CN110408790A - A kind of method that pressure leaching v-bearing steel slag produces vanadium product - Google Patents
A kind of method that pressure leaching v-bearing steel slag produces vanadium product Download PDFInfo
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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
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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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
- C22B7/04—Working-up slag
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Abstract
The present invention relates to a kind of method that pressure leaching v-bearing steel slag produces vanadium product, the methods are as follows: by v-bearing steel slag, ammonium sulfate and/or ammonium hydrogen sulfate mixing, heating pressurization are leached, and obtain leaching slurry containing vanadium；Vanadium leaching slurry will be contained to flash, obtain ammonia and mixed serum, liquid and tailings after leaching containing vanadium are obtained after gained mixed serum is separated by solid-liquid separation；Sulfuric acid is added into liquid after leaching containing vanadium and carries out precipitation, obtains liquid after ammonium poly-vanadate and precipitation after separation of solid and liquid；Obtained ammonia is passed through after precipitation in liquid, acquired solution returns to leaching step and is recycled.The present invention is using ammonium sulfate and/or ammonium hydrogen sulfate as leaching agent, the vanadium in v-bearing steel slag is extracted using the method that direct weighting leaches, it is matched to introduce flash evaporation technology simultaneously, improve the leaching rate of vanadium, high purity vanadium product, whole preparation process clean and environmental protection are obtained, ammonium salt medium can be recycled, reduce production cost, with good economic efficiency and application prospect.
Description
Technical field
The present invention relates to vanadium chemical fields, and in particular to a kind of method that pressure leaching v-bearing steel slag produces vanadium product.
Background technique
Vanadium slag is important vanadium extraction raw material, and v-bearing steel slag is then the byproduct for smelting vanadium titano-magnetite, is vanadium-bearing hot metal
Steel-making is formed by containing V2O5In the steel slag (its calcium content is big compared with vanadium slag) of 2%-10%, approach there are two types of processes is generated,
One is vanadium remaining in half steel to aoxidize after making steel into slag, and another kind is that the molten iron direct steelmaking without the vanadium slag that blows obtains
To v-bearing steel slag.V-bearing steel slag has a characteristic that (1) CaO and iron content are high, and crystallization is perfect, and quality is closely knit, and degree of dissociation is poor；
(2) complicated component, and fluctuate larger；(3) content of vanadium is lower, and vanadium Dispersed precipitate is in a variety of mine phases, complicated occurrence state.It is based on
The above feature, v-bearing steel slag vanadium extraction are still sciences problems.
Discharge every year nearly million tons of v-bearing steel slag of China, not only pollute environment, and cause the loss of valuable element vanadium.Mesh
Before, v-bearing steel slag vanadium extraction mainly has 2 kinds of approach, first is that v-bearing steel slag returns to ironmaking Vanadium Concentrationin, produces height containing vanadium slag, further
Vanadium extraction, i.e., add as flux using v-bearing steel slag and enter blast furnace process in sinter, and vanadium is fused in molten iron, is blown vanadium and obtain height
Grade vanadium slag, as vanadium extraction or the raw material of smelting ferrovanadium alloy.The technique can not only recycle the valuable elements such as iron, manganese, and reduce
The energy consumption of iron steel ratio, but phosphorus circulation collection in molten iron is easily caused, aggravate steel slag dephosphorization task；And steel slag impurity is more, effective CaO
Content is relatively fewer, can reduce grade of sinter, increases ironmaking processes energy consumption, therefore the method fails to be promoted.Another kind contains
The processing method of vanadium steel slag is direct vanadium extracting method, there is the techniques such as sodium roasting, calcification baking, the roasting of drop calcium and direct acidleach.Sodium
Changing roasting is that Low Valent Vanadium is oxidized to the soluble sodium salt of 5 valence vanadium by roasting using salt or soda as additive, using water or
Carbonating leaches.The technique vanadium turns that leaching rate is lower, and sodium salt consumption is big, and roasting process pollution air is difficult to administer, and the technique
Be not suitable for V2O5The converter slag that content is low, CaO content is high.Calcification baking is to be soaked with the works roasting flux such as lime using carbonating
Equal Leaching Vanadiums out.The problems such as this method has certain selectivity to material, and that there are conversion ratios is relatively low, high expensive to general steel slag,
It is unsuitable for large-scale production.Dropping calcium roasting is proposed by Amiri, high its purpose is to solve CaO content in v-bearing steel slag
The problem of causing vanadium difficulty to leach.Dropping calcium roasting is by steel slag and Na3PO4,Na2CO3It is baking mixed, Na3PO4It is formed in conjunction with CaO
Ca3(PO4)2, vanadium and sodium generates water-soluble sodium vanadate, then water logging, that is, leachable vanadium.But the method only rests on laboratory research
Stage, and phosphatic proportion is big, at high cost, there is presently no industrialization promotions.Direct acidleach refers to without calcining process, complete
Whote-wet method vanadium extraction but due in steel slag CaO content it is high, acid consumes larger, higher cost；Acidleach process need in strong acid solution into
Row, obtained leachate impurity are more, it is difficult to carry out later separation.
CN102071321A discloses the side that a kind of potassium hydroxide medium with high alkalinity extracts vanadium, chromium from v-bearing steel slag
Method, the method do not need high-temperature roasting, and reaction temperature is reduced to 160~240 DEG C, and wet process vanadium extraction chromium effectively prevents in the process
C12、HCl、SO2, the atmosphere pollutions such as dust, and reduce waste water yield and discharge amount；The disadvantage is that KOH medium is expensive,
And KOH with the mass ratio of steel slag is 3:1 to 5:1, to react alkali concentration be 60%~90%, then the KOH medium being lost is more, causes
Production cost is higher, and product benefit reduces.However, there are no the related report that vanadium slag sodium carbonate direct weighting leaches vanadium extraction at present
Road.
CN102094123A discloses a kind of method that the sodium hydroxide medium with high concentration extracts vanadium from v-bearing steel slag,
This method reaction temperature is 180~240 DEG C, wet process vanadium extraction, in the process without exhaust gas, dust pollution；The disadvantage is that alkali concentration is higher, alkali
Degree is 65%~90%, then the heat that evaporation and concentration when causing medium circulation to utilize needs is higher, then production cost is higher, and
Remaining V amount is higher in finishing slag, and leaching rate is not high, and V content is 0.3%~0.5% in finishing slag.
CN107236871A discloses the method for a kind of mixing vanadium slag and v-bearing steel slag pressurization vanadium extraction, the method are as follows: will
Vanadium slag, v-bearing steel slag mixture mixed with sodium hydroxide solution, be passed through oxygen under pressure and reacted；It will reaction
The slurry obtained afterwards is separated by solid-liquid separation, and is obtained containing vanadium leachate.Roasting process is not needed in this method treatment process, and is saved subsequent
Desiliconization removal of impurities process, but whole process is to carry out under strongly alkaline conditions, reaction condition is not mild, and what is obtained contains vanadium leachate
Middle vanadium concentration is too low, and sodium is introduced in leachate, influences the purity of vanadium product.
