CN102534232A - Method for decomposing vanadium slag under normal pressure by adding carbon-containing substance into sodium hydroxide solution - Google Patents
Method for decomposing vanadium slag under normal pressure by adding carbon-containing substance into sodium hydroxide solution Download PDFInfo
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- CN102534232A CN102534232A CN2012100049108A CN201210004910A CN102534232A CN 102534232 A CN102534232 A CN 102534232A CN 2012100049108 A CN2012100049108 A CN 2012100049108A CN 201210004910 A CN201210004910 A CN 201210004910A CN 102534232 A CN102534232 A CN 102534232A
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Abstract
The invention relates to a method for decomposing vanadium slag under normal pressure and extracting vanadium and chromium by adding a carbon-containing substance into a sodium hydroxide solution. The method comprises the following steps of: uniformly mixing the vanadium slag and the carbon-containing substance, and adding the mixture, water and NaOH into a normal pressure reactor; introducing oxidizing gas for oxidization reaction, and diluting reaction slurry obtained by the reaction by using a diluent to obtain mixed slurry containing NaOH, sodium vanadate, sodium chromate, sodium silicate and tailings; and filtering and separating the mixed slurry to obtain the tailings, and an alkaline solution containing the vanadium and the chromium. The operating temperature of the method is below the boiling point of the solution, and the method can be implemented under normal pressure, and is easy to implement and high in safety; and the operating temperature is far lower than the temperature of the traditional vanadium extracting process, the extraction ratio of the vanadium is high, the chromium can be partially extracted synchronously, the total vanadium contained in the tailings is 0.2 to 0.6 weight percent (based on V2O5), and the leaching rate of the chromium is 8-20 percent.
Description
Technical field
The present invention relates to a kind of method of wet processing vanadium slag, particularly a kind of sodium hydroxide solution adds the method that carbonaceousmaterial normal pressure decomposing vanadium slag extracts vanadium and chromium.
Background technology
Vanadium slag is a kind of vanadium enrichment material that under the oxygen-containing gas existence condition, is blown out 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 the composition of working method and vanadium titano-magnetite, and in general, vanadium slag is by V
2O
5, SiO
2, Al
2O
3, MgO, Cr
2O
3, TiO
2, component such as CaO forms, each factory's vanadium slag composition difference is also very big, but its phase structure is basic identical, by compositions such as spinel, peridotites, quartz.
The enterprise that with the vanadium titano-magnetite is raw material production iron, vanadium product all adopts traditional vanadium slag sodium roasting technology vanadium extraction from vanadium slag at present, climbing steel, hold steel, sea, South Africa Wilder, New Zealand Steel Ltd. etc. like China.The ultimate principle of sodium roasting technology is with Na
2CO
3Be additive; The vanadium of lower valency is converted into the sodium salt of water-soluble pentavalent vanadium through high temperature sodium roasting (750~850 ℃); Again to the direct water logging of sodium roasting product; Obtain containing the leaching liquid of vanadium, make the ammonium poly-vanadate deposition, after reducing roasting, obtain the oxide product of vanadium through purifying back adding ammonium salt.Sodium roasting technology vanadium recovery is low, and single roasting vanadium recovery is about 70%, and the recovery of vanadium also is merely 80% after roasting repeatedly; Maturing temperature high (750~850 ℃), and need repeatedly roasting, energy consumption is high; In roasting process, can produce deleterious HCl, Cl
2Deng corrosive gases, contaminate environment.
CN 101215005A 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, and this patent is applicable to that high silicon hangs down the vanadium vanadium slag, and maturing temperature is 700~820 ℃; The multiple temperature sections roasting; Through controlled temperature system and salt proportioning, can prevent the furnace charge sintering, make the technology direct motion; Also reduced the roasting soaking time, V in the tailings
2O
5Content can reach 0.5~1%;
CN 101215005 discloses a kind of method of utilizing vanadium slag to produce Vanadium Pentoxide in FLAKES: in vanadium slag, add an alkali metal salt; Fully mixing obtains mixture; Resulting mixture placed carry out oxidizing roasting in the stoving oven, obtain the vanadium slag grog, cool off fast and carry out water logging; The filtration removal of impurities adjustment pH value back that obtains filtrating adds ammonium salt and carries out precipitation, calcines the precipitation filter cake and obtains Vanadium Pentoxide in FLAKES.This method is simple and easy to use, equipment requirements is low, easy to operate, the material consumption cost is low, and the residual quantity of Vanadium Pentoxide in FLAKES is 0.55%~1.0% in the waste, has good economic benefits and social benefit.
