CN109081374A - A method of preparing the spherical ammonium poly-vanadate of big granularity - Google Patents
A method of preparing the spherical ammonium poly-vanadate of big granularity Download PDFInfo
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Abstract
The present invention relates to a kind of methods for preparing the spherical ammonium poly-vanadate of big granularity, the method are as follows: vanadium scavenging solution will be contained and be added in crystallizer, control heating rate is 0.1-3 DEG C/h, and the temperature of the scavenging solution containing vanadium is warming up to 85-95 DEG C, ammonium salt is added in temperature-rise period and adjusts pH；After the temperature of the scavenging solution containing vanadium reaches predetermined value, continue that scavenging solution containing vanadium is added into crystallizer, control heating rate is 6-10 DEG C/h, and the temperature of the scavenging solution containing vanadium is made to be maintained at 85-95 DEG C, ammonium salt is added in temperature-rise period and adjusts pH, and crystallization obtains 150 μm of granularity or more of spherical ammonium poly-vanadate.The spherical ammonium poly-vanadate that granularity is greater than 150 μm has been prepared in the present invention, and gained ammonium poly-vanadate product sphericity is high, and granule strength is high, can satisfy the requirement of vanadium alloy and V electrolyte field to vanadic anhydride product granularity, has a good application prospect.
Description
Technical field
The present invention relates to vanadium chemical fields, and in particular to a method of prepare the spherical ammonium poly-vanadate of big granularity.
Background technique
Vanadium has excellent intensity, ductility, heat resistance, can significantly improve the performance of steel, is that production high-strength steel can not
The important element lacked, referred to as " monosodium glutamate of modern industry ".
The vanadic anhydride granularity obtained using traditional ammonium salt precipitation method is small, generally at 80 μm hereinafter, small five oxygen of granularity
Change that two vanadium wellabilities are weak, and air-flow transporting is poor, is not able to satisfy the production needs of energy storage field different valence state V electrolyte.In addition,
Preparing vanadium alloy as raw material using the small vanadic anhydride of granularity will inevitably cause more serious gas, material to fly upward, and overflow
The entrainment of furnace gas will cause the smelting of expensive vanadium oxide to lose out.Ammonium poly-vanadate is the important source material for preparing vanadic anhydride, because
This, the granularity for improving ammonium poly-vanadate is to obtain one of the important means of big granularity vanadic anhydride.
CN104760996A discloses a kind of method of low temperature crystallization ammonium poly-vanadate, and seed content is added in vanadium liquid, stirs
Mix dissolution；Then acid adding adjusts the pH value of vanadium liquid to 1.0~7.0；Continuing stirring is precipitated ammonium poly-vanadate crystal, is obtained by filtration more
Ammonium vanadate crystal；The seed content is one or more of mixing of water-soluble organic amine class and its derivative.It is obtained more
Ammonium vanadate crystallographic grain degree is smaller, it is difficult to meet the requirement for preparing big granularity vanadic anhydride.
A kind of method that continous way is added ammonium sulfate to prepare spherical ammonium poly-vanadate, but the party are disclosed in CN1258642A
Method is difficult to control the addition of ammonium sulfate, need in addition increase automatic control equipment, to increase Meteorological.
CN102502823A discloses a kind of preparation method of the ammonium poly-vanadate of high-tap density, and this method includes following step
It is rapid: ammonium poly-vanadate crystal seed and sulfuric acid a) being added under conditions of the pH of solution containing vanadium is 5.0-5.5 and temperature is 60 DEG C -90 DEG C
Ammonium；B) pH of solution containing vanadium obtained in step a is adjusted to 2.2-2.4 and its temperature is increased to 90 DEG C -95 DEG C, quickly stirred
Mix lower precipitating ammonium poly-vanadate；C) after adding ammonium sulfate twice to solution containing vanadium obtained in step b, it is more to precipitate to reduce mixing speed
Ammonium vanadate；D) it is filtered, washs, being dried to obtain high-tap density ammonium poly-vanadate, this method needs substep acid adding, and operation is multiple
It is miscellaneous.