Summary of the invention
In view of problems of the prior art, the object of the present invention is to provide a kind of pressure leaching v-bearing steel slag systems
The method for taking vanadium product, the present invention are mentioned using ammonium sulfate and/or ammonium hydrogen sulfate as leaching agent using the method that direct weighting leaches
The vanadium in v-bearing steel slag is taken, while it is matched to introduce flash evaporation technology, overcomes a series of problems existing in the prior art,
The leaching rate for improving vanadium has obtained high purity vanadium product, and whole preparation process clean and environmental protection, ammonium salt medium is Ke Xunhuanliyong, drop
Low production cost, with good economic efficiency and application prospect.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides a kind of methods that pressure leaching v-bearing steel slag produces vanadium product, which is characterized in that the method
The following steps are included:
(1) v-bearing steel slag and ammonium salt solution are mixed, heating pressurization is leached, and obtains leaching slurry containing vanadium after the reaction was completed
Liquid；The ammonium salt is ammonium sulfate and/or ammonium hydrogen sulfate；
(2) leaching slurry containing vanadium obtained after leaching step (1) flashes, and ammonia and mixed serum is obtained, by institute
It obtains and obtains liquid and tailings after leaching containing vanadium after mixed serum is separated by solid-liquid separation；
(3) sulfuric acid is added in liquid after leaching to what step (2) obtained containing vanadium and carries out precipitation, obtains more vanadic acid after separation of solid and liquid
Liquid after ammonium and precipitation；
(4) ammonia that step (2) obtains is passed through after the precipitation that step (3) obtains in liquid, obtains ammonium sulfate and/or sulfuric acid
Hydrogen ammonium salt solution, acquired solution are back in step (1) and leach to v-bearing steel slag.
V-bearing steel slag main component be calcium vanadate, calcium oxide, calcium silicates, calcium ferrite, iron oxide and titanomagnetite, wherein
The content of CaO accounts for the 30-40% of steel slag quality, these calcium salts high temperature, high pressure ammonium sulfate or ammonium bisulfate solution in can send out
Raw decomposition reaction generates calcium sulfate, and the vanadium in steel slag is dissociateed to come, and pass into solution generates ammonium vanadate, to realize mentioning for vanadium
It takes.Reaction equation is as follows:
CaO.V2O5+(NH4)2SO4=CaSO4+2NH4VO3
CaO+(NH4)2SO4+H2O=CaSO4+2NH3.H2O
The leaching rate of vanadium can be improved using the method for pressure leaching using ammonium sulfate and/or ammonium hydrogen sulfate as leaching agent.
The extraction rate of vanadium is directly proportional to ammonium sulfate concentrations, in order to realize the high efficiency extraction of vanadium, NH in ammonium sulfate or ammonium hydrogen sulfate4 +Concentration
It need to control as 10-25g/L.Due to generating ammonium hydroxide in leaching process, leaching process has ammonia partial pressure to generate.
After reaction, material is discharged into flash tank from pressure reaction still, and ammonium salt pressure leaching technology phase
The ammonium hydroxide for reacting generation before quickly can be decomposed thoroughly and generate ammonia, while greatly improved containing in vanadium leachate by cooperation
The concentration of vanadium is conducive to the vanadium product for obtaining high-purity.Reaction equation is as follows:
NH3.H2O=H2O+NH3↑
Slurries filtration after flash distillation obtains Ammonium Vanadate Solution, and ammonium poly-vanadate, ammonium poly-vanadate can be obtained in precipitation after sulfuric acid is added
Decomposition can get final vanadic anhydride product.Sulphur can be recombined using liquid absorption after acid precipitation by flashing the ammonia generated
Sour ammonium or ammonium hydrogen sulfate.Ammonium sulfate or ammonium hydrogen sulfate return to leaching process and are reused, not only can be to avoid the nothing of ammonia
Emission problem is organized, and realizes medium circulation utilization, no waste generates.
Na, Si, P are the major impurities that conventional method obtains vanadium product, leach V-alloyed steel using ammonium sulfate or ammonium hydrogen sulfate
The method of slag is free of Na in gained vanadium liquid, can avoid the appearance of Na impurity in product.And the spy that steel slag has Ca content high
Property, Si and P be easy to generate calcium silicates and calcium phosphate in conjunction with Ca, be fixed in tailings, and Si and P content are extremely low in vanadium liquid, because
This, this method can prepare high purity vanadium product.