CN 1884597A, CN 86108218A etc. have carried out different improvement to the additive and the temperature schedule of sodium roasting technology, and ultimate principle all is through using the additive (Na of different proportionings
2CO
3, NaCl, Na
2SO
4, Na
2SO
3Deng) and the different temperature system come index such as extraction yield, roasting time, furnace charge sintering to improve and improve to vanadium; But above technology 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.
The high temperature vanadium slag that CN 1082617A has proposed blowing is obtained is handled 900~1300 ℃ of direct oxygen blast; Impel the low price vanadium in the slag to be oxidized into the pentavalent vanadium; After the slag cooling fragmentation, the vanadium under certain temperature, alkali concn, oxygen partial pressure in the leached mud, this method needn't high-temperature roasting once more after the vanadium slag cooling; Energy consumption greatly reduces, and the environmental pollution of having avoided sodium roasting to cause.
The calcification baking method is present a kind of environment friendly and pollution-free extraction vanadium method, does not have the harmful smoke discharging aborning, the waste water permanent loops.It is to add in the navajoite soil with lime carbonate, after high-temperature roasting, leaches through pickling process, and spent ion exchange resin absorption again, impurity removal and purification forms then.
CN 101161831A has proposed a kind of method of vanadium slag calcification baking; Compare with sodium roasting technology; Need not the process that process low temperature progressively heats up to high temperature during calcification baking, but directly high-temperature roasting is controlled the temperature of stoving oven more easily; And shortened roasting time, the production capacity of equipment also increases.But the maturing temperature of calcification baking still very high (600~950 ℃).
The existing at present technology of utilizing Leaching of Vanadium from Vanadium slag behind the vanadium slag ball milling after the vanadium titano-magnetite steel-making, directly leaches with sulfuric acid, and without sinter process, but the leaching yield of vanadium is lower.
CN 102127656A relates to a kind of method of liquid-phase oxidation decomposing vanadium slag, with NaOH, NaNO
3According to the certain mass ratio, place normal-pressure reaction kettle, vanadium slag is added after being warming up to 330-480 ℃, and feed oxidizing gas and carry out liquid phase oxidation reaction, react and obtain reaction paste after 0.5-6 hour; Reaction paste is used diluent, and dilute filtration separates the aqueous solution that obtains tailings and contain vanadium, chromium.This method temperature of reaction is low, atmospheric operation, and security is good, is easy to industrial implementation, can realize that vanadium chromium is carried and vanadium chromium resource utilization ratio height altogether in the vanadium slag, but service temperature is high, has added NaNO
3Oxidizing medium has increased the later separation operating unit.
CN 102127655A relates to the method for a kind of sodium hydroxide solution normal pressure decomposing vanadium slag vanadium extraction, adds normal pressure reactor with vanadium slag or through pretreated vanadium slag with water, NaOH; Under the oxidizing gas existence condition, carry out oxidizing reaction, again the reaction paste that obtains is diluted with thinner, obtain containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr and tailings; Mixed slurry is carried out filtering separation, obtain the tailings and the aqueous solution that contains vanadium.The extraction yield of vanadium is not high enough in this method, contain in the tailings vanadium total amount at 0.5-1wt% (with V
2O
5Meter).In addition, this invention can not realize that vanadium chromium carries altogether.
Summary of the invention
The object of the present invention is to provide a kind of method of in sodium hydroxide solution, adding carbonaceousmaterial normal pressure decomposing vanadium slag simultaneous extraction vanadium and chromium.This method can be carried out the vanadium slag treatment process under the atmospheric low-temperature condition, do not need high-temperature roasting, has reduced temperature of reaction, realizes the single high efficiency extraction of vanadium, and chromium also can partly obtain simultaneous extraction.
