CN109207728A - A kind of method that high-temperature roasting method extracts chromium and vanadium from slag containing chrome alum - Google Patents
A kind of method that high-temperature roasting method extracts chromium and vanadium from slag containing chrome alum Download PDFInfo
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- CN109207728A CN109207728A CN201710551972.3A CN201710551972A CN109207728A CN 109207728 A CN109207728 A CN 109207728A CN 201710551972 A CN201710551972 A CN 201710551972A CN 109207728 A CN109207728 A CN 109207728A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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Abstract
A kind of method that the present invention relates to high-temperature roasting methods to extract chromium and vanadium from slag containing chrome alum, the method are as follows: will contain after chrome alum slag is mixed with additive and roast, and obtain roasting clinker；The additive is the combination of calcium source and sodium salt；Roasting clinker leach with water and mentions chromium, leachate containing chromium and rich vanadium clinker are obtained after separation of solid and liquid；Rich vanadium clinker is subjected to leaching vanadium extraction, is obtained after separation of solid and liquid containing vanadium leachate and tailings.The present invention realizes the subsequent substep separation of vanadium, chromium by adding sodium salt, calcium source additive package in high-temperature roasting；Avoid finishing the generation of kiln, ring formation phenomenon simultaneously.The high efficiency extraction of vanadium chromium can be achieved in the present invention, the content of vanadium, chromium 1% hereinafter, efficiently solve the vanadium chromium of slag containing chrome alum separation problem, from the separation of source realization vanadium, chromium simultaneously in tailings, obtained leachate is easy to subsequent and vanadium, chromium product is prepared, and has a good application prospect.
Description
Technical field
The invention belongs to vanadium slag hydrometallurgys and vanadium chemical field, and in particular to a kind of high-temperature roasting method is from slag containing chrome alum
The method for extracting chromium and vanadium.
Background technique
Vanadium titano-magnetite is the great characteristic Polymetallic Minerals resource in China, and reserves rank the third of the world position, and storage has been verified in China
For amount more than 10,000,000,000 tons, prospective reserves is mainly distributed on Panxi, Sichuan (Panzhihua-Xichang), Chengde up to 30,000,000,000 tons or more
It is regional with Anhui Maanshan etc..More metal symbiosis such as vanadium, titanium, iron, chromium in vanadium titano-magnetite, comprehensive utilization of resources value is very high,
The especially nearly 3,600,000,000 tons of high-chromic vanadium-titanium ferroferrites (Panzhihua Hongge Deposit) of Panxi Diqu are associated with chromium resource abundant, reserves
About 9,000,000 tons (with Cr2O3Meter), it is equivalent to chromium resource has been verified in China 80%, chromium content therein even content of vanadium
Twice.In default of the common extractive technique of vanadium chromium of economical and efficient, Hongge Deposit fails to develop and use so far.
Vanadium slag sodium roasting is the main stream approach of vanadium titano-magnetite vanadium extraction.Vanadium titano-magnetite is through blast furnace or direct-reduction process
The pig iron containing vanadium of production enters clinker after aoxidizing vanadium, obtains the higher vanadium of content of vanadium further by selective oxidation molten iron
Slag.During vanadium is blown in converter, because vanadium, chromium property are close, also oxidation enters vanadium slag to the chromium in mine together, obtains slag containing chrome alum.
Slag containing chrome alum is the raw material of further recycling vanadium, chromium, since vanadium, chromium property are quite similar, from vanadium chromium slag how economical and effective
Ground extracts and separation vanadium, chromium are always the core technology problem of Hongge Deposit comprehensive development and utilization, and can restrict Hongge Deposit big
The principal element of scale development.
Vanadium in Vanadium Residue containing chromium is roasted with the presence of chromohercynite structure in vanadium slag sodium with the presence of vanadium iron spinel structure, chromium
Vanadium extracting process is burnt, vanadium iron spinelle, which can react under 750-850 DEG C of roasting condition with sodium salt, generates sodium vanadate, passes through subsequent leaching
Vanadium enters liquid phase.The decomposition temperature of chromohercynite is higher, at 950-1150 DEG C, under the conditions of existing 850 DEG C of Leaching of Vanadium from Vanadium slag, and chromium
Hercynite cannot be decomposed substantially, and chromium cannot recycle substantially, and unused chromium resource is discarded with tailings, easily cause secondary dirt
Dye.Importantly, dioxide-containing silica reaches 15-25% or so, high-temperature calcination process composition based on silicate in vanadium slag
Fusing vitreum be wrapped in around spinelle, hinder the mass transfer of oxygen, the generation of diffusion and vanadate, and improve reaction temperature will
Increase the amount of liquid phase in roasting material significantly, material easily bonds, and causes reaction mass transfer effect to be deteriorated and causes ring formation knot kiln, even
Cause roasting apparatus cannot normal direct motion.Therefore, high, the low-melting limitation of sodium salt product by silicone content in vanadium slag, it is difficult to pass through
The method for improving temperature realizes the recycling of chromium.
CN101161831A proposes a kind of method of vanadium slag calcification baking, compared with sodium roasting technique, calcification baking
Solve the ammonia nitrogen waste water pollution problem with high salt of sodium roasting process, but the still very high (600-950 of the maturing temperature of calcification baking
DEG C), and the rate of recovery of vanadium is low (about 80%), chromium can not synchronize recycling.
A kind of method that CN105112678A discloses vanadium chromium slag vanadium extraction and tailings reduction magnetic separation smelting chromium irons, first will
Vanadium chromium slag roasting direct, it is acid-leaching vanadium-extracted, add ammonium salt precipitation containing vanadium solution obtained by acidleach, product is used to prepare vanadic anhydride, acid
Leaching gained tailings containing chromium is first restored with reducing agent, then levigate sieving, then its low intensity magnetic separation is obtained Iron concentrate, and then high intensity magnetic separation obtains
To ferrochrome fine powder, Iron concentrate returns to blast furnace ironmaking, and ferrochrome fine powder and reducing agent, slag former fusion smelting obtain ferrochrome and furnace
Slag, clinker is for producing cement or construction material.The leaching rate of this method vanadium is then hardly leached (chromium up to 99%, chromium
Leaching rate < 0.5%), realize vanadium, chromium efficiently separates.
CN103614566A discloses a kind of addition Na2CO3The method that substep roasts vanadium extraction chromium, the first step is at 700-850 DEG C
Roasting water logging obtains solution containing vanadium, and second step is obtained in 800-1050 DEG C of roasting water logging containing chrome liquor.Patent CN104178637B is disclosed
A kind of first segment is acid-leaching vanadium-extracted using calcification baking-, and second step uses sodium roasting-flooding chromium method.Such method
Vanadium and chromium turn leaching rate height and convenient for vanadium and chromium later separations, but because to roast again after leaching, roasting-leaching operates repeatedly
Two-stage roasting energy consumption is high
CN102127654A discloses a kind of method for decomposing vanadium and chromium-containing slag using sodium hydroxide fused salt, reaction temperature 500-
600 DEG C, which can realize that vanadium chromium mentions altogether, but fused salt reaction process temperature is higher；CN102127656A discloses a kind of liquid phase
The method of oxygenolysis vanadium slag, by using sodium hydroxide, sodium nitrate blending agent, oxygenolysis vanadium slag process is strengthened,
It is reduced compared with sodium hydroxide fused-salt medium reaction temperature, but introduces sodium nitrate medium, subsequent separation process step increases；
CN101812588A proposes a kind of method of decomposing vanadium slag with solution of potassium hydroxide under normal pressure, reacts at 180-260 DEG C, temperature is significantly
It reduces, and can realize that vanadium chromium mentions altogether, the disadvantage is that potassium hydroxide medium higher cost；It is molten that CN102531056A proposes a kind of NaOH
The method of liquid pressurization decomposing chromium-containing vanadium slag, reaction temperature realize the high efficiency extraction of the chromium of Vanadium in Vanadium Residue containing chromium at 200-300 DEG C；
CN103060843A, CN103421950B, CN104294040B use electrochemical field reinforcement technique, realize slag containing chrome alum and exist
In KOH solution, NaOH solution it is mild under the conditions of vanadium chromium high efficiency extraction.Liquid phase oxidation technical effect is good, advantageously accounts for vanadium chromium
Problem is proposed altogether, but because the mainstream technology of present vanadium chemical industry is rotary kiln baking route, liquid phase oxidation entirety alternative cost height, cost
Greatly, technological industrialization pushes slow.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides it is a kind of using high-temperature roasting method extracted from slag containing chrome alum vanadium with
The method of chromium realizes and leaches to chromium, vanadium substep in slag containing chrome alum, the separation to vanadium, chromium realized from source, while can
It avoids generating knot kiln, ring formation phenomenon in the high-temperature roasting stage, and then has achieved the purpose that vanadium chromium high efficiency extraction.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of method that the present invention provides high-temperature roasting methods to extract chromium and vanadium from slag containing chrome alum, the method includes with
Lower step:
(1) it will contain after chrome alum slag is mixed with additive and roast, and obtain roasting clinker；The additive is calcium source and sodium
The combination of salt；
(2) roasting clinker that step (1) obtains leach with water and mentions chromium, obtained after separation of solid and liquid leachate containing chromium with
Rich vanadium clinker；
(3) the rich vanadium clinker for obtaining step (2) carries out leaching vanadium extraction, is obtained after separation of solid and liquid containing vanadium leachate and tail
Slag.
On the one hand present invention selection uses vanadium, chromium object phase in the additive package of high-temperature roasting stage addition calcium source and sodium salt
The subsequent substep separation for generating calcium vanadate, the property of sodium chromate realization vanadium, chromium respectively in roasting, avoids conventional method liquid phase
The problems such as middle vanadium chromium separation needs to adjust solution ph fractional precipitation, long flow path, and separation is not thorough, passes through vanadium, the substep of chromium
It leaches, the separation of vanadium, chromium is realized from source, obtained solution is easy to subsequent and vanadium, chromium product is prepared；On the other hand, in height
Warm firing stage addition calcium source can be avoided the generation of roasting sintering oven, ring formation phenomenon, go on smoothly roasting.
In step (1) of the present invention after roasting, the vanadium in slag containing chrome alum is changed into calcium vanadate, and chromium is changed into sodium chromate.
According to the present invention, slag containing chrome alum described in step (1) is by vanadium titano-magnetite through blast furnace or direct-reduction process production
The molten iron containing vanadium and chromium mentioned under the high temperature conditions using oxygen or air as oxide isolation using shaking ladle vanadium extraction, ladle again
The vanadium slag that the production processes such as vanadium and various top blast combined blown converter vanadium extractions are formed.
According to the present invention, the slag containing chrome alum is pre-processed before mixing in step (1), the pretreatment is that will contain
Chrome alum slag is crushed to partial size less than 0.125mm, for example, can be 0.0001mm, 0.001mm, 0.01mm, 0.02mm, 0.03mm,
0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm, 0.10mm, 0.11mm, 0.12mm or 0.124mm, and
Other are less than the numerical value of 0.125mm, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (1) calcium source is lime and/or lime stone.
According to the present invention, in terms of the CaO in calcium source, with V in slag containing chrome alum2O5Molar ratio be 1-3, such as can be
1, the specific point value between 1.2,1.5,1.8,2,2.3,2.5,2.7 or 3 and above-mentioned numerical value, as space is limited and for simplicity
The considerations of, the present invention no longer exclusive list.
According to the present invention, step (1) sodium salt is any one in sodium carbonate, sodium sulphate or sodium chloride or at least two
The combination of kind；Such as it can be any one in sodium carbonate, sodium sulphate or sodium chloride, typical but non-limiting combination are as follows:
Sodium carbonate and sodium sulphate；Sodium carbonate and sodium chloride；Sodium sulphate and sodium chloride；Sodium carbonate, sodium sulphate and sodium chloride.
According to the present invention, with the Na in sodium salt2O meter, with Cr in slag containing chrome alum2O3Molar ratio be 1.5-2.5, such as
It can be specific between 1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4 or 2.5 and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the temperature of step (1) described roasting be 700-1100 DEG C, such as can be 700 DEG C, 750 DEG C,
Specific point value between 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C or 1100 DEG C and above-mentioned numerical value, is limited to
Length and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the time of step (1) described roasting be 30-150min, such as can be 30min, 40min,
50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min or 150min, and
Specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (1) it is described roasting carried out in rotary kiln or multiple hearth furnace, preferably in rotary kiln into
Row.
According to the present invention, step (2) water and roasting clinker mass ratio be (1-4): 1, for example, can be 1:1,
Specific point value between 1.5:1,2:1,2.5:1,3:1,3.5:1 or 4:1 and above-mentioned numerical value, as space is limited and for simplicity
The considerations of, the present invention no longer exclusive list.
According to the present invention, the temperature that step (2) leaching mentions chromium is 40-100 DEG C, such as can be 40 DEG C, 45 DEG C, 50
DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, it is specific between 95 DEG C or 100 DEG C and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (3) is described when leaching vanadium extraction, and the liquid-solid ratio of leachate and rich vanadium clinker is (2-30): 1, it is excellent
It is selected as (5-20): 1；Such as can be 2:1,5:1,8:1,10:1,12:1,15:1,18:1,20:1,23:1,25:1,28:1 or
Specific point value between 30:1 and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
The unit of liquid-solid ratio of the present invention is ml/g.
According to the present invention, step (3) temperature for leaching vanadium extraction is 20-150 DEG C, preferably 50-100 DEG C；Such as it can
Be 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or
Specific point value between 150 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (3) time for leaching vanadium extraction is 0.5-6h, preferably 1-5h；Such as it can be
Specific point value between 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h and above-mentioned numerical value,
As space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the rich vanadium clinker that step (2) obtains is carried out using ammonium salt solution or sodium salt solution in step (3)
Leach vanadium extraction.
According to the present invention, the ammonium salt solution is that ammonium bicarbonate soln, sal volatile, ammonium oxalate solution, ammonium phosphate are molten
In liquid or ammonia spirit any one or at least two combination；Such as it can be ammonium bicarbonate soln, sal volatile, grass
Any one in acid ammonium solution, ammonium phosphate solution or ammonia spirit, typical but non-limiting combination are as follows: ammonium bicarbonate soln
And sal volatile；Ammonium oxalate solution and ammonium phosphate solution；Ammonium bicarbonate soln and ammonium oxalate solution；Ammonium phosphate solution and ammonium hydroxide
Solution；Ammonium bicarbonate soln, sal volatile and ammonia spirit etc., as space is limited and for concise consideration, the present invention is no longer
Exclusive list.
According to the present invention, NH in the ammonium salt solution4 +Concentration be 5-300g/L, preferably 20-150g/L；Such as it can be with
Be 5g/L, 10g/L, 20g/L, 50g/L, 80g/L, 100g/L, 120g/L, 150g/L, 180g/L, 200g/L, 220g/L,
Specific point value between 250g/L, 280g/L or 300g/L and above-mentioned numerical value, as space is limited and for concise consideration, originally
Invention no longer exclusive list.
According to the present invention, the sodium salt solution is sodium carbonate liquor and/or sodium hydroxide solution.
According to the present invention, Na in the sodium salt solution+Concentration be 5-300g/L, preferably 20-150g/L, further it is excellent
It is selected as 30-100g/L；Such as can be 5g/L, 10g/L, 20g/L, 50g/L, 80g/L, 100g/L, 120g/L, 150g/L,
Specific point value between 180g/L, 200g/L, 220g/L, 250g/L, 280g/L or 300g/L and above-mentioned numerical value, is limited to a piece
Width and for concise consideration, the present invention no longer exclusive list.
The present invention selects means well known in the art to be separated by solid-liquid separation, such as can choose filtering, suction filtration, centrifugation or heavy
Drop etc. modes carry out, but it is non-be only limitted to this, should be advisable in order to operate.
The present invention contains vanadium leachate and containing vanadium leachate progress subsequent extracted to what is obtained using conventional method.
Compared with prior art, the present invention at least has the advantages that
(1) present invention is by adding sodium salt, calcium source additive package in high-temperature roasting, through vanadium, chromium object phase in roasting
Calcium vanadate, sodium chromate are generated respectively, realize the subsequent substep separation of vanadium, chromium；Adding calcium source simultaneously can effectively avoid roasting knot
The generation of kiln, ring formation phenomenon goes on smoothly roasting.
(2) high efficiency extraction of vanadium chromium can be achieved in the present invention, and vanadium, chromium are (with V in tailings2O5、Cr2O3Meter) content 1%
Below.
(3) present invention, which solves vanadium chromium in conventional method liquid phase and separates, needs to adjust solution ph fractional precipitation, long flow path,
And the problems such as being not thorough is separated, it is leached by the substep to vanadium, chromium, the separation of vanadium, chromium is realized from source, obtained solution is easy to
It is subsequent that vanadium, chromium product is prepared, it has a good application prospect.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment uses in slag containing chrome alum containing V2O512.64%, Cr2O313.28%.
(1) it will contain after chrome alum slag is mixed with lime, sodium carbonate and be roasted in rotary kiln, the additive amount of lime is with CaO
Meter and V in slag containing chrome alum2O5Molar ratio is 3, and the additive amount of sodium carbonate is with Na2O meter and Cr in slag containing chrome alum2O3Molar ratio is 2；Roasting
Burning temperature is 1000 DEG C, and calcining time 120min, the vanadium after roasting in slag containing chrome alum is changed into calcium vanadate, and chromium is changed into chromic acid
Sodium obtains roasting clinker；
(2) the roasting clinker that step (1) obtains leach with water and mention chromium, the mass ratio of water and roasting clinker is 2, leaching
Temperature is 90 DEG C out, and leachate containing chromium and rich vanadium clinker are obtained after filtering；
(3) rich vanadium clinker obtained by step (2) is leached into vanadium extraction, NH in ammonium bicarbonate soln in ammonium bicarbonate soln4 +Matter
Amount concentration is 50g/L, and the liquid-solid ratio of solution and rich vanadium clinker is 10:1, and extraction temperature is 90 DEG C, extraction time 3h, after filtering
It obtains containing vanadium leachate and tailings.
After testing, V in the obtained tailings of the present embodiment2O5For 0.95%, Cr2O3It is 0.84%.
Embodiment 2
The present embodiment uses in slag containing chrome alum containing V2O513.85%, Cr2O35.69%.
(1) it will contain after chrome alum slag is mixed with lime, sodium carbonate, sodium chloride and be roasted in rotary kiln, the addition of lime
Amount V in terms of CaO and in slag containing chrome alum2O5Molar ratio is 2, and the additive amount of sodium carbonate is with Na2O meter and Cr in slag containing chrome alum2O3Mole
Than being 2.5；Maturing temperature is 950 DEG C, and calcining time 150min, the vanadium after roasting in slag containing chrome alum is changed into calcium vanadate, chromium
It is changed into sodium chromate, obtains roasting clinker；
(2) the roasting clinker that step (1) obtains leach with water and mention chromium, the mass ratio of water and roasting clinker is 3, leaching
Temperature is 100 DEG C out, and leachate containing chromium and rich vanadium clinker are obtained after filtering；
(3) rich vanadium clinker obtained by step (2) is leached into vanadium extraction, Na in sodium carbonate liquor in sodium carbonate liquor+Quality is dense
Spending is 150g/L, and the liquid-solid ratio of solution and rich vanadium clinker is 20:1, and extraction temperature is 150 DEG C, extraction time 2h, after filtering
To containing vanadium leachate and tailings.