According to the present invention, NH in step (1) described ammonium salt solution4 +Concentration is 10-25g/L, for example, can be 10g/L,
Specific point value between 13g/L, 15g/L, 18g/L, 20g/L, 23g/L or 25g/L and above-mentioned numerical value as space is limited and goes out
In concise consideration, the present invention no longer exclusive list.
According to the present invention, the mass ratio of step (1) ammonium salt solution and v-bearing steel slag is (3-8): 1, such as can be
It is specific between 3:1,3.5:1,4:1,4.5:1,5:1,5.5:1,6:1,6.5:1,7:1,7.5:1 or 8:1 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, the pressure in step (1) described leaching process be 0.2-1.0MPa, such as can be 0.2MPa,
It is specific between 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa or 1MPa 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, the temperature of step (1) described leaching process is 105-180 DEG C, such as can be 105 DEG C, 110
DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, specific point value between 170 DEG C or 180 DEG C and above-mentioned numerical value, be 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 leaching process be 0.5-2h, such as can be 0.5h, 0.8h, 1h,
Specific point value between 1.2h, 1.5h, 1.8h or 2h 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 (2) flash distillation carries out in flash tank, and the pressure of the flash process is 0-
0.1MPa, for example, can be 0MPa, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa,
Specific point value between 0.8MPa, 0.9MPa or 1MPa and above-mentioned numerical value, as space is limited and for concise consideration, this hair
Bright no longer exclusive list.
According to the present invention, the pH of liquid is 1.8-2.5 after leaching during step (3) described precipitation containing vanadium, such as be can be
1.8, specific point value between 1.9,2,2.1,2.2,2.3,2.4 or 2.5 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 of step (3) the precipitation process is 85-97 DEG C, such as can be 85 DEG C, 88 DEG C, 90
DEG C, 92 DEG C, specific point value between 95 DEG C or 97 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, the time of step (3) the precipitation process be 0.3-1.0h, such as can be 0.3h, 0.4h,
Specific point value between 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h and above-mentioned numerical value, as space is limited and for simplicity
Consider, the present invention no longer exclusive list.
According to the present invention, step (4) ammonia absorb when temperature be 40-80 DEG C, such as can be 40 DEG C, 45 DEG C,
Specific point value between 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 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 (4) ammonia absorb when time be 0.5-1h, such as can be 0.5h, 0.6h,
Specific point value between 0.7h, 0.8h, 0.9h or 1h and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
The operation that the present invention uses means commonly used in the art to be separated by solid-liquid separation, particular determination is not done to this, such as can
Be filtering, filter, sedimentation etc., but it is non-be only limitted to this, other suitable solid-liquid separation means are equally applicable to the present invention.
As a preferred technical solution, the method for the invention the following steps are included:
(1) according to (3-8): 1 liquid consolidates mass ratio, by v-bearing steel slag and NH4 +The ammonium salt solution that concentration is 10-25g/L is mixed
It closes, leaches 0.5-2h under conditions of 105-180 DEG C, 0.2-1.0MPa, obtain leaching slurry containing vanadium after the reaction was completed；The ammonium
Salt is ammonium sulfate and/or ammonium hydrogen sulfate；
(2) leaching slurry containing vanadium obtained after leaching step (1) is placed in flash tank, dodges under the pressure of 0-0.1MPa
It steams, obtains ammonia and mixed serum, liquid and tailings after leaching containing vanadium are obtained after gained mixed serum is separated by solid-liquid separation；
(3) sulfuric acid is added in liquid after leaching to what step (2) obtained containing vanadium, adjusting pH is 1.8-2.5, at 85-97 DEG C
Precipitation 0.3-1.0h obtains liquid after ammonium poly-vanadate and precipitation after separation of solid and liquid；
(4) ammonia that step (2) obtains is passed through after the precipitation that step (3) obtains in liquid, absorbs 0.5- at 40-80 DEG C
1h, obtains ammonium sulfate and/or ammonium bisulfate solution, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Compared with prior art, the present invention is at least had the advantages that
(1) present invention is contained using ammonium sulfate and/or ammonium hydrogen sulfate as leaching agent using the method extraction that direct weighting leaches
Vanadium in vanadium steel slag, obtained Ammonium Vanadate Solution can directly acid adding precipitation, avoid the addition of sodium salt while saving roasting process
Energy consumption, and generated without harmful kiln gas is roasted.