For reaching this purpose, the present invention adopts following technical scheme:
A kind of sodium hydroxide solution adds the method for carbonaceousmaterial normal pressure decomposing vanadium slag, may further comprise the steps:
(1) batching: vanadium slag is mixed the back with carbonaceousmaterial add normal pressure reactor with water, NaOH, wherein, the mass ratio of NaOH and vanadium slag is 2.5: 1~8: 1; The mass ratio of vanadium slag and carbonaceousmaterial is 3: 1~10: 1; The mass concentration of sodium hydroxide solution is 52~93wt%;
(2) reaction: step (1) prepared material is reacted under the condition that feeds oxidizing gas, and airshed is stabilized in 0.2~1.2L/min, and control reaction temperature is 180~240 ℃, and reaction times 1~7h obtains reaction paste; The reaction decomposes process is undertaken by following mode:
FeO·V
2O
3+6NaOH+5/4O
2→1/2Fe
2O
3+3H
2O+2Na
3VO
4;
FeO·Cr
2O
3+4NaOH+7/4O
2→1/2Fe
2O
3+2H
2O+2Na
2CrO
4;
(3) dilution: step (2) is obtained reaction paste, and to be diluted to naoh concentration be 100~500g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
(4) filtering separation: the mixed slurry that step (3) is obtained carries out filtering separation at 80~130 ℃, obtains tailings and the alkaline solution that contains vanadium, chromium.
The mass ratio of said NaOH of step of the present invention (1) and vanadium slag can be selected arbitrarily according to practical situation in the scope at 2.5: 1~8: 1, and for example 2.6: 1,3.2: 1; 4: 1,5.5: 1,5.6: 1; 6.5: 1,7.3: 1,7.9: 1 etc.; Preferred 3: 1~7: 1, further preferred 4.5: 1~6: 1, more preferably 5: 1.
The mass ratio of vanadium slag and carbonaceousmaterial is 3: 1~10: 1, for example 3.5: 1,4: 1,5.2: 1,6: 1,8: 1,9.8: 1 etc., is preferably 4.5: 1~7: 1, further preferred 5: 1.
The mass concentration of sodium hydroxide solution is that 52~93wt% all can be used for the present invention, 55wt% for example, 62wt%, 68wt%, 75wt%, 84wt%, 92wt% etc., preferred 60~90wt%, further preferred 65~80wt%, more preferably 75wt%.
The said airshed of step of the present invention (2) is stabilized in 0.2~1.2L/min, 0.3L/min for example, 0.55L/min; 0.7L/min 0.96L/min, 1.18L/min etc. all can be used for embodiment of the present invention; Preferred 0.2~1L/min, further preferred 0.5~0.8L/min, more preferably 0.6L/min.
Control reaction temperature is 180~240 ℃, for example 183 ℃, and 204 ℃, 210 ℃, 217 ℃, 220 ℃, 228 ℃, 238 ℃ etc., preferred 200~225 ℃, further preferred 215 ℃;
Reaction times is 1~7h, 1.2h for example, 1.6h, 2.2h, 3h, 3.6h, 4.2h, 4.5h, 5.1h, 5.8h etc., preferred 2~6h, further preferred 3.5~5h, more preferably 4h;
Mixing speed is made as 500~800rpm, 510rpm for example, 565rpm, 600rpm, 635rpm, 660rpm, 715rpm, 750rpm, but equal embodiment of the present invention such as 790rpm, preferred 650~720rpm, further preferred 700rpm.
It is 100~500g/L scope that the reaction paste that step according to the invention (3) obtains step (2) is diluted to naoh concentration, 120g/L for example, 160g/L, 200g/L; 260g/L, 315g/L, 340g/L, 384g/L; 412g/L, 460g/L, 480g/L etc.; Preferred 180~450g/L, further preferred 250~350g/L, more preferably 300g/L.
The service temperature of step of the present invention (4) is 80~130 ℃, for example 85 ℃, 96 ℃, 105 ℃, 120 ℃, 128 ℃ etc., can select suitable temp arbitrarily.
The preferred porous carbonaceous material of carbonaceousmaterial according to the invention, further preferred gac and/or coke.Gac and coke all have very strong adsorption, can the adsorption of oxygen promotes oxidn the carrying out of reaction, the two also all has very strong adsorption to chromium.In addition, porous carbonaceous material can enlarge reaction contact area, improves reaction efficiency, to playing of oxidizing reaction very strong katalysis, improved extraction yield greatly.