After testing, V in the obtained tailings of the present embodiment2O5For 0.73%, Cr2O3It is 0.94%.
Embodiment 3
The present embodiment uses in slag containing chrome alum containing V2O511.21%, Cr2O34.43%.
(1) it will contain after chrome alum slag is mixed with lime stone, sodium carbonate, sodium sulphate and be roasted in rotary kiln, lime adds
Dosage V in terms of CaO and in slag containing chrome alum2O5Molar ratio is 1, and the additive amount of sodium carbonate is with Na2O meter and Cr in slag containing chrome alum2O3It rubs
You are than being 1.5；Maturing temperature is 1000 DEG C, and calcining time 140min, the vanadium after roasting in slag containing chrome alum is changed into calcium vanadate,
Chromium is changed into sodium chromate, obtains roasting clinker；
(2) the roasting clinker that step (1) obtains leach with water and mention chromium, the mass ratio of water and roasting clinker is 4, leaching
Temperature is 70 DEG C out, and leachate containing chromium and rich vanadium clinker are obtained after filtering；
(3) rich vanadium clinker obtained by step (2) is leached into vanadium extraction, Na in sodium hydroxide solution in sodium hydroxide solution+Matter
Amount concentration is 200g/L, and the liquid-solid ratio of solution and rich vanadium clinker is 5:1, and extraction temperature is 90 DEG C, extraction time 2h, after filtering
It obtains containing vanadium leachate and tailings.
After testing, V in the obtained tailings of the present embodiment2O5For 0.98%, Cr2O3It is 0.94%.
Embodiment 4
The present embodiment uses in slag containing chrome alum containing V2O512.64%, Cr2O313.28%.
(1) chrome alum slag and lime stone will be contained, roasted in rotary kiln after sodium carbonate mixes, the additive amount of lime with
CaO meter and V in slag containing chrome alum2O5Molar ratio is 3, and the additive amount of sodium carbonate is with Na2O meter and Cr in slag containing chrome alum2O3Molar ratio is
2；Maturing temperature is 1050 DEG C, and calcining time 100min, the vanadium after roasting in slag containing chrome alum is changed into calcium vanadate, and chromium is changed into
Sodium chromate obtains roasting clinker；
(2) the roasting clinker that step (1) obtains leach with water and mention chromium, the mass ratio of water and roasting clinker is 4, leaching
Temperature is 100 DEG C out, and leachate containing chromium and rich vanadium clinker are obtained after filtering；
(3) rich vanadium clinker obtained by step (2) is leached into vanadium extraction, Na in sodium hydroxide solution in sodium hydroxide solution+Matter
Amount concentration is 400g/L, and the liquid-solid ratio of solution and rich vanadium clinker is 10:1, and extraction temperature is 120 DEG C, extraction time 6h, filtering
After obtain containing vanadium leachate and tailings.
After testing, V in the obtained tailings of the present embodiment2O5For 0.98%, Cr2O3It is 0.97%.
Embodiment 5
The present embodiment uses in slag containing chrome alum containing V2O511.21%, contain Cr2O34.43%.
(1) chrome alum slag and lime stone will be contained, roasted in rotary kiln after sodium carbonate mixes, the additive amount of lime with
CaO meter and V in slag containing chrome alum2O5Molar ratio is 3, and the additive amount of sodium carbonate is with Na2O meter and Cr in slag containing chrome alum2O3Molar ratio is
2.5；Maturing temperature is 850 DEG C, calcining time 150min, and the vanadium after roasting in slag containing chrome alum is changed into calcium vanadate, chromium transformation
For sodium chromate, roasting clinker is obtained；
(2) the roasting clinker that step (1) obtains leach with water and mention chromium, the mass ratio of water and roasting clinker is 3, leaching
Temperature is 40 DEG C out, and leachate containing chromium and rich vanadium clinker are obtained after filtering；
(3) rich vanadium clinker obtained by step (2) is leached into vanadium extraction, NH in ammonium oxalate solution in ammonium oxalate solution4 +Quality is dense
Spending is 150g/L, and the liquid-solid ratio of solution and rich vanadium clinker is 10:1, and extraction temperature is 100 DEG C, extraction time 6h, after filtering
To containing vanadium leachate and tailings.