(2) invention introduces flash evaporation technologies to handle leaching slurry, and ammonium salt pressure leaching technology matches, on the one hand
The ammonia in solution is rapidly removed, and itself and ammonium salt synthesis procedure are implemented in combination with and recycled, on the other hand greatly improved
Concentration containing vanadium in vanadium leachate is conducive to the vanadium product for obtaining high-purity.
(3) present invention is using cheap ammonium sulfate and/or ammonium hydrogen sulfate as leaching agent, and not only production cost is low, and
Under conditions of heating pressurization, the leaching rate of vanadium is higher, up to 97% or more.
(4) present invention is the technique of a circular treatment on the whole, and ammonium salt medium used is Ke Xunhuanliyong, no waste water row
Put, be it is a kind of cleaning, efficient steel slag extraction vanadium method.
(5) present invention is using the method vanadium extraction of direct ammonium leaching, and in combination with flash evaporation technology, Na, Si, P impurity contain in vanadium liquid
Extremely low, the step of eliminating subsequent removal of impurities is measured, high purity vanadium product can be directly obtained.
Detailed description of the invention
Fig. 1 is the process flow chart that a kind of specific embodiment of the present invention provides.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment 1
As shown in Figure 1, to v-bearing steel slag pressure leaching produce vanadium product method the following steps are included:
(1) v-bearing steel slag and ammonium sulfate are added in pressure reaction still, control NH in ammonium sulfate4 +Concentration is
It is 3:1 that the liquid of 10g/L, solution and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization is reacted, and is reacted
Temperature is 105 DEG C, reaction pressure 0.3MPa, reaction time 0.5h, obtains leaching slurry containing vanadium, the leaching of vanadium after the reaction was completed
Rate is 97.5%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.05MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 18g/L in liquid after leaching；
(3) it is 2 that sulphur acid for adjusting pH, which is added, in liquid after leaching to what step (2) obtained containing vanadium, precipitation 0.3h, mistake at 85 DEG C
Liquid after ammonium poly-vanadate and precipitation is obtained after filter；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, is absorbed at 40 DEG C
0.5h, obtains ammonium sulfate, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.7%, Na content
0.05%, Si content 0.03%, P content 0.005%.
Embodiment 2
(1) v-bearing steel slag and ammonium sulfate are added in pressure reaction still, control NH in ammonium sulfate4 +Concentration is
It is 5:1 that the liquid of 25g/L, solution and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization is reacted, and is reacted
Temperature is 180 DEG C, reaction pressure 1MPa, reaction time 1.8h, obtains leaching slurry containing vanadium, the leaching rate of vanadium after the reaction was completed
It is 97.8%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.05MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 25g/L in liquid after leaching；
(3) to step (2) obtains leached containing vanadium after sulphur acid for adjusting pH is added in liquid is 2.2, the precipitation 0.3h at 96 DEG C,
Liquid after ammonium poly-vanadate and precipitation is obtained after filtering；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, is absorbed at 50 DEG C
0.55h, obtains ammonium sulfate, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.6%, Na content
0.1%, Si content 0.03%, P content 0.006%.