Ammonium poly-vanadate granularity obtained in the above method is unsatisfactory, and needs additional addition external equipment, is unfavorable for big
Scale is promoted.Therefore, it is necessary to a kind of method for preparing big granularity ammonium poly-vanadate be developed, to meet vanadium alloy and V electrolyte etc.
Demand of the field to vanadic anhydride product granularity.
Summary of the invention
In view of problems of the prior art, the present invention provides a kind of sides for preparing the spherical ammonium poly-vanadate of big granularity
Method solves the problems, such as that ammonium poly-vanadate grain size number is small under natural conditions, the ammonium poly-vanadate granularity of preparation can reach 150 μm with
On, sphericity is high, and granule strength is high, can satisfy vanadium alloy and V electrolyte field to the need of vanadic anhydride product granularity
It asks；And automation degree of equipment is high, technological operation is simple, is conducive to industrialized production, has a good application prospect.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides a kind of methods for preparing the spherical ammonium poly-vanadate of big granularity, the described method comprises the following steps:
(1) vanadium scavenging solution will be contained to be added in crystallizer, control heating rate is 0.1-3 DEG C/h, by the temperature of the scavenging solution containing vanadium
Degree is warming up to 85-95 DEG C, and ammonium salt is added in temperature-rise period and adjusts pH；
(2) after the temperature of step (1) scavenging solution containing vanadium reaches 85-95 DEG C, continue to be added into crystallizer containing vanadium
Scavenging solution, control heating rate are 6-10 DEG C/h, so that the temperature of the scavenging solution containing vanadium is maintained at 85-95 DEG C, add in temperature-rise period
Ammonium salt simultaneously adjusts pH, and crystallization obtains 150 μm of granularity or more of spherical ammonium poly-vanadate.
The present invention is realized by the control for above-mentioned crystallization process parameter to the spherical ammonium poly-vanadate of big granularity (> 150
μm) preparation.Wherein, the present invention heats up at 0.1-3 DEG C/h first, under this rate, is conducive to make reaction generation
Ammonium poly-vanadate forms biggish nucleus；It is subsequent will heat up rate increase be 6-10 DEG C/h, it is fast to be conducive to newly-generated ammonium poly-vanadate
Speed is reunited around the nucleus formed before, and then obtains spherical ammonium poly-vanadate of the granularity at 150 μm or more.
According to the present invention, the heating rate of control crystallizer is 0.1-3 DEG C/h in step (1), for example, can be 0.1 DEG C/
H, the specific point value between 0.5 DEG C/h, 1 DEG C/h, 1.5 DEG C/h, 2 DEG C/h, 2.5 DEG C/h or 3 DEG C/h and above-mentioned numerical value, is limited to
Length and for concise consideration, the present invention no longer exclusive list.
As the heating rate in step (1) excessively slow (0.1 DEG C/h of <), crystallization time is too long, and the nucleus of generation has been analysed
Out, subsequent to be difficult to obtain the ammonium poly-vanadate of big granularity, while reducing production efficiency；As heating rate too fast (3 DEG C/h of >),
Big nucleus quantity is reduced, and is unfavorable for preparing the ammonium poly-vanadate of big granularity.
According to the present invention, the heating rate of control crystallizer is 6-10 DEG C/h in step (2), for example, can be 6 DEG C/h,
Between 6.5 DEG C/h, 7 DEG C/h, 7.5 DEG C/h, 8 DEG C/h, 8.5 DEG C/h, 9 DEG C/h, 9.5 DEG C/h or 10 DEG C/h and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
As heating rate excessively slow (6 DEG C/h of <) in step (2), ammonium poly-vanadate reunion rate is slack-off, and it is big to be unfavorable for preparation
The ammonium poly-vanadate of granularity；As heating rate too fast (10 DEG C/h of >), heating is too fast to cause heat to be unevenly distributed, and what is obtained is more
Ammonium vanadate shape of product is irregular, is unfavorable for subsequent applications.