After testing, V in the obtained tailings of the present embodiment2O5For 0.89%, Cr2O3It is 0.98%.
Comparative example 1
Compared with Example 1, in addition in step (1) slag containing chrome alum do not mixed with lime, sodium carbonate, i.e., to contain chrome alum
Slag carries out outside blank roasting, and other conditions are same as Example 1.
As the result is shown: can effectively extract the vanadium in slag containing chrome alum, but chromium therein can not effectively be extracted.This comparison
V in the obtained tailings of example2O5For 0.96%, Cr2O3It is 14.39%.
Comparative example 2
Compared with Example 1, in addition in step (1) slag containing chrome alum only with lime carry out it is baking mixed other than (in terms of CaO and contain
V in chrome alum slag2O53) molar ratio remains as, other conditions are same as Example 1.
As the result is shown: can effectively extract the vanadium in slag containing chrome alum, but chromium therein can not effectively be extracted.This comparison
V in the obtained tailings of example2O5For 0.89%, Cr2O3It is 14.24%.
Comparative example 3
Compared with Example 1, in addition in step (1) slag containing chrome alum only with sodium carbonate carry out it is baking mixed other than (with Na2O meter
With Cr in slag containing chrome alum2O32) molar ratio remains as, other conditions are same as Example 1.
As the result is shown: can be to the effective extraction of chromium and vanadium progress part in slag containing chrome alum, but because roasting process does not have calcium
The addition in source, independent sodium-salt calcination ring formation phenomenon is serious, and obtained liquid phase is vanadium chromium mixed liquor, and later separation is complicated, no
It is able to achieve the source separation of vanadium, chromium.V in the obtained tailings of this comparative example2O5For 2.89%, Cr2O3It is 6.38%.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of method that high-temperature roasting method extracts chromium and vanadium from slag containing chrome alum, which is characterized in that the method includes following
Step:
(1) it will contain after chrome alum slag is mixed with additive and roast, and obtain roasting clinker；The additive is calcium source and sodium salt
Combination；
(2) the roasting clinker that step (1) obtains leach with water and mention chromium, leachate containing chromium and rich vanadium are obtained after separation of solid and liquid
Clinker；
(3) the rich vanadium clinker for obtaining step (2) carries out leaching vanadium extraction, is obtained after separation of solid and liquid containing vanadium leachate and tailings.
2. the method as described in claim 1, which is characterized in that step (1) before mixing locates the slag containing chrome alum in advance
Reason；
Preferably, the pretreatment is crushed to partial size less than 0.125mm for that will contain chrome alum slag.
3. method according to claim 1 or 2, which is characterized in that step (1) calcium source is lime and/or lime stone；
Preferably, in terms of the CaO in calcium source, with V in slag containing chrome alum2O5Molar ratio be 1-3.
4. the method according to claim 1, which is characterized in that step (1) sodium salt is sodium carbonate, sodium sulphate
In sodium chloride any one or at least two combination；
Preferably, with the Na in sodium salt2O meter, with Cr in slag containing chrome alum2O3Molar ratio be 1.5-2.5.
5. method according to any of claims 1-4, which is characterized in that the temperature of step (1) described roasting is 700-
1100℃；
Preferably, the time of step (1) described roasting is 30-150min；
Preferably, step (1) roasting carries out in rotary kiln or multiple hearth furnace, carries out preferably in rotary kiln.
6. the method according to claim 1 to 5, which is characterized in that the quality of step (2) water and roasting clinker
Than for (1-4): 1.