Oxidizing gas according to the invention is the mixed gas of air, oxygen or air and oxygen.The ratio of mixed gas air and oxygen can be selected reasonable numerical value arbitrarily according to practical situation and technician's operating experience, does not have particular restriction.The present invention is preferably oxygen.Other oxidizing gas that those skilled in the art can be known all can be used for the present invention.
The thinner that the said dilution operation of step of the present invention (3) is used is water or sodium hydroxide solution.Other can play diluting effect to reaction paste, and the thinner of not bringing new impurity into all can be used for the present invention, and those skilled in the art can carry out choose reasonable according to common practise and practical experience.Said water can be selected the ordinary test water for use, preferred pure water or ultrapure water, further preferred ultrapure water.The concentration of said sodium hydroxide solution is 0~400g/L, 5g/L for example, 80g/L, 240g/L, 300g/L, 385g/L etc.
Vanadium slag according to the invention for by vanadium titano-magnetite through blast furnace or vanadium (chromium) pig iron (water) that contains that reduces directly that flow process produces under hot conditions, be the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction production process to form with oxygen or air.The present invention can at first grind pre-treatment with said vanadium slag process, and sieves out 150~400 purpose vanadium slags as raw material.The particle diameter of vanadium slag is more little, helps enlarging reaction contact area more, improves reaction efficiency, finally helps the extraction of vanadium and chromium.
Compare with the prior art scheme, beneficial effect of the present invention is:
1) sodium hydroxide solution provided by the invention adds the method that carbonaceousmaterial normal pressure decomposing vanadium slag extracts vanadium and chromium, and temperature of reaction is 180~240 ℃, compares with traditional technology, greatly reduces temperature of reaction; In addition, the cost of sodium hydroxide helps reducing cost well below Pottasium Hydroxide;
2) contain the vanadium total amount at 0.2~0.6wt% in the tailings that the present invention obtains, improved the extraction yield of vanadium greatly;
3) the present invention through add gac or coke realized vanadium slag at a middle or low price chromium be oxidized to sexavalent chrome and stripping can make chromium stripping 8%~20%, realize the simultaneous extraction of vanadium and chromium;
4) service temperature of the present invention is below the solution boiling point, and process only needs just can carry out easy handling under the normal pressure;
5) reaction system of the present invention is stable, and it is good to be easy to control and security.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Down in the face of further explain of the present invention.But following instance only is a simple and easy example of the present invention, does not represent or limits rights protection scope of the present invention, and interest field of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
Embodiment 1:
Present embodiment uses vanadium slag to contain V
2O
510.45wt%, be by vanadium titano-magnetite through blast furnace process production contain vanadium (chromium) pig iron (water), under hot conditions, be the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction process to form again with the air.
1) batching: will be sized to 200 purpose vanadium slags with gac mix Hou Heshui, NaOH adds normal pressure reactor, wherein, the mass ratio of NaOH and vanadium slag is 4: 1; The mass ratio of vanadium slag and gac is 10: 1; The mass concentration of sodium hydroxide solution is 80wt%; Promptly take by weighing NaOH200g, vanadium slag 50g, gac 5g, water 50ml;
2) reaction: the step 1) prepared material is packed in the normal pressure reactor, and bubbling air carries out oxidizing reaction, and wherein, the flow control of air is at 1L/min, and control reaction temperature is 220 ℃, mixing speed 700rpm, and the reaction times is 6h, obtains reaction paste;
3) dilution: when step 2) after the end, water dilutes the reaction paste in the reactor drum, and being diluted to the slurry naoh concentration is about 500g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
4) filtering separation: the mixed slurry that step 3) is obtained carries out filtering separation at 80 ℃, obtain tailings and contain the alkaline solution of vanadium and chromium, with tailings washing, dry back mensuration its to contain total vanadium amount be that 0.37wt% is (with V
2O
5Meter), the solubility rate of chromium is 15%.
Embodiment 2:
Present embodiment uses vanadium slag to contain V
2O
58.2wt% is to contain vanadium (chromium) pig iron (water) by vanadium titano-magnetite through what direct reduction flow process was produced, under hot conditions, is the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction process to form with oxygen again.