According to the present invention, the temperature of the scavenging solution containing vanadium in crystallizer is warming up to 85-95 DEG C in step (1), such as can
To be between 85 DEG C, 86 DEG C, 87 DEG C, 88 DEG C, 89 DEG C, 90 DEG C, 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C or 95 DEG C and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the pH of control scavenging solution containing vanadium is 1.9-2.3 in step (1), for example, can be 1.9,1.9,2,
2.1, the specific point value between 2.2 or 2.3 and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer poor
It enumerates to the greatest extent.
According to the present invention, the temperature of the scavenging solution containing vanadium in step (2) in control crystallizer is 85-95 DEG C, such as can be with
It is between 85 DEG C, 86 DEG C, 87 DEG C, 88 DEG C, 89 DEG C, 90 DEG C, 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C or 95 DEG C and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the pH of control scavenging solution containing vanadium is 1.9-2.3 in step (2), for example, can be 1.9,1.9,2,
2.1, the specific point value between 2.2 or 2.3 and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer poor
It enumerates to the greatest extent.
According to the present invention, in the scavenging solution containing vanadium vanadium concentration be 20-40g/L, such as can be 20g/L, 23g/L,
Specific point value between 25g/L, 28g/L, 30g/L, 33g/L, 35g/L, 38g/L or 40g/L and above-mentioned numerical value, is limited to a piece
Width and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the crystallizer is OSLO crystallizer or DTB crystallizer.
According to the present invention, the ammonium salt is ammonium sulfate.
According to the present invention, during the addition ammonium salt, NH in ammonium salt is controlled4 +With the molar ratio of V in scavenging solution containing vanadium
For (0.7-1.0): 1, such as can be 0.7:1,0.75:1,0.8:1,0.85:1,0.9:1,0.95:1 or 1.0:1, Yi Jishang
The specific point value between numerical value is stated, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, hot water flow is adjusted by heat-exchanger pump and recycles the heating speed that pump frequency controls solution in crystallizer
Rate.
According to the present invention, the temperature difference≤5 that crystallizer adds solution in hot water backwater and crystallizer are controlled during entire crystallization
DEG C, when 5 DEG C of temperature difference > of the two, easily scabs in heat exchange interface (exchanger tube wall) and heat exchanger is caused to block.
According to the present invention, the pH of sulfuric acid regulation solution is added in crystallization process.
According to the present invention, liquid level reaches overflow port in control crystallizer in step (1), in step (2) in control crystallizer
Liquid level is higher than overflow port.
According to the present invention, the spherical ammonium poly-vanadate crystallized in crystallizer is filtered, is washed, it is dry.
It according to the present invention, is 0.1-10m by the flow that feed pump controls the scavenging solution containing vanadium in step (2)3/ h, accordingly
Adjustment discharging pump frequency makes liquid level in crystallizer be higher than overflow port, to guarantee that charging and discharging reach balance.
The method of the present invention for preparing the spherical ammonium poly-vanadate of big granularity includes following step as a preferred technical solution,
It is rapid:
(1) feed pump is opened, the scavenging solution containing vanadium that vanadium concentration is 20-40g/L is added in crystallizer, is overflow until liquid level reaches
Head piece；
(2) heating pump and circulating pump are opened, control heating rate is 0.1-3 DEG C/h, by scavenging solution containing vanadium in crystallizer
Temperature rise to 85-95 DEG C；Control crystallizer adds the temperature difference≤5 DEG C of solution in hot water backwater and crystallizer, presses in temperature-rise period
According to (0.7-1.0): ammonium sulfate is added in 1 ammonium vanadium molar ratio, while it is 1.9-2.3 that sulfuric acid regulation solution pH, which is added,；
(3) it after the temperature of the scavenging solution containing vanadium reaches 85-95 DEG C in device to be crystallized, opens feed pump and continues to add into crystallizer
Enter scavenging solution containing vanadium, control heating rate is 6-10 DEG C/h, so that the temperature of the scavenging solution containing vanadium is maintained at 85-95 DEG C, control crystallization
Device adds the temperature difference≤5 DEG C of solution in hot water backwater and crystallizer, and according to (0.7-1.0) in temperature-rise period: 1 ammonium vanadium molar ratio adds
Enter ammonium sulfate, while it is 1.9-2.3 that sulfuric acid regulation solution pH, which is added,；Discharging pump discharging is opened, liquid level in crystallizer is controlled and is higher than
Overflow port；
(4) after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
Compared with prior art, the present invention is at least had the advantages that
(1) spherical more vanadic acid that granularity is greater than 150 μm have been prepared by the state modulator to crystallization process in the present invention
Ammonium, gained ammonium poly-vanadate product sphericity is high, and granule strength is high, can satisfy vanadium alloy and V electrolyte field to five oxidations two
The requirement of vanadium product granularity；
(2) present device high degree of automation, technological operation is simple, is conducive to industrialized production, has good answer
Use prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the crystallizer 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.
The method for preparing the spherical ammonium poly-vanadate of big granularity that a kind of specific embodiment of the present invention provides can be using in Fig. 1
The crystallizer of offer carries out.In preparation process, the solution in ammonium poly-vanadate solution surge tank is added to by feed pump first
In crystallizer, until liquid level reaches overflow port；It is then turned on heating pump and circulating pump, by adjusting hot water flow and circulation pumping frequency
Rate controls the temperature of solution in crystallizer, and crystallizer is added in the solution in ammonium sulfate tank in temperature-rise period, is added simultaneously
Sulfuric acid regulation solution pH；After the temperature of the scavenging solution containing vanadium reaches predetermined value in device to be crystallized, opens feed pump and continue to crystallizer
Middle addition scavenging solution containing vanadium, controls the temperature of solution in crystallizer, while ammonium sulfate and sulfuric acid is added, and open discharging and pump out
Material, crystallization process control the temperature difference that liquid level in crystallizer adds solution in hot water backwater and crystallizer higher than overflow port and crystallizer
≤ 5 DEG C, after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
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
(1) feed pump is opened, the vanadium scavenging solution that vanadium concentration is 30.12g/L is added in crystallizer, is overflow until liquid level reaches
Head piece；
(2) heating pump and circulating pump are opened, by adjusting the heating of hot water flow and circulation pump frequency control crystallizer
Rate is 1 DEG C, and the temperature of the scavenging solution containing vanadium in crystallizer is risen to 90 DEG C；Control crystallizer add hot water backwater with it is molten in crystallizer
The temperature difference≤2 DEG C of liquid are slowly added to ammonium sulfate according to the ammonium vanadium molar ratio of 0.8:1 in temperature-rise period, while being slowly added to sulfuric acid
Adjusting pH value of solution is 2；
(3) it after the temperature of the scavenging solution containing vanadium reaches 90 DEG C in device to be crystallized, opens feed pump and continues to be added into crystallizer
Scavenging solution containing vanadium, feed rate 8m3/ h, control heating rate are 8 DEG C/h, and the temperature of the scavenging solution containing vanadium is made to be maintained at 90 DEG C,
Control crystallizer adds the temperature difference≤2 DEG C of solution in hot water backwater and crystallizer, according to the ammonium vanadium molar ratio of 0.8:1 in temperature-rise period
Ammonium sulfate is added, while it is 2 that sulfuric acid regulation solution pH, which is added,；Discharging pump discharging is opened, liquid level in crystallizer is controlled and is higher than overflow
Mouthful；
(4) after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
Through detecting: 150 μm of partial size > and<300 μm of content are 70wt% in obtained ammonium poly-vanadate product, partial size>=
300 μm of content is 30wt%.
Embodiment 2
(1) feed pump is opened, the vanadium scavenging solution that vanadium concentration is 35.64g/L is added in crystallizer, is overflow until liquid level reaches
Head piece；
(2) heating pump and circulating pump are opened, by adjusting hot water flow and circulation pump frequency control crystallizer heating speed
Rate is 2 DEG C, and the temperature of the scavenging solution containing vanadium in crystallizer is risen to 85 DEG C；Control crystallizer adds solution in hot water backwater and crystallizer
The temperature difference≤4 DEG C, be slowly added to ammonium sulfate according to the ammonium vanadium molar ratio of 0.9:1 in temperature-rise period, while being slowly added to sulfuric acid tune
Saving pH value of solution is 2.2；
(3) it after the temperature of the scavenging solution containing vanadium reaches 85 DEG C in device to be crystallized, opens feed pump and continues to be added into crystallizer
Scavenging solution containing vanadium, feed rate 4m3/ h, control heating rate are 6 DEG C/h, and the temperature of the scavenging solution containing vanadium is made to be maintained at 85 DEG C,
Control crystallizer adds the temperature difference≤4 DEG C of solution in hot water backwater and crystallizer, according to the ammonium vanadium molar ratio of 0.9:1 in temperature-rise period
Ammonium sulfate is added, while it is 2.2 that sulfuric acid regulation solution pH, which is added,；Discharging pump discharging is opened, liquid level, which is higher than, in control crystallizer overflows
Head piece；
(4) after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
Through detecting: 150 μm of partial size > and<300 μm of content are 63wt% in obtained ammonium poly-vanadate product, partial size>=
300 μm of content is 37wt%.
Embodiment 3
(1) feed pump is opened, the vanadium scavenging solution that vanadium concentration is 24.95g/L is added in crystallizer, is overflow until liquid level reaches
Head piece；
(2) heating pump and circulating pump are opened, by adjusting hot water flow and circulation pump frequency control crystallizer heating speed
Rate is 3 DEG C, and the temperature of the scavenging solution containing vanadium in crystallizer is risen to 88 DEG C；Control crystallizer adds solution in hot water backwater and crystallizer
The temperature difference≤5 DEG C, be slowly added to ammonium sulfate according to the ammonium vanadium molar ratio of 1:1 in temperature-rise period, while being slowly added to sulfuric acid adjusting
PH value of solution is 1.9；
(3) it after the temperature of the scavenging solution containing vanadium reaches 88 DEG C in device to be crystallized, opens feed pump and continues to be added into crystallizer
Scavenging solution containing vanadium, feed rate 1m3/ h, control heating rate are 9 DEG C/h, and the temperature of the scavenging solution containing vanadium is made to be maintained at 88 DEG C,
Control crystallizer adds the temperature difference≤4 DEG C of solution in hot water backwater and crystallizer, adds in temperature-rise period according to the ammonium vanadium molar ratio of 1:1
Enter ammonium sulfate, while it is 1.9 that sulfuric acid regulation solution pH, which is added,；Discharging pump discharging is opened, liquid level in crystallizer is controlled and is higher than overflow
Mouthful；
(4) after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
Through detecting: 150 μm of partial size > and<300 μm of content are 68wt% in obtained ammonium poly-vanadate product, partial size>=
300 μm of content is 32wt%.
Embodiment 4
(1) feed pump is opened, the vanadium scavenging solution that vanadium concentration is 20.31g/L is added in crystallizer, is overflow until liquid level reaches
Head piece；
(2) heating pump and circulating pump are opened, by adjusting hot water flow and circulation pump frequency control crystallizer heating speed
Rate is 0.5 DEG C, and the temperature of the scavenging solution containing vanadium in crystallizer is risen to 92 DEG C；Control crystallizer add hot water backwater with it is molten in crystallizer
The temperature difference≤2 DEG C of liquid are slowly added to ammonium sulfate according to the ammonium vanadium molar ratio of 0.75:1 in temperature-rise period, while being slowly added to sulfuric acid
Adjusting pH value of solution is 2.3；
(3) it after the temperature of the scavenging solution containing vanadium reaches 92 DEG C in device to be crystallized, opens feed pump and continues to be added into crystallizer
Scavenging solution containing vanadium, feed rate 1.5m3/ h, control heating rate are 10 DEG C/h, and the temperature of the scavenging solution containing vanadium is made to be maintained at 95
DEG C, control crystallizer adds the temperature difference≤3 DEG C of solution in hot water backwater and crystallizer, rubs in temperature-rise period according to the ammonium vanadium of 0.8:1
You are than being added ammonium sulfate, while it is 2.0 that sulfuric acid regulation solution pH, which is added,；Discharging pump discharging is opened, it is high to control liquid level in crystallizer
In overflow port；
(4) after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
Through detecting: 150 μm of partial size > and<300 μm of content are 62wt% in obtained ammonium poly-vanadate product, partial size>=
300 μm of content is 38wt%.
Embodiment 5
(1) feed pump is opened, the vanadium scavenging solution that vanadium concentration is 39.41g/L is added in crystallizer, is overflow until liquid level reaches
Head piece；
(2) heating pump and circulating pump are opened, by adjusting hot water flow and circulation pump frequency control crystallizer heating speed
Rate is 1.5 DEG C, and the temperature of the scavenging solution containing vanadium in crystallizer is risen to 95 DEG C；Control crystallizer add hot water backwater with it is molten in crystallizer
The temperature difference≤3 DEG C of liquid are slowly added to ammonium sulfate according to the ammonium vanadium molar ratio of 0.9:1 in temperature-rise period, while being slowly added to sulfuric acid
Adjusting pH value of solution is 2.1；
(3) it after the temperature of the scavenging solution containing vanadium reaches 95 DEG C in device to be crystallized, opens feed pump and continues to be added into crystallizer
Scavenging solution containing vanadium, feed rate 9m3/ h, control heating rate are 7 DEG C/h, and the temperature of the scavenging solution containing vanadium is made to be maintained at 91 DEG C,
Control crystallizer adds the temperature difference≤3 DEG C of solution in hot water backwater and crystallizer, according to the ammonium vanadium mole of 0.85:1 in temperature-rise period
Than ammonium sulfate is added, while it is 2.1 that sulfuric acid regulation solution pH, which is added,；Discharging pump discharging is opened, liquid level in crystallizer is controlled and is higher than
Overflow port；
(4) after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
Through detecting: 150 μm of partial size > and<300 μm of content are 66wt% in obtained ammonium poly-vanadate product, partial size>=
300 μm of content is 34wt%.
Comparative example 1
Compared with Example 1, other than the heating rate of crystallizer in step (2) is adjusted to 0.05 DEG C/h, other steps
Rapid and condition is identical with embodiment 1.
The results show that crystallization time is too long, the nucleus of generation has been precipitated, partial size in subsequent obtained ammonium metavanadate product
Generally it is less than≤150 μm.
Comparative example 2
Compared with Example 1, other than the heating rate of crystallizer in step (2) is adjusted to 4 DEG C, other steps and item
Part is identical with embodiment 1.
Through detecting: the content of partial size≤150 μm is 31% in obtained ammonium poly-vanadate product, 150 μm of partial size > and < 300 μ
The content of m is 66wt%, and the content of partial size >=300 μm is 3wt%.
Comparative example 3
Compared with Example 1, other than the heating rate of crystallizer in step (3) is adjusted to 4 DEG C, other steps and item
Part is identical with embodiment 1.
Through detecting: the content of partial size≤150 μm is 23% in obtained ammonium poly-vanadate product, 150 μm of partial size > and < 300 μ
The content of m is 72wt%, and the content of partial size >=300 μm is 5wt%.
Comparative example 4
Compared with Example 1, other than the heating rate of crystallizer in step (3) is adjusted to 12 DEG C, other steps and
Condition is identical with embodiment 1.
Through detecting: obtained ammonium poly-vanadate product has spherical shape, ellipse, polygon etc., and form is irregular, affects product
Application performance.
Comparative example 5
Compared with Example 1, in addition in step (3) crystallizer add the temperature difference of solution in hot water backwater and crystallizer to be 6 DEG C
Outside, other steps and condition are identical with embodiment 1.
The results show that scabbing on tube wall makes line clogging, the process of crystallization is affected.