7. as the method according to claim 1 to 6, which is characterized in that the temperature that step (2) leaching mentions chromium is 40-
100℃。
8. the method according to claim 1 to 7, which is characterized in that when step (3) the leaching vanadium extraction leachate with
The liquid-solid ratio of rich vanadium clinker is (2-30): 1, preferably (5-20): 1；
Preferably, step (3) temperature for leaching vanadium extraction is 20-150 DEG C, preferably 50-100 DEG C；
Preferably, step (3) time for leaching vanadium extraction is 0.5-6h, preferably 1-5h.
9. the method according to claim 1, which is characterized in that molten using ammonium salt solution or sodium salt in step (3)
Liquid carries out leaching vanadium extraction to the rich vanadium clinker that step (2) obtains；
Preferably, the ammonium salt solution is ammonium bicarbonate soln, sal volatile, ammonium oxalate solution, ammonium phosphate solution or ammonium hydroxide
In solution any one or at least two combination；
Preferably, NH in the ammonium salt solution4 +Concentration be 5-300g/L, preferably 20-150g/L.
10. method as claimed in claim 9, which is characterized in that the sodium salt solution is sodium carbonate liquor and/or sodium hydroxide
Solution；
Preferably, Na in the sodium salt solution+Concentration be 5-300g/L, preferably 20-150g/L, further preferably 30-
100g/L。
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| CN112011692A (en) * | 2020-09-23 | 2020-12-01 | 攀钢集团研究院有限公司 | Method for extracting vanadium by composite roasting of solid waste slag |
| CN112267028A (en) * | 2020-12-24 | 2021-01-26 | 矿冶科技集团有限公司 | Method for extracting vanadium and chromium from vanadium slag and application thereof |
| CN113528861A (en) * | 2021-06-23 | 2021-10-22 | 河钢承德钒钛新材料有限公司 | Clean vanadium extraction method and system for vanadium-containing material |
| CN115959706A (en) * | 2022-08-10 | 2023-04-14 | 新疆盛安新材料科技有限公司 | Method for converting vanadium by co-roasting vanadium slag with sodium calcium |
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| CN105420519A (en) * | 2015-12-21 | 2016-03-23 | 中南大学 | Method for extracting vanadium and chromium from materials containing vanadium or/and chromium |
| CN105714102A (en) * | 2016-03-03 | 2016-06-29 | 中国科学院过程工程研究所 | Method for extracting vanadium by leaching vanadium-contained raw material roasting clinkers through ammonium phosphate |
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| CA1053910A (en) * | 1973-08-07 | 1979-05-08 | Ontario Research Foundation | Productions of metals |
| CN103924096A (en) * | 2014-04-28 | 2014-07-16 | 攀枝花学院 | Method for recycling vanadium-chromium resources |
| CN105420519A (en) * | 2015-12-21 | 2016-03-23 | 中南大学 | Method for extracting vanadium and chromium from materials containing vanadium or/and chromium |
| CN105714102A (en) * | 2016-03-03 | 2016-06-29 | 中国科学院过程工程研究所 | Method for extracting vanadium by leaching vanadium-contained raw material roasting clinkers through ammonium phosphate |
Cited By (4)
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| CN112011692A (en) * | 2020-09-23 | 2020-12-01 | 攀钢集团研究院有限公司 | Method for extracting vanadium by composite roasting of solid waste slag |
| CN112267028A (en) * | 2020-12-24 | 2021-01-26 | 矿冶科技集团有限公司 | Method for extracting vanadium and chromium from vanadium slag and application thereof |
| CN113528861A (en) * | 2021-06-23 | 2021-10-22 | 河钢承德钒钛新材料有限公司 | Clean vanadium extraction method and system for vanadium-containing material |
| CN115959706A (en) * | 2022-08-10 | 2023-04-14 | 新疆盛安新材料科技有限公司 | Method for converting vanadium by co-roasting vanadium slag with sodium calcium |
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