CN107008498B - A method of preparing phosphato-molybdic heteropolyacid solution - Google Patents
A method of preparing phosphato-molybdic heteropolyacid solution Download PDFInfo
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- CN107008498B CN107008498B CN201710230938.6A CN201710230938A CN107008498B CN 107008498 B CN107008498 B CN 107008498B CN 201710230938 A CN201710230938 A CN 201710230938A CN 107008498 B CN107008498 B CN 107008498B
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses a kind of method for preparing phosphato-molybdic heteropolyacid solution, including the following steps: molybdate solution (or mixed solution of molybdenum and phosphorus) carries out first segment bipolar membrane electrodialysis, and solution ph is made to be reduced to 5.5~7.5；Electrodialysis solution is with progress thermal conversion (or solution after electrodialysis of mixed solution for molybdenum and phosphorus is directly heated conversion) after phosphorus；Second segment bipolar membrane electrodialysis is carried out after solution is cooling, control pH value is 1.0~3.0, obtains phosphato-molybdic heteropolyacid salting liquid；Phosphato-molybdic heteropolyacid solution is obtained after ion exchange transition removal of impurities.The present invention does not consume inorganic acid, does not introduce impurity anions, not only realizes the acidification of molybdate solution, also achieves the removing of most of salt cation, greatly reduces the burden that subsequent ion exchange removes salt cation.The phosphato-molybdic heteropolyacid solution that the present invention obtains can be used for preparing the phosphato-molybdic heteropolyacid product of high-quality, be a kind of phosphato-molybdic heteropolyacid solution preparation process of clean and effective.
Description
Technical field
The invention belongs to heteropoly acid preparation technical field, specifically a kind of method for preparing phosphato-molybdic heteropolyacid solution.
Background technique
Heteropoly compound is a kind of novel excellent acid due to certainty, acidity and oxidation-reduction quality with structure
Catalyst and oxidation reduction catalyst and a kind of multifunctional novel catalyst.It does that catalyst is fast with reproduction speed, urges
Change the features such as effect is good, and no pollution to the environment.Phosphato-molybdic heteropolyacid have relative molecular mass is high, hydrauture is high, in water with
And in certain organic solvents the features such as solubility height, strong oxidation performance, highly acid, in functional material preparation, catalysis, phase transfer etc.
Multiple fields are widely applied.
Although there are many preparation process of phosphato-molybdic heteropolyacid, essentially, it is all based on " acidification " and " separation " two
A basic step.Under the conditions of temperature is higher, it is acidified after molybdate solution and the soluble solution containing P are mixed,
Just phosphato-molybdic heteropolyacid salt is formed.Classify in the way of acidification, mainly there is classical acidization, flow back acidization and electrolytical acidification method
Deng.Compared with classical acidization and reflux acidization, electrolytical acidification method can be mentioned it is not necessary that additional acid is added into solution for acidification
For slow uniform advantage, the time for reaching balance is reduced, improves production efficiency, and waste will not be generated.But tradition
Phosphato-molybdic heteropolyacid solution is directly contacted with electrode in electrolytical acidification technique, since heteropoly acid corrosivity is stronger, is wanted to electrode material
Ask high, cost of investment is big, and energy consumption is high, is not used widely in the industry at present.It is miscellaneous more that phosphorus molybdenum is prepared using prior art
Acid is still unavoidable from the use of inorganic acid in acidization, therefore big, safety is low, heavy corrosion there are still polluting
The problems such as equipment.Inorganic acid tune acid introduces a large amount of impurity anions, reagent consumption is increased, to phosphato-molybdic heteropolyacid product
Quality brings adverse effect.
The method for separating heteropoly acid from aqueous solution then has aether extraction and ion-exchange etc..Currently, internal reagent
Preparation process used by manufacturer and laboratory synthesize still is traditional acidification-aether extraction.Into molybdate solution
Acetic acid is added, adjusting the pH value of solution is about 6, is 1/12 dropwise addition sodium radio-phosphate,P-32 solution by P/Mo atomic ratio and is heated to boiling, after stirring
Concentrated hydrochloric acid is added dropwise, is extracted after cooling with ether, so that ether is volatilized after being separated from water, phosphato-molybdic heteropolyacid can be obtained.But
Ether boiling point is very low, and only 34.5 DEG C, highly volatile is toxic inflammable, in operation necessary significant care, the production safety of technique
Property is poor, and ether can not recycle.Phosphato-molybdic heteropolyacid salting liquid directlys adopt ion-exchange, and to be transformed into phosphorus molybdenum miscellaneous
When polyacid, since cation such as Na+ ion concentration is higher in salting liquid, need to be diluted solution before exchanging, obtained phosphorus
The problems such as molybdenum heteropolyacid solution concentration is lower, and there are ion-exchange process burden is heavy, and production capacity is limited, and impurity-eliminating effect is poor.
Summary of the invention
Need to add a large amount of inorganic acids and bring series of problems to solve existing preparation method, the present invention provides one kind
The new method for preparing phosphato-molybdic heteropolyacid solution, is combined using bipolar membrane electrodialysis and ion-exchange and prepares phosphato-molybