CN106011469B - The method of the continuous precipitation of high vanadium concentrations solution - Google Patents
The method of the continuous precipitation of high vanadium concentrations solution Download PDFInfo
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Abstract
The present invention relates to the method for the method of the precipitation of high vanadium concentrations solution, the more particularly to continuous precipitation of high vanadium concentrations solution, belong to metallurgical technology field.The present invention comprises the following steps that：A, one-level precipitation；B, two level precipitation；C, vanadium reclaims；D, precipitation devil liquor recovery；High vanadium concentrations solution is carried out two-stage continuous precipitation by the present invention, and technique is simply efficient, and equipment investment is few；Waste water yield is few, unit precipitating reagent dosage and less energy consumption, and production efficiency is high, reduces production cost；Reaction condition is gentle, is not easy heavy useless, obtained good product quality；Liquid phase vanadium concentration is low after precipitation, vanadium high income.
Description
Technical field
The present invention relates to the side of the method for the precipitation of high vanadium concentrations solution, the more particularly to continuous precipitation of high vanadium concentrations solution
Method, belong to metallurgical technology field.
Background technology
Vanadium resource is scarce resource important in the world, and without the vanadium mineral that can individually adopt, its distribution in nature is very
Scattered, main association is in sulphur navajoite VS2Or V2S5, lead navajoite (or vanadinite) Pb5(VO4)C3, vanadium marble KV2(AlSi2O10)
(OH)2, potassium vanadate uranium ore K2(UO2)(VO4)2 3H2In the mineral such as O and vanadium titano-magnetite.Raw material type for vanadium extraction is very
More, 88% vanadium is obtained from vanadium titano-magnetite in the world, and remaining vanadium extraction raw material has bone coal, dead catalyst, oil lime-ash, carbon
Matter shale etc..Because of vanadium raw materials species, mineral characteristic and wherein content of vanadium differs greatly, from vanadium-containing material extract vanadium technique and
Method is also varied, mainly there is pyrometallurgical smelting, wet-leaching and pyrogenic process-wet method combined extraction process.
1. pyrometallurgical smelting
Generally using vanadium titano-magnetite as primary raw material, vanadium-bearing hot metal is obtained by blast furnace or other ironmaking flows, then turning
Oxygen is blown into stove makes the vanadium oxidization enrichment in metal into slag.Obtain containing V when bessemerizing using duplex2O58~20% vanadium
Slag and the half steel containing C 3.6%, obtain containing V when blowing using single converter slag-making2O52~5% v-bearing steel slag and molten steel.
To vanadium slag or v-bearing steel slag carry out subsequent extracted by roasting-leaching or the mode that directly leaches.
2. wet-leaching
Such a technique is relatively applied to the waste such as dead catalyst, flying dust and oil lime-ash, also have be applied on a small quantity in bone coal,
The raw ores such as vanadium titano-magnetite, but because wherein vanadium all mainly exists in the form of the trivalent vanadium of indissoluble, directly leach compared with pyrometallurgical smelting
It is lower with pyrogenic process-wet method combined extraction process rate of recovery.At present the technique that directly leaches mainly have acidleach, alkali leaching, Bioleaching,
Pressurized acid leaching etc..
3. pyrogenic process-wet method combined extraction
Due to existing in the form of relatively stable trivalent vanadium more than vanadium in raw ore, it usually needs be calcined under oxidizing atmosphere it turn
High price compound is melted into favor of leaching.For the bone coal resource in China, its vanadium resource total amount contained accounts for national total vanadium
87%, for vanadium grade 0.13~1.2%, pyrogenic process-wet method combined extraction process of development has traditional sodium-salt calcination-water logging, sky
White roasting-acidleach (alkali leaching), few salt roasting-circulating leaching and calcium salt roasting-acidleach (alkali leaching) etc..
No matter it can be seen that the vanadium solution that can be all leached using which kind of method vanadium extraction, vanadium solution needs further processing ability
Separated with impurity, obtain the higher barium oxide of purity, typically take the techniques such as precipitation-calcining, solvent extraction-back extraction to obtain most
Whole vanadium product.The method of precipitation has many kinds, different according to precipitating reagent, be divided into calcium precipitation, molysite deposition, hydrolytic precipitation,
Ammonium salt precipitation etc.；Different depending on the pH value of solution during precipitation, the ammonium salt precipitation method are divided into the alkalescent ammonium salt precipitation method, faintly acid ammonium salt again
The precipitation method.
Current domestic precipitation uses batch (-type) acid ammonium salt precipitation mostly, because the vanadium solution of high concentration uses traditional ammonium salt
APV (ammonium poly-vanadate) facile hydrolysis of precipitation generation, obtains the hydrolysis prods of vanadium, it is difficult to separation of solid and liquid, so precipitation concentration is basic
Control is within 35g/L.Therefore the high vanadium concentrations solution for leaching to obtain from various navajoites needs to be sunk again after first diluting
Vanadium, but precipitation concentration is lower, wastewater flow rate is bigger caused by unit product, not only increases production cost, also increases trend of environmental protection
Danger, in addition, after vanadium solution dilution, the consumption of acid and ammonium salt is big, it is seen that the precipitation method of exploitation high vanadium concentrations solution has very
Important meaning.
The method that Application No. 201610152359.X Chinese patent discloses precipitation in a kind of high sodium solution from high vanadium,
It is studied for the early stage of the present inventor, and obtained product purity is high, and impurity is few, but the vanadium solution concentration handled is with vanadic anhydride
45~100g/L is calculated as, that is, vanadium 25~55.9g/L of concentration in the high sodium solution of high vanadium handled, the vanadium solution concentration of processing is still not
Enough height.The Chinese patent of application number 201510847816.2 discloses a kind of low-cost high-efficiency precipitation method, and its technical scheme is
A large amount of recovery precipitation waste liquid diluting high-concentration vanadium solutions, the dosage of acid and precipitation agent, but its method high energy consumption, production can be saved
Cost is high, and obtained product impurity is higher, and the rate of recovery of vanadium is relatively low.
The content of the invention
In order to solve the above-mentioned technical problem, continuously the vanadium in high vanadium concentrations solution can be settled out the invention provides a kind of
Next method, this method is continuous, product impurity that is simple, economic, environmentally friendly, efficient and obtaining is few.
The method of the continuous precipitation of high vanadium concentrations solution of the present invention comprises the following steps：
A, one-level precipitation：A small amount of dilution first adds to the first-stage reactor of precipitation, then by the saturated solution of precipitation agent, pre-
The high vanadium concentrations solution and pH adjusting agent of heat to 60~90 DEG C are continuously added to the first-stage reactor of precipitation simultaneously, are protected after reaction balance
1~20g/L of vanadium concentration in liquid phase is held, for temperature control at 85~98 DEG C, pH value is maintained at 1.8~3.0, adds ammonium coefficient to maintain
0.7~1.4, reaction starts continuous discharge to two level precipitation reactor after reaching balance and control material is in first-stage reactor
10~120min of mean residence time；
The vanadium concentration of wherein described high vanadium concentrations solution is 35~200g/L, and solution is sufficiently stirred in course of reaction；
B, two level precipitation：The material of first-stage reactor is continuously passed into second reactor, and heating keeps boiling, fully stirred
Mix, keep pH value to be maintained at 2.0~3.0 after reaction balance, vanadium concentration is less than 0.35g/L in liquid phase, and reaction is opened after reaching balance
Beginning continuous discharge carries out separation of solid and liquid, mean residence time 2~60min of the control material in second reactor；
C, vanadium reclaims：The solid ammonium poly-vanadate that two-stage precipitation obtains is separated with liquid, ammonium poly-vanadate is scrubbed, after calcining
Obtain vanadic anhydride；
D, precipitation devil liquor recovery：By precipitation devil liquor recovery, the preparation for the saturated solution of precipitation agent in a steps.
Wherein, a small amount of dilution refers to the minimum flow of dilution needed for stirring reaction in step a, with the size of reactor and
Type is relevant.
Further, ammonium precipitation agent described in a steps can be the one or more in ammonium sulfate, ammonium chloride, ammoniacal liquor.
Further, precipitation agent described in a steps plus ammonium coefficient preferably 0.8~1.2.
Further, pH value regulator described in a steps can be one or both of sulfuric acid and hydrochloric acid.
Further, dilution described in a steps can be the waste water and precipitation non-solid-liquid point after water, precipitation separation of solid and liquid
From slurry in one or more.
Further, mean residence time preferably 20~60min described in a steps.
Further, 2~10g/L of vanadium concentration in liquid phase is kept after reaction balance described in a steps.
Further, the preferably 5~30min of mean residence time described in b step.
The vanadic anhydride K obtained described in step c after precipitation after the caused scrubbed calcination of ammonium poly-vanadate2O+Na2O contains
Amount is less than 0.01% less than 0.5%, S contents.
High vanadium concentrations solution is carried out the continuous precipitation of two-stage by the method for the continuous precipitation of high vanadium concentrations solution of the present invention, can be located
Vanadium concentration is high in the raw material of reason, need not adjust the pH of vanadium solution before precipitation in addition, and the dosage of precipitation agent is few, and energy consumption is low, production effect
Rate is high, substantially reduces production cost.
The method of the present invention has advantage as is evident below compared with existing precipitation method：
1st, two-stage continuous precipitation is carried out using high vanadium concentrations solution, technique is simply efficient, and equipment investment is few；
2nd, waste water yield is few, unit precipitating reagent dosage and less energy consumption, and production efficiency is high, reduces production cost；
3rd, reaction condition is gentle, is not easy heavy useless, obtained good product quality；
4th, liquid phase vanadium concentration is low after precipitation, vanadium high income.
Brief description of the drawings
Fig. 1 is the process chart of the continuous precipitation of high vanadium concentrations solution of the present invention
Embodiment
The method of the continuous precipitation of high vanadium concentrations solution of the present invention comprises the following steps：
A, one-level precipitation：A small amount of dilution first adds to the first-stage reactor of precipitation, then by the saturated solution of precipitation agent, pre-
The high vanadium concentrations solution and pH adjusting agent of heat to 60~90 DEG C are continuously added to the first-stage reactor of precipitation simultaneously, are protected after reaction balance
1~20g/L of vanadium concentration in liquid phase is held, for temperature control at 85~98 DEG C, pH value is maintained at 1.8~3.0, adds ammonium coefficient to maintain
0.7~1.4, reaction starts continuous discharge to two level precipitation reactor after reaching balance and control material is in first-stage reactor
10~120min of mean residence time；
The vanadium concentration of wherein described high vanadium concentrations solution is 35~200g/L, and solution is sufficiently stirred in course of reaction；
B, two level precipitation：The material of first-stage reactor is continuously passed into second reactor, and heating keeps boiling, fully stirred
Mix, keep pH value to be maintained at 2.0~3.0 after reaction balance, vanadium concentration is less than 0.35g/L in liquid phase, and reaction is opened after reaching balance
Beginning continuous discharge carries out separation of solid and liquid, mean residence time 2~60min of the control material in second reactor；
C, vanadium reclaims：The solid ammonium poly-vanadate that two-stage precipitation obtains is separated with liquid, ammonium poly-vanadate is scrubbed, after calcining
Obtain vanadic anhydride；
D, precipitation devil liquor recovery：By precipitation devil liquor recovery, the preparation for the saturated solution of precipitation agent in a steps.
Wherein, a small amount of dilution refers to the minimum flow of dilution needed for stirring reaction in step a, with the size of reactor and
Type is relevant.
When one-level precipitation reaction starts, vanadium solution is continuously added in dilution, and the vanadium concentration in dilution is begun to ramp up, on
While liter, the vanadium in liquid phase precipitates into APV solids, and the vanadium solution for continuously entering reactor is continuously generated APV, after reaction balances
Continuous discharge can be started to second reactor.After reaction balances again, the inlet of vanadium is equal to the APV generated and consolidated in reactor
The scale of construction and the vanadium sum being discharged in second reactor slurry liquid phase, according to the parameter, feed rate and discharge velocity of reactor,
Mean residence time of the control material in first-stage reactor is 10~120min, when controlling the average stop in second reactor
Between be 2~60min.
The mean residence time of continuous flow reactor can be measured with tracer response method, can also be by establishing model
Calculated, such as plug flow model and complete mixing flow model, the measure of continuous flow reactor mean residence time or be calculated as
Existing method.