Embodiment 3
(1) v-bearing steel slag and ammonium sulfate are added in pressure reaction still, control NH in ammonium sulfate4 +Concentration is
It is 3:1 that the liquid of 15g/L, solution and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization is reacted, and is reacted
Temperature is 110 DEG C, reaction pressure 0.21MPa, reaction time 1.6h, obtains leaching slurry containing vanadium, the leaching of vanadium after the reaction was completed
Extracting rate is 98.3%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.06MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 19g/L in liquid after leaching；
(3) to step (2) obtains leached containing vanadium after sulphur acid for adjusting pH is added in liquid is 2.1, the precipitation 0.5h at 93 DEG C,
Liquid after ammonium poly-vanadate and precipitation is obtained after filtering；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, absorbs 1h at 60 DEG C,
Ammonium sulfate is obtained, acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.7%, Na content
0.07%, Si content 0.04%, P content 0.007%.
Embodiment 4
(1) v-bearing steel slag and ammonium sulfate are added in pressure reaction still, control NH in ammonium sulfate4 +Concentration is
It is 8:1 that the liquid of 18g/L, solution and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization is reacted, and is reacted
Temperature is 108 DEG C, reaction pressure 0.2MPa, reaction time 1.2h, obtains leaching slurry containing vanadium, the leaching of vanadium after the reaction was completed
Rate is 98.1%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.07MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 22g/L in liquid after leaching；
(3) to step (2) obtains leached containing vanadium after sulphur acid for adjusting pH is added in liquid is 2.3, the precipitation 0.7h at 90 DEG C,
Liquid after ammonium poly-vanadate and precipitation is obtained after filtering；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, is absorbed at 80 DEG C
0.9h, obtains ammonium sulfate, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.8%, Na content
0.08%, Si content 0.02%, P content 0.008%.
Embodiment 5
(1) v-bearing steel slag and ammonium sulfate are added in pressure reaction still, control NH in ammonium sulfate4 +Concentration is
It is 7:1 that the liquid of 22g/L, solution and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization is reacted, and is reacted
Temperature is 115 DEG C, reaction pressure 0.22MPa, reaction time 0.9h, obtains leaching slurry containing vanadium, the leaching of vanadium after the reaction was completed
Extracting rate is 97.3%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.08MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 21g/L in liquid after leaching；
(3) to step (2) obtains leached containing vanadium after sulphur acid for adjusting pH is added in liquid is 2.5, the precipitation 0.8h at 89 DEG C,
Liquid after ammonium poly-vanadate and precipitation is obtained after filtering；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, is absorbed at 54 DEG C
0.9h, obtains ammonium sulfate, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.9%, Na content
0.09%, Si content 0.03%, P content 0.009%.
Embodiment 6
(1) v-bearing steel slag and ammonium bisulfate solution are added in pressure reaction still, control NH in ammonium bisulfate solution4 +Concentration
For 24g/L, it is 6:1 that the liquid of solution and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization is reacted, instead
It answers temperature to be 120 DEG C, reaction pressure 0.35MPa, reaction time 0.8h and obtains leaching slurry containing vanadium after the reaction was completed, vanadium
Leaching rate is 97.8%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.09MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 20g/L in liquid after leaching；
(3) it is 1.8 that sulphur acid for adjusting pH, which is added, in liquid after leaching to what step (2) obtained containing vanadium, precipitation 1h, mistake at 88 DEG C
Liquid after ammonium poly-vanadate and precipitation is obtained after filter；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, is absorbed at 66 DEG C
0.7h, obtains ammonium bisulfate solution, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.7%, Na content
0.12%, Si content 0.04%, P content 0.01%.
Embodiment 7
(1) by v-bearing steel slag, the mixed solution of ammonium sulfate and ammonium hydrogen sulfate is added in pressure reaction still, is controlled in solution
NH4 +Concentration is 12g/L, and it is 5:1 that the liquid of solution and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization carries out
Reaction, reaction temperature are 155 DEG C, reaction pressure 0.7MPa, reaction time 1.5h, obtain leaching slurry containing vanadium after the reaction was completed
Liquid, the leaching rate of vanadium are 98.0%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.1MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 17g/L in liquid after leaching；
(3) to step (2) obtains leached containing vanadium after sulphur acid for adjusting pH is added in liquid is 1.9, the precipitation 0.8h at 95 DEG C,
Liquid after ammonium poly-vanadate and precipitation is obtained after filtering；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, is absorbed at 52 DEG C
0.6h, obtains ammonium sulfate, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.6%, Na content
0.11%, Si content 0.01%, P content 0.005%.