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 for preparing the spherical ammonium poly-vanadate of big granularity, which is characterized in that the described method comprises the following steps:
(1) vanadium scavenging solution will be contained to be added in crystallizer, control heating rate is 0.1-3 DEG C/h, by the temperature liter of the scavenging solution containing vanadium
Temperature adds ammonium salt to 85-95 DEG C, in temperature-rise period and adjusts pH；
(2) after the temperature of step (1) scavenging solution containing vanadium reaches 85-95 DEG C, continue to be added into crystallizer containing vanadium purification
Liquid, control heating rate are 6-10 DEG C/h, so that the temperature of the scavenging solution containing vanadium is maintained at 85-95 DEG C, add ammonium salt in temperature-rise period
And pH is adjusted, crystallization obtains 150 μm of granularity or more of spherical ammonium poly-vanadate.
2. the method as described in claim 1, which is characterized in that the concentration of vanadium is 20-40g/L in the scavenging solution containing vanadium.
3. method according to claim 1 or 2, which is characterized in that the crystallizer is OSLO crystallizer or DTB crystallizer.
4. the method according to claim 1, which is characterized in that the ammonium salt is ammonium sulfate.
5. method according to any of claims 1-4, which is characterized in that during the addition ammonium salt, control ammonium salt
Middle NH4 +Molar ratio with V in scavenging solution containing vanadium is (0.7-1.0): 1.
6. the method according to claim 1 to 5, which is characterized in that control crystallizer heats water during entire crystallization
The temperature difference≤5 DEG C of solution in return water and crystallizer.
7. as the method according to claim 1 to 6, which is characterized in that sulfuric acid is added in step (1) and step (2) and adjusts
The pH of solution is 1.9-2.3.
8. the method according to claim 1 to 7, which is characterized in that liquid level reaches in control crystallizer in step (1)
Overflow port；
Preferably, liquid level is higher than overflow port in control crystallizer in step (2).
9. the method according to claim 1, which is characterized in that the spherical more vanadic acid crystallized in crystallizer
Ammonium is filtered, and is washed, dry.
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) feed pump is opened, the scavenging solution containing vanadium that vanadium concentration is 20-40g/L is added in crystallizer, until liquid level reaches overflow
Mouthful；
(2) heating pump and circulating pump are opened, control heating rate is 0.1-3 DEG C/h, by the temperature of the scavenging solution containing vanadium in crystallizer
Degree rises to 85-95 DEG C；Control crystallizer adds the temperature difference≤5 DEG C of solution in hot water backwater and crystallizer, in temperature-rise period according to
(0.7-1.0): ammonium sulfate is added in 1 ammonium vanadium molar ratio, while it is 1.9-2.3 that sulfuric acid regulation solution pH, which is added,；
(3) it after the temperature of the scavenging solution containing vanadium reaches 85-95 DEG C in device to be crystallized, opens feed pump and continues to be added into crystallizer to contain
Vanadium scavenging solution, control heating rate are 6-10 DEG C/h, so that the temperature of the scavenging solution containing vanadium is maintained at 85-95 DEG C, control crystallizer adds
The temperature difference≤5 DEG C of solution in hot water backwater and crystallizer, according to (0.7-1.0) in temperature-rise period: sulphur is added in 1 ammonium vanadium molar ratio
Sour ammonium, while it is 1.9-2.3 that sulfuric acid regulation solution pH, which is added,；Discharging pump discharging is opened, liquid level in crystallizer is controlled and is higher than overflow
Mouthful；
(4) after discharging pump discharging, by filtering, washing obtains 150 μm of granularity or more of spherical ammonium poly-vanadate after dry.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250111A (en) * | 2020-10-29 | 2021-01-22 | 攀枝花市山青钒业有限公司 | Method for purifying ammonium polyvanadate and recycling waste water |