Reaction balance before continuous discharge is started described in a steps refers to：Reaction temperature is kept in 85~98 DEG C, pH value
In 1.8~3.0, liquid phase during 1~20g/L of vanadium concentration；Reaction after continuous discharge is started described in a steps can be put down again
Weighing apparatus, reaction temperature now are maintained at 1.8~3.0 in 85~98 DEG C, pH value, 1~20g/L of vanadium concentration and reactor in liquid phase
The vanadium sum that the inlet of interior vanadium is equal to the APV amount of solid of generation and is discharged in second reactor slurry liquid phase.
Reaction balance before continuous discharge is started described in b step refers to：Solution keeps boiling, pH value to be maintained at 2.0
~3.0, when vanadium concentration is less than 0.35g/L in liquid phase；Reaction after continuous discharge is started described in b step can balance again,
Now solution keeps boiling, pH value to be maintained at 2.0~3.0, and vanadium concentration is entered less than vanadium in 0.35g/L and reactor in liquid phase
Enter the vanadium concentration sum that amount is equal to the APV amount of solid of generation and is discharged in waste water.
Ammonium sulfate, ammonium chloride, ammoniacal liquor in the inventive method, first can be prepared precipitation agent as the precipitation agent of the present invention
Into the aqueous solution, saturated aqueous solution is formulated as, instead of the direct addition solid precipitation agent in traditional handicraft, optimizes ammonium ion and vanadium
The dynamic condition of acid ion reaction, has the characteristics of rapid reaction is uniform.Meanwhile it also avoid the sediments such as ammonium metavanadate
Produce, method of the invention is gone for the precipitation of the vanadium solution of higher concentration.
The addition of precipitation agent solution can be according to adding ammonium coefficient to determine, it adds ammonium coefficient to refer to the additions of ammonium sulfate solids
Quality and the mass ratio of vanadium in high vanadium solution, ammonium chloride and ammoniacal liquor can be scaled ammonium sulfate according to the molal quantity of ammonium ion and enter
Row calculates, for example, the ammonium root of 2mol ammonium chloride is identical with the ammonium root quantity of 1mol ammonium sulfate, then 2mol ammonium chloride conversion
Quality for ammonium sulfate is 132g, it is preferred that precipitation agent described in a steps adds ammonium coefficient to be 0.8~1.2.
Further, pH value regulator described in a steps is one or both of sulfuric acid and hydrochloric acid.
Further, dilution described in a steps is water, the waste water after precipitation separation of solid and liquid and the non-separation of solid and liquid of precipitation
One or more in slurry.
The process of precipitation be precipitate nucleation formed, the process grown up, it is necessary to certain breed and the reaction aging time, a steps
Mean residence time preferably 20~60min described in rapid.
Further, vanadium concentration preferably 2~10g/L in liquid phase after reaction balances described in a steps.
Further, the preferably 5~30min of mean residence time described in b step.
Caused ammonium poly-vanadate is scrubbed after precipitation described in step c, obtained vanadic anhydride K after calcination2O+Na2O contains
Amount is less than 0.01% less than 0.5%, S contents, wherein K2O+Na2O content refers to K2O mass percent and Na2O quality
Percentage sum, S contents refer to S mass percent.
High vanadium concentrations solution is carried out the continuous precipitation of two-stage by the method for the continuous precipitation of high vanadium concentrations solution of the present invention, specifically
Fig. 1 is shown in technological process.
The present invention can reduce waste water yield, reduce the dosage of precipitating reagent, and energy consumption is low, and production efficiency is high, substantially reduces life
Cost is produced, obtained product impurity is few, and purity is high.
The embodiment of the present invention is further described with reference to embodiment, therefore not limited the present invention
System is among described scope of embodiments.
Embodiment 1
It is 11, vanadium concentration 195.2g/L vanadium solutions by pH value, is preheated to 80 DEG C.Add pH value into precipitation first-stage reactor
2.5 vanadium wastewater 5m3, vanadium solution, ammonium sulfate saturated solution and pH adjusting agent sulfuric acid are continuously added to first-stage reactor simultaneously and entered
Row precipitation, add ammonium coefficient 0.8, it is 1.8~3.0 that solution ph is controlled during precipitation, 95 DEG C of temperature, is sufficiently stirred solution, is put down
Equal residence time 120min, vanadium concentration 9.9g/L in liquid phase after reaction balance, after reaction balance continuous discharge to second reactor,
It is 2.0~3.0 to control solution ph, is heated to seething with excitement and keeps seething with excitement, and is sufficiently stirred solution, mean residence time 60min, puts down
Liquid phase liquid vanadium concentration 0.31g/L after weighing apparatus, start continuous discharge after balance and carry out separation of solid and liquid, the ammonium poly-vanadate that separation of solid and liquid obtains
The vanadic anhydride K obtained after scrubbed, calcination2O+Na2O content 0.49%, S contents<0.01%.
Embodiment 2
By the vanadium solution that pH value is 10.5, vanadium concentration 110.2g/L, 70 DEG C are preheated to.Add pH into precipitation first-stage reactor
The vanadium wastewater 5m of value 2.53, vanadium solution, ammoniacal liquor and pH adjusting agent hydrochloric acid are continuously added to first-stage reactor simultaneously and carry out precipitation, is added
Ammonium coefficient 1.0, it is 1.8~3.0 that solution ph is persistently adjusted during precipitation, 93 DEG C of temperature, is sufficiently stirred solution, average to stop
Time 20min, vanadium concentration 4.8g/L in liquid phase after reaction balances, continuous discharge is lasting to adjust to second reactor after reaction balances
It is 2.0~3.0 to save solution ph, is heated to seething with excitement and keeps seething with excitement, and is sufficiently stirred solution, mean residence time 5min, balance
Liquid phase liquid vanadium concentration 0.28g/L afterwards, start continuous discharge after balance and carry out separation of solid and liquid, the ammonium poly-vanadate warp that separation of solid and liquid obtains
The vanadic anhydride K obtained after washing, calcination2O+Na2O content 0.45%, S contents<0.01%.
Embodiment 3
By the vanadium solution that pH value is 9.5, vanadium concentration 45.3g/L, 90 DEG C are preheated to.Add pH value into precipitation first-stage reactor
2.5 vanadium wastewater 5m3, vanadium solution, ammonium chloride saturated solution and pH adjusting agent sulfuric acid are continuously added to first-stage reactor simultaneously and entered
Row precipitation, add ammonium coefficient 1.2, it is 1.8~3.0 that solution ph is persistently adjusted during precipitation, 90 DEG C of temperature, is sufficiently stirred molten
Liquid, mean residence time 10min, vanadium concentration 6.1g/L in liquid phase after reaction balances, continuous discharge is anti-to two level after reaction balances
Device is answered, it is 2.0~3.0 persistently to adjust solution ph, is heated to seething with excitement and keeps seething with excitement, solution is sufficiently stirred, when averagely stopping
Between 15min, liquid phase liquid vanadium concentration 0.21g/L after balance, start continuous discharge after balance and carry out separation of solid and liquid, separation of solid and liquid obtains
Ammonium poly-vanadate is scrubbed, obtained vanadic anhydride K after calcination2O+Na2O content 0.42%, S contents<0.01%.
Embodiment 4
By the vanadium solution that pH value is 10.5, vanadium concentration 110.2g/L, 60 DEG C are preheated to.Add pH into precipitation first-stage reactor
The vanadium wastewater 5m of value 2.53, vanadium solution, ammonium sulfate saturated solution and pH adjusting agent sulfuric acid are continuously added to first-stage reactor simultaneously
Precipitation is carried out, adds ammonium coefficient 1.1, it is 1.8~3.0 that solution ph is persistently adjusted during precipitation, 85 DEG C of temperature, is sufficiently stirred molten
Liquid, mean residence time 60min, vanadium concentration 3.1g/L in liquid phase after reaction balances, continuous discharge is anti-to two level after reaction balances
Device is answered, it is 2.0~3.0 persistently to adjust solution ph, is heated to seething with excitement and keeps seething with excitement, solution is sufficiently stirred, when averagely stopping
Between 30min, liquid phase liquid vanadium concentration 0.18g/L after balance, start continuous discharge after balance and carry out separation of solid and liquid, separation of solid and liquid obtains
Ammonium poly-vanadate is scrubbed, obtained vanadic anhydride K after calcination2O+Na2O content 0.43%, S contents<0.01%.
Embodiment 5
By the vanadium solution that pH value is 10.5, vanadium concentration 110.2g/L, 70 DEG C are preheated to.Add pH into precipitation first-stage reactor
The vanadium wastewater 5m of value 2.53, vanadium solution, ammonium chloride saturated solution and pH adjusting agent sulfuric acid are continuously added to first-stage reactor simultaneously
Precipitation is carried out, adds ammonium coefficient 1.4, it is 1.8~3.0 that solution ph is persistently adjusted during precipitation, 98 DEG C of temperature, is sufficiently stirred molten
Liquid, mean residence time 20min, vanadium concentration 1g/L in liquid phase after reaction balance, continuous discharge is to second order reaction after reaction balance
Device, it is 2.0~3.0 persistently to adjust solution ph, is heated to seething with excitement and keeps seething with excitement, is sufficiently stirred solution, mean residence time
2min, liquid phase liquid vanadium concentration 0.30g/L after balance, start continuous discharge after balance and carry out separation of solid and liquid, what separation of solid and liquid obtained
The vanadic anhydride K that ammonium poly-vanadate is scrubbed, is obtained after calcination2O+Na2O content 0.50%, S contents<0.01%.
Comparative example 1
By the vanadium solution that pH value is 10.5, vanadium concentration 110.2g/L, with traditional precipitation technique precipitation, obtained product containing vanadium
The hydrolysis prods of all vanadium, it is difficult to separation of solid and liquid, the vanadic anhydride K obtained after scrubbed, calcination2O+Na2O content
5.57%, S content 0.52%.
Comparative example 2
By the vanadium solution that pH value is 10.5, vanadium concentration 110.2g/L, it is 7.0 with sulphur acid for adjusting pH value, is heated to 75 DEG C, adds
Ammonium sulfate.Vanadium solution is added into vanadium settling tank and carries out precipitation, it is 1.8~3.0 that solution ph is persistently adjusted during precipitation, is added altogether
Vanadium solution 15m3, after precipitation terminates, the hydrolysis prods of the obtained all vanadium of product containing vanadium, it is difficult to separation of solid and liquid, scrubbed, forging
The vanadic anhydride K obtained after burning2O+Na2O content 5.45%, S contents 0.51%.
Comparative example 3
By the vanadium solution 15m that pH value is 10.5, vanadium concentration 110.2g/L3, add water 5m3, it is 7.0 with sulphur acid for adjusting pH value,
75 DEG C are heated to, adds ammonium sulfate.Vanadium solution is added into vanadium settling tank and carries out precipitation, solution ph is persistently adjusted during precipitation is
1.8~3.0, after precipitation terminates, the hydrolysis prods of the obtained all vanadium of product containing vanadium, it is difficult to separation of solid and liquid, scrubbed, calcination
The vanadic anhydride obtained afterwards, impurity K2O+Na2O content 5.18%, S contents 0.49%.
Comparative example 4
By the vanadium solution 15m that pH value is 10.5, vanadium concentration 110.2g/L3, using in application number 201510847816.2
Method disclosed in state's patent, after precipitation terminates, the hydrolysis prods of the obtained all vanadium of product containing vanadium, it is difficult to separation of solid and liquid, warp
The vanadic anhydride obtained after washing, calcination, impurity K2O+Na2O content 4.35%, S contents 0.41%.
Therefore the vanadium solution of the method energy continuous processing high concentration using the present invention, product impurity is few, and purity is high；
In addition technique is simply efficient, and equipment investment is few, and waste water yield is few, and precipitating reagent dosage and energy consumption are low, reduces production cost, tool
There is good application prospect.
Claims (30)
1. the method for the continuous precipitation of high vanadium concentrations solution, it is characterised in that comprise the following steps：
A, one-level precipitation：First by a small amount of dilution add precipitation first-stage reactor, then by the saturated solution of precipitation agent, be preheated to
60~90 DEG C of high vanadium concentrations solution and pH adjusting agent is continuously added to the first-stage reactor of precipitation simultaneously, and liquid is kept after reaction balance
1~20g/L of vanadium concentration in phase, for temperature control at 85~98 DEG C, pH value is maintained at 1.8~3.0, add ammonium coefficient maintain 0.7~
1.4, reaction reach balance after start continuous discharge to two level precipitation reactor and control material being averaged in first-stage reactor
10~120min of residence time；
The vanadium concentration of wherein described high vanadium concentrations solution is 110.2~200g/L, and solution is sufficiently stirred in course of reaction；
B, two level precipitation：The material of first-stage reactor is continuously passed into second reactor, and heating keeps boiling, is sufficiently stirred, instead
PH value is kept to be maintained at 2.0~3.0 after should balancing, vanadium concentration is less than 0.35g/L in liquid phase, and reaction starts continuously after reaching balance
Discharging carries out separation of solid and liquid, mean residence time 2~60min of the control material in second reactor；
C, vanadium reclaims：The solid ammonium poly-vanadate that two-stage precipitation obtains is separated with liquid, ammonium poly-vanadate is scrubbed, is obtained after calcining
Vanadic anhydride；
D, precipitation devil liquor recovery：By precipitation devil liquor recovery, the preparation for the saturated solution of precipitation agent in a steps.
2. the method for the continuous precipitation of high vanadium concentrations solution according to claim 1, it is characterised in that precipitation described in a steps
Agent is the one or more in ammonium sulfate, ammonium chloride, ammoniacal liquor.
3. the method for the continuous precipitation of high vanadium concentrations solution according to claim 1 or 2, it is characterised in that described in a steps
Precipitation agent adds ammonium coefficient to be 0.8~1.2.
4. the method for the continuous precipitation of high vanadium concentrations solution according to claim 1 or 2, it is characterised in that described in a steps
PH value regulator is one or both of sulfuric acid and hydrochloric acid.
5. the method for the continuous precipitation of high vanadium concentrations solution according to claim 3, it is characterised in that pH value described in a steps
Conditioning agent is one or both of sulfuric acid and hydrochloric acid.
6. the method for the continuous precipitation of high vanadium concentrations solution according to any one of claim 1,2,5, it is characterised in that a steps
Described in dilution be one or more in the slurry of water, the waste water after precipitation separation of solid and liquid and the non-separation of solid and liquid of precipitation.
7. the method for the continuous precipitation of high vanadium concentrations solution according to claim 3, it is characterised in that diluted described in a steps
Liquid is the one or more in the slurry of water, the waste water after precipitation separation of solid and liquid and the non-separation of solid and liquid of precipitation.
8. the method for the continuous precipitation of high vanadium concentrations solution according to claim 4, it is characterised in that diluted described in a steps
Liquid is the one or more in the slurry of water, the waste water after precipitation separation of solid and liquid and the non-separation of solid and liquid of precipitation.
9. the method for the continuous precipitation of high vanadium concentrations solution according to any one of claim 1,2,5,7~8, it is characterised in that
The mean residence time of material in the reactor described in a steps is 20~60min.
10. the method for the continuous precipitation of high vanadium concentrations solution according to claim 3, it is characterised in that thing described in a steps
The mean residence time of material in the reactor is 20~60min.
11. the method for the continuous precipitation of high vanadium concentrations solution according to claim 4, it is characterised in that thing described in a steps
The mean residence time of material in the reactor is 20~60min.
12. the method for the continuous precipitation of high vanadium concentrations solution according to claim 6, it is characterised in that thing described in a steps
The mean residence time of material in the reactor is 20~60min.
13. the method for the continuous precipitation of high vanadium concentrations solution according to any one of claim 1,2,5,7~8,10~12, its
2~10g/L of vanadium concentration in liquid phase is kept after being characterised by reaction balance described in a steps.
14. the method for the continuous precipitation of high vanadium concentrations solution according to claim 3, it is characterised in that anti-described in a steps
2~10g/L of vanadium concentration in liquid phase is kept after should balancing.
15. the method for the continuous precipitation of high vanadium concentrations solution according to claim 4, it is characterised in that anti-described in a steps
2~10g/L of vanadium concentration in liquid phase is kept after should balancing.
16. the method for the continuous precipitation of high vanadium concentrations solution according to claim 6, it is characterised in that anti-described in a steps
2~10g/L of vanadium concentration in liquid phase is kept after should balancing.
17. the method for the continuous precipitation of high vanadium concentrations solution according to claim 9, it is characterised in that anti-described in a steps
2~10g/L of vanadium concentration in liquid phase is kept after should balancing.
18. the continuous precipitation of high vanadium concentrations solution according to any one of claim 1,2,5,7~8,10~12,14~17
Method, it is characterised in that the mean residence time of material described in b step in the reactor is 5~30min.
19. the method for the continuous precipitation of high vanadium concentrations solution according to claim 3, it is characterised in that thing described in b step
The mean residence time of material in the reactor is 5~30min.
20. the method for the continuous precipitation of high vanadium concentrations solution according to claim 4, it is characterised in that thing described in b step
The mean residence time of material in the reactor is 5~30min.
21. the method for the continuous precipitation of high vanadium concentrations solution according to claim 6, it is characterised in that thing described in b step
The mean residence time of material in the reactor is 5~30min.
22. the method for the continuous precipitation of high vanadium concentrations solution according to claim 9, it is characterised in that thing described in b step
The mean residence time of material in the reactor is 5~30min.
23. the method for the continuous precipitation of high vanadium concentrations solution according to claim 13, it is characterised in that thing described in b step
The mean residence time of material in the reactor is 5~30min.
24. the high vanadium concentrations solution according to any one of claim 1,2,5,7~8,10~12,14~17,19~23 connects
The method of continuous precipitation, it is characterised in that five oxygen obtained described in step c after precipitation after the caused scrubbed calcination of ammonium poly-vanadate
Change two vanadium K2O+Na2O content is less than 0.01% less than 0.5%, S contents.
25. the method for the continuous precipitation of high vanadium concentrations solution according to claim 3, it is characterised in that sunk described in step c
The vanadic anhydride K obtained after vanadium after the caused scrubbed calcination of ammonium poly-vanadate2O+Na2O content is less than less than 0.5%, S contents
0.01%.
26. the method for the continuous precipitation of high vanadium concentrations solution according to claim 4, it is characterised in that sunk described in step c
The vanadic anhydride K obtained after vanadium after the caused scrubbed calcination of ammonium poly-vanadate2O+Na2O content is less than less than 0.5%, S contents
0.01%.
27. the method for the continuous precipitation of high vanadium concentrations solution according to claim 6, it is characterised in that sunk described in step c
The vanadic anhydride K obtained after vanadium after the caused scrubbed calcination of ammonium poly-vanadate2O+Na2O content is less than less than 0.5%, S contents
0.01%.
28. the method for the continuous precipitation of high vanadium concentrations solution according to claim 9, it is characterised in that sunk described in step c
The vanadic anhydride K obtained after vanadium after the caused scrubbed calcination of ammonium poly-vanadate2O+Na2O content is less than less than 0.5%, S contents
0.01%.
29. the method for the continuous precipitation of high vanadium concentrations solution according to claim 13, it is characterised in that sunk described in step c
The vanadic anhydride K obtained after vanadium after the caused scrubbed calcination of ammonium poly-vanadate2O+Na2O content is less than less than 0.5%, S contents
0.01%.
30. the method for the continuous precipitation of high vanadium concentrations solution according to claim 18, it is characterised in that sunk described in step c
The vanadic anhydride K obtained after vanadium after the caused scrubbed calcination of ammonium poly-vanadate2O+Na2O content is less than less than 0.5%, S contents
0.01%.
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| CN109081374B (en) * | 2018-10-19 | 2021-03-02 | 河钢股份有限公司承德分公司 | Method for preparing large-particle-size spherical ammonium polyvanadate |
| CN109112300A (en) * | 2018-11-14 | 2019-01-01 | 攀钢集团钒钛资源股份有限公司 | Improve the method and device of precipitation APV heap density |
| CN116102062A (en) * | 2021-11-11 | 2023-05-12 | 中国科学院过程工程研究所 | Method for continuously precipitating ammonium polyvanadate and method for establishing mathematical model of ammonium polyvanadate |
| CN115676886B (en) * | 2022-11-15 | 2024-05-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for reducing vanadium precipitation wastewater of high-concentration vanadium solution |
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| CN202744347U (en) * | 2012-08-28 | 2013-02-20 | 攀钢集团攀枝花钢钒有限公司 | Vanadium settling device |
| CN105603221A (en) * | 2016-03-17 | 2016-05-25 | 攀钢集团攀枝花钢钒有限公司 | Method for precipitating vanadium from high-vanadium high-sodium solution |
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| CN202744347U (en) * | 2012-08-28 | 2013-02-20 | 攀钢集团攀枝花钢钒有限公司 | Vanadium settling device |
| CN105603221A (en) * | 2016-03-17 | 2016-05-25 | 攀钢集团攀枝花钢钒有限公司 | Method for precipitating vanadium from high-vanadium high-sodium solution |
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