1) batching: will be sized to 200 purpose vanadium slags with gac mix the back and the NaOH aqueous solution add normal pressure reactor, wherein, the mass ratio of NaOH and vanadium slag is 6: 1; The mass ratio of vanadium slag and gac is 3: 1; The mass concentration of sodium hydroxide solution is 60wt%; Promptly take by weighing NaOH300g, vanadium slag 50g, gac 16.67g, ultrapure water 200ml;
2) reaction: the step 1) prepared material is packed in the normal pressure reactor; Aerating oxygen is that 1: 1 mixed gas carries out oxidizing reaction with AIR Proportional; Wherein the flow control of gas is at 0.8L/min, and control reaction temperature is 200 ℃, mixing speed 600rpm; Reaction times is 4h, obtains reaction paste;
3) dilution: when step 2) after the end, water dilutes the reaction paste in the reactor drum, and being diluted to the slurry naoh concentration is 400g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
4) filtering separation: the mixed slurry that step 3) is obtained carries out filtering separation about 90 ℃, obtain tailings and contain the alkaline solution of vanadium and chromium, with tailings washing, dry back mensuration its to contain total vanadium amount be that 0.5wt% is (with V
2O
5Meter), the solubility rate of chromium is 13%.
Embodiment 3:
Present embodiment uses vanadium slag to contain V
2O
511.68wt%, be by vanadium titano-magnetite through blast furnace process production contain vanadium (chromium) pig iron (water), under hot conditions, be the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction process to form again with the air.
1) batching: will be sized to 150 purpose vanadium slags with gac mix Hou Heshui, NaOH adds normal pressure reactor, wherein, the mass ratio of NaOH and vanadium slag is 5: 1, the mass ratio of vanadium slag and gac is 10: 1; The mass concentration of sodium hydroxide solution is 70wt%; Promptly take by weighing NaOH250g, vanadium slag 50g, gac 5g, ultrapure water 107ml;
2) reaction: the step 1) prepared material is packed in the normal pressure reactor, and aerating oxygen carries out oxidizing reaction, and wherein, the flow control of oxygen is at 0.4L/min, and control reaction temperature is 240 ℃, mixing speed 800rpm, and the reaction times is 5h, obtains reaction paste;
3) dilution: when step 2) after the end, water dilutes the reaction paste in the reactor drum, and being diluted to the slurry naoh concentration is about 300g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
4) filtering separation: the mixed slurry that step 3) is obtained carries out filtering separation at 130 ℃, obtain tailings and contain the alkaline solution of vanadium and chromium, with tailings washing, dry back mensuration its to contain total vanadium amount be that 0.30wt% is (with V
2O
5Meter), the solubility rate of chromium is 16%.
Embodiment 4:
Present embodiment uses vanadium slag to contain V
2O
57.75wt% is to contain vanadium (chromium) pig iron (water) by vanadium titano-magnetite through what direct reduction flow process was produced, under hot conditions, is the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction process to form with the air again.
1) batching: will be sized to 400 purpose vanadium slags with gac mix Hou Heshui, NaOH adds normal pressure reactor, wherein, the mass ratio of NaOH and vanadium slag is 8: 1; The mass ratio of vanadium slag and gac is 5: 1, and the mass concentration of sodium hydroxide solution is 93wt%; Promptly take by weighing NaOH350g, vanadium slag 43.75g, gac 8.75g, ultrapure water 26.34ml;
2) reaction: the step 1) prepared material is packed in the normal pressure reactor, and aerating oxygen carries out oxidizing reaction, and the flow control of gas is at 0.2L/min, and control reaction temperature is 180 ℃, mixing speed 500rpm, and the reaction times is 7h, obtains reaction paste;
3) dilution: when step 2) after the end; Sodium hydroxide solution with 200g/L dilutes the reaction paste in the reactor drum; Being diluted to the slurry naoh concentration is about 150g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
4) filtering separation: the mixed slurry that step 3) is obtained carries out filtering separation at 130 ℃, obtain tailings and contain the alkaline solution of vanadium and chromium, with tailings washing, dry back mensuration its to contain total vanadium amount be that 0.23wt% is (with V
2O
5Meter), the solubility rate of chromium is 9%.
Embodiment 5:
Present embodiment uses vanadium slag to contain V
2O
58.33wt% is to contain vanadium (chromium) pig iron (water) by vanadium titano-magnetite through what direct reduction flow process was produced, under hot conditions, is the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction process to form with the air again.
1) batching: will be sized to 200 purpose vanadium slags with coke mix Hou Heshui, NaOH adds normal pressure reactor, wherein, the mass ratio of NaOH and vanadium slag is 2.5: 1; The mass ratio of vanadium slag and coke is that the mass concentration of 10: 1 sodium hydroxide solutions is 80wt%; Promptly take by weighing NaOH200g, vanadium slag 80g, coke 8g, ultrapure water 50ml;
2) reaction: the step 1) prepared material is packed in the normal pressure reactor, and aerating oxygen carries out oxidizing reaction, and the flow control of gas is at 1.2L/min, and control reaction temperature is 220 ℃, mixing speed 650rpm, and the reaction times is 5h, obtains reaction paste;
3) dilution: when step 2) after the end, water dilutes the reaction paste in the reactor drum, and being diluted to the slurry naoh concentration is about 100g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
4) filtering separation: the mixed slurry that step 3) is obtained carries out filtering separation at 100 ℃, obtain tailings and contain the alkaline solution of vanadium and chromium, with tailings washing, dry back mensuration its to contain total vanadium amount be that 0.31wt% is (with V
2O
5Meter), the solubility rate of chromium is 13%.
Embodiment 6:
Present embodiment uses vanadium slag to contain V
2O
59.36wt% is to contain vanadium (chromium) pig iron (water) by vanadium titano-magnetite through what direct reduction flow process was produced, under hot conditions, is the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction process to form with the air again.
1) batching: will be sized to 300 purpose vanadium slags with coke mix Hou Heshui, NaOH adds normal pressure reactor, wherein, the mass ratio of NaOH and vanadium slag is 3: 1; The mass ratio of vanadium slag and coke is that the mass concentration of 10: 1 sodium hydroxide solutions is 52wt%; Promptly take by weighing NaOH150g, vanadium slag 50g, coke 5g, ultrapure water 138ml;
2) reaction: the step 1) prepared material is packed in the normal pressure reactor, and aerating oxygen carries out oxidizing reaction, and the flow control of gas is at 1L/min, and control reaction temperature is 240 ℃, mixing speed 700rpm, and the reaction times is 1h, obtains reaction paste;
3) dilution: when step 2) after the end, with ultrapure water the reaction paste in the reactor drum is diluted, being diluted to the slurry naoh concentration is about 100g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
4) filtering separation: the mixed slurry that step 3) is obtained carries out filtering separation at 120 ℃, obtain tailings and contain the alkaline solution of vanadium and chromium, with tailings washing, dry back mensuration its to contain total vanadium amount be that 0.25wt% is (with V
2O
5Meter), the solubility rate of chromium is 10%.
In the above-described embodiments, be common process with the mixed slurry filtering separation that obtains in the step 3), be those skilled in the art can be implemented according to common practise.
The total vanadium amount of disclosed tailings is compared among total vanadium amount in the tailings that the above embodiment of the invention is measured and the CN 102127655A, can find out obviously that the total vanadium amount of tailings of the present invention is at most 0.5wt%; And the minimum 0.52wt% that is merely of the total vanadium amount of the disclosed tailings of embodiment among the CN 102127655A; That is to say that total vanadium amount is lower in the tailings that obtains through technology of the present invention, has improved the extraction yield of vanadium in the vanadium slag greatly; Compared with prior art, have significantly, remarkable advantages more.The present invention can also realize that vanadium chromium carries altogether, when improving the vanadium extraction yield, and can stripping part chromium.