Embodiment 8
(1) v-bearing steel slag and ammonium sulfate are added in pressure reaction still, control NH in solution4 +Concentration is 16g/L, molten
It is 5:1 that the liquid of liquid and steel slag, which consolidates mass ratio, and pressure reaction still is sealed, and then heating pressurization is reacted, reaction temperature 175
DEG C, reaction pressure 0.9MPa, reaction time 2h obtain leaching slurry containing vanadium after the reaction was completed, and the leaching rate of vanadium is 98.5%；
(2) leaching slurry containing vanadium that step (1) obtains is transferred in flash tank and carries out flash distillation cooling, flash tank internal pressure is tried hard to keep
Hold 0.05MPa, obtain ammonia and mixed serum after flash distillation, will gained mixed serum be separated by solid-liquid separation after obtain containing vanadium leach after liquid and
Tailings, V concentration is 18g/L in liquid after leaching；
(3) to step (2) obtains leached containing vanadium after sulphur acid for adjusting pH is added in liquid is 2.1, the precipitation 0.9h at 97 DEG C,
Liquid after ammonium poly-vanadate and precipitation is obtained after filtering；
(4) the obtained ammonia of step (2) flash distillation is passed through after the precipitation that step (3) obtains in liquid, is absorbed at 75 DEG C
0.5h, obtains ammonium sulfate, and acquired solution is back in step (1) and leaches to v-bearing steel slag.
Obtained ammonium poly-vanadate crystal is calcined to obtain product vanadic anhydride, product purity 99.5%, Na content
0.03%, Si content 0.02%, P content 0.006%.
Comparative example 1
Compared with Example 2, in addition to used ammonium salt is ammonium carbonate, remaining condition is identical.The results show that same
Ammonium salt concentration (the NH of sample4 +25g/L) and under the conditions of temperature (180 DEG C), reaction pressure 3.2MPa, the leaching rate of vanadium is 82%.
Conversion ratio is lower than in the case of ammonium sulfate, and reaction pressure obviously increases.This is because sal volatile occurs under normal pressure
It decomposes, generates ammonia partial pressure, and as the increase of temperature and ammonium salt concentration, pressure increase are more and more obvious, this makes same
Under the reaction condition of sample, reaction kettle pressure increases 200% or more, and very big security risk is brought to operating process.
Comparative example 2
(1) with 1 step of embodiment (1)；
(2) slurry after reacting is without flash distillation, the cooling down directly in kettle, when being cooled to 100 DEG C or less, kettle internal pressure
Power will be 0, then open reaction kettle, mixed slurry is separated by filtration to liquid and tailings after being leached.
The ingredient discovery for analyzing liquid and slag, V concentration is only 3g/L in liquid after leaching, the ammonium metavanadate almost all of generation with
Tailings mixes.This is because, the concentration of ammonium sulfate is still very high in reaction rear slurry, due to NH4 +Salting-out effect, it is raw
At ammonium metavanadate solubility it is very low, be still present in slag with crystal form, vanadium product caused to be difficult to separate with tailings, contain vanadium
Slag need to be further processed, and complicate process for extracting vanadium process.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method that pressure leaching v-bearing steel slag produces vanadium product, which is characterized in that the described method comprises the following steps:
(1) v-bearing steel slag and ammonium salt solution are mixed, heating pressurization is leached, and obtains leaching slurry containing vanadium after the reaction was completed；
The ammonium salt is ammonium sulfate and/or ammonium hydrogen sulfate；
(2) leaching slurry containing vanadium obtained after leaching step (1) flashes, and obtains ammonia and mixed serum, gained is mixed
It closes and obtains liquid and tailings after leaching containing vanadium after slurries are separated by solid-liquid separation；
(3) to step (2) obtains leached containing vanadium after sulfuric acid be added in liquid carry out precipitation, obtained after separation of solid and liquid ammonium poly-vanadate and
Liquid after precipitation；
(4) ammonia that step (2) obtains is passed through after the precipitation that step (3) obtains in liquid, obtains ammonium sulfate and/or ammonium hydrogen sulfate
Solution, acquired solution are back in step (1) and leach to v-bearing steel slag.