| CN114229893A (en) * | 2021-12-10 | 2022-03-25 | 河钢承德钒钛新材料有限公司 | Preparation method of ammonium polyvanadate |
| 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 |
| CN115072778A (en) * | 2022-07-27 | 2022-09-20 | 西安航天华威化工生物工程有限公司 | Ammonium polyvanadate continuous reaction crystallization process |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258642A (en) * | 1998-12-29 | 2000-07-05 | 攀枝花攀宏钒制品有限公司 | Continuous precipitation process of prodcing globular ammonium polyvanadate |
| CN101412540A (en) * | 2008-11-18 | 2009-04-22 | 攀钢集团研究院有限公司 | Method for producing vanadia by extraction technology |
| CN102351245A (en) * | 2011-07-12 | 2012-02-15 | 河北钢铁股份有限公司承德分公司 | Continuous production method for ammonium vanadate |
| CN104692461A (en) * | 2015-02-16 | 2015-06-10 | 河北钢铁股份有限公司承德分公司 | Method for preparing high-purity powdered vanadium oxide |
| CN105174308A (en) * | 2015-10-20 | 2015-12-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of ammonium polyvanadate |
| CN105967233A (en) * | 2016-07-15 | 2016-09-28 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium precipitation method capable of reducing vanadium precipitation wastewater |
| CN106011469A (en) * | 2016-06-29 | 2016-10-12 | 攀钢集团攀枝花钢钒有限公司 | Continuous vanadium precipitation method for high-concentration vanadium solution |
| CN106241871A (en) * | 2016-07-15 | 2016-12-21 | 攀钢集团攀枝花钢铁研究院有限公司 | High vanadium concentrations liquid acid ammonium salt precipitation method |
| CN107381637A (en) * | 2017-09-04 | 2017-11-24 | 河钢股份有限公司承德分公司 | A kind of method of preventing scaring in ammonium metavanadate crystallization process |
| CN107500352A (en) * | 2017-08-26 | 2017-12-22 | 袁安会 | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate |
-
2018
- 2018-10-19 CN CN201811222065.5A patent/CN109081374B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258642A (en) * | 1998-12-29 | 2000-07-05 | 攀枝花攀宏钒制品有限公司 | Continuous precipitation process of prodcing globular ammonium polyvanadate |
| CN101412540A (en) * | 2008-11-18 | 2009-04-22 | 攀钢集团研究院有限公司 | Method for producing vanadia by extraction technology |
| CN102351245A (en) * | 2011-07-12 | 2012-02-15 | 河北钢铁股份有限公司承德分公司 | Continuous production method for ammonium vanadate |
| CN104692461A (en) * | 2015-02-16 | 2015-06-10 | 河北钢铁股份有限公司承德分公司 | Method for preparing high-purity powdered vanadium oxide |
| CN105174308A (en) * | 2015-10-20 | 2015-12-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of ammonium polyvanadate |
| CN106011469A (en) * | 2016-06-29 | 2016-10-12 | 攀钢集团攀枝花钢钒有限公司 | Continuous vanadium precipitation method for high-concentration vanadium solution |
| CN105967233A (en) * | 2016-07-15 | 2016-09-28 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium precipitation method capable of reducing vanadium precipitation wastewater |
| CN106241871A (en) * | 2016-07-15 | 2016-12-21 | 攀钢集团攀枝花钢铁研究院有限公司 | High vanadium concentrations liquid acid ammonium salt precipitation method |
| CN107500352A (en) * | 2017-08-26 | 2017-12-22 | 袁安会 | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate |
| CN107381637A (en) * | 2017-09-04 | 2017-11-24 | 河钢股份有限公司承德分公司 | A kind of method of preventing scaring in ammonium metavanadate crystallization process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250111A (en) * | 2020-10-29 | 2021-01-22 | 攀枝花市山青钒业有限公司 | Method for purifying ammonium polyvanadate and recycling waste water |
| CN114229893A (en) * | 2021-12-10 | 2022-03-25 | 河钢承德钒钛新材料有限公司 | Preparation method of ammonium polyvanadate |
| CN114229893B (en) * | 2021-12-10 | 2023-08-04 | 河钢承德钒钛新材料有限公司 | Preparation method of ammonium polyvanadate |
| 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 |
| CN114275813B (en) * | 2021-12-30 | 2022-09-02 | 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 |
| CN115072778A (en) * | 2022-07-27 | 2022-09-20 | 西安航天华威化工生物工程有限公司 | Ammonium polyvanadate continuous reaction crystallization process |
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