) the mixture slip that step (1) obtains is placed in normal pressure electrolyzer, passes into oxidizing gas and apply mechanical stirring, anodic current density is 250A/m
2above, carry out more than electrolysis 1h, obtained reaction slurry;
Wherein, electrolytic anode is a kind in nickel plate, stainless steel plate, pure iron plate, cast iron plate, nickel rod, stainless steel bar, pure iron rod or cast iron bar, and electrolysis cathode is a kind in stainless steel bar, iron staff or cast iron bar;
(3) reaction slurry that step (2) obtains is diluted at the aqueous sodium hydroxide solution of below 300g/L by water or concentration, the content making the sodium hydroxide diluted in rear slip is 100-500g/L, obtains starching containing the solution of sodium hydroxide, vanadic acid sodium, Sodium chromate and water-soluble impurity component and the Solid-liquid mixture of rich iron tailings; Then under 60-100 DEG C of condition, the mixed slurry obtained is carried out filtering separation, obtain rich iron tailings and the alkaline solution containing vanadium, chromium respectively.
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