2. the method as described in claim 1, which is characterized in that NH in step (1) described ammonium salt solution4 +Concentration is 10-25g/
L。
3. method according to claim 1 or 2, which is characterized in that the quality of step (1) ammonium salt solution and v-bearing steel slag
Than for (3-8): 1.
4. the method according to claim 1, which is characterized in that the pressure in step (1) described leaching process is
0.2-1.0MPa。
5. method according to any of claims 1-4, which is characterized in that the temperature of step (1) described leaching process is
105-180℃；
Preferably, the time of step (1) described leaching process is 0.5-2h.
6. the method according to claim 1 to 5, which is characterized in that step (2) flash distillation carries out in flash tank；
Preferably, the pressure of step (2) described flash process is 0-0.1MPa.
7. as the method according to claim 1 to 6, which is characterized in that contain vanadium leaching during step (3) described precipitation
The pH of liquid is 1.8-2.5 afterwards.
8. the method according to claim 1 to 7, which is characterized in that the temperature of step (3) the precipitation process is 85-
97℃；
Preferably, the time of step (3) the precipitation process is 0.3-1.0h.
9. the method according to claim 1, which is characterized in that step (4) ammonia absorb when temperature be
40-80℃；
Preferably, time when step (4) ammonia absorbs is 0.5-1h.
10. such as the described in any item methods of claim 1-9, which is characterized in that the described method comprises the following steps:
(1) according to (3-8): 1 liquid consolidates mass ratio, by v-bearing steel slag and NH4 +The ammonium salt solution that concentration is 10-25g/L mixes, In
105-180 DEG C, leach 0.5-2h under conditions of 0.2-1.0MPa, obtain leaching slurry containing vanadium after the reaction was completed；The ammonium salt is
Ammonium sulfate and/or ammonium hydrogen sulfate；
(2) leaching slurry containing vanadium obtained after leaching step (1) is placed in flash tank, flashes, obtains under the pressure of 0-0.1MPa
To ammonia and mixed serum, liquid and tailings after leaching containing vanadium are obtained after gained mixed serum is separated by solid-liquid separation；
(3) sulfuric acid is added after leaching to what step (2) obtained containing vanadium in liquid, adjusting pH is 1.8-2.5, the precipitation at 85-97 DEG C
0.3-1.0h obtains liquid after ammonium poly-vanadate and precipitation after separation of solid and liquid；
(4) ammonia that step (2) obtains is passed through after the precipitation that step (3) obtains in liquid, absorbs 0.5-1h at 40-80 DEG C,
Ammonium sulfate and/or ammonium bisulfate solution are obtained, acquired solution is back in step (1) and leaches to v-bearing steel slag.
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| CN114262799A (en) * | 2021-12-28 | 2022-04-01 | 中国科学院过程工程研究所 | Method for cleanly extracting vanadium from vanadium-containing steel slag |
| CN114275813A (en) * | 2021-12-30 | 2022-04-05 | 中国科学院过程工程研究所 | Method for flash evaporation, cooling and crystallization of sodium vanadate in alkali liquor system |
| CN114293035A (en) * | 2021-12-28 | 2022-04-08 | 中国科学院过程工程研究所 | Method for preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag |
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Application publication date: 20191105 |