The present invention relates to a kind of sodium hydroxide solution and add the method that carbonaceousmaterial normal pressure decomposing vanadium slag extracts vanadium and chromium; This method mixes Hou Heshui, NaOH or the NaOH aqueous solution with vanadium slag with carbonaceousmaterial and adds reactor drum; Control the weight ratio of NaOH, water, vanadium slag in the process, control reaction temperature, control stirring velocity; Reaction back to solution dilute, liquid-solid separation, obtain containing the alkaline solution of vanadium and chromium.The invention has the advantages that: service temperature is below the solution boiling temperature, and process only needs under normal pressure, just can carry out, and easy handling and security are good; Service temperature is significantly less than traditional process for extracting vanadium temperature, and the extraction yield of vanadium is high, contain in the tailings vanadium total amount at 0.2~0.6wt% (with V
2O
5Meter), chromium can obtain simultaneous extraction, and solubility rate reaches 8%~20%.
Applicant statement, the present invention explains the method for the present invention's simultaneous extraction vanadium and chromium from vanadium slag through the foregoing description, but the present invention is not limited to the aforesaid operations step, does not mean that promptly the present invention must rely on the aforesaid operations step and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of raw material that the present invention selects for use and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (8)
1. a sodium hydroxide solution adds the method for carbonaceousmaterial normal pressure decomposing vanadium slag, may further comprise the steps:
(1) batching: vanadium slag is mixed the back with carbonaceousmaterial add normal pressure reactor with water, NaOH, wherein, the mass ratio of NaOH and vanadium slag is 2.5: 1~8: 1; The mass ratio of vanadium slag and carbonaceousmaterial is 3: 1~10: 1; The mass concentration of sodium hydroxide solution is 52~93wt%;
(2) reaction: step (1) prepared material is reacted under the condition that feeds oxidizing gas, and airshed is stabilized in 0.2~1.2L/min, and control reaction temperature is 180~240 ℃, and reaction times 1~7h obtains reaction paste;
(3) dilution: step (2) is obtained reaction paste, and to be diluted to naoh concentration be 100~500g/L, obtains containing the mixed slurry of sodium hydroxide, vanadic acid sodium, Sodium chromate-51Cr, water glass and tailings;
(4) filtering separation: the mixed slurry that step (3) is obtained carries out filtering separation at 80~130 ℃, obtains tailings and the alkaline solution that contains vanadium, chromium.
2. method according to claim 1 is characterized in that, preferred 3: 1~7: 1 of the mass ratio of said NaOH of step (1) and vanadium slag, further preferred 4.5: 1~6: 1, more preferably 5: 1;
The mass ratio of vanadium slag and carbonaceousmaterial is preferably 4.5: 1~and 7: 1, further preferred 5: 1;
Preferred 60~the 90wt% of the mass concentration of sodium hydroxide solution, further preferred 65~80wt%, more preferably 75wt%.
3. method according to claim 1 and 2 is characterized in that, the preferred 0.2~1L/min of the said airshed of step (2), further preferred 0.5~0.8L/min, more preferably 0.6L/min;
Preferred 200~225 ℃ of temperature of reaction, further preferred 215 ℃;
Preferred 2~6h of reaction times, further preferred 3.5~5h, more preferably 4h;
Mixing speed is made as 500~800rpm, preferred 650~720rpm, further preferred 700rpm.
4. according to the described method of one of claim 1-3, it is characterized in that it is 180~450g/L that the reaction paste that said step (3) obtains step (2) preferably is diluted to naoh concentration, further preferred 250~350g/L, more preferably 300g/L.
5. according to the described method of one of claim 1-4, it is characterized in that the preferred porous carbonaceous materials of said carbonaceousmaterial, further preferred gac and/or coke; Said oxidizing gas is the mixed gas of air, oxygen or air and oxygen, is preferably oxygen.
6. according to the described method of one of claim 1-5, it is characterized in that the thinner that the said dilution operation of step (3) is used is water or sodium hydroxide solution; The preferred ultrapure water of said water; The concentration of said sodium hydroxide solution is 0~400g/L.
7. according to the described method of one of claim 1-6; It is characterized in that, said vanadium slag for by vanadium titano-magnetite through blast furnace or vanadium (chromium) pig iron (water) that contains that reduces directly that flow process produces under hot conditions, be the vanadium slag that oxidizing medium adopts top blast combined blown converter vanadium extraction production process to form with oxygen or air.
8. according to the described method of one of claim 1-7, it is characterized in that preceding optional the carrying out of step (1): the vanadium slag process is ground pre-treatment, and sieve out 150~400 purpose vanadium slags as raw material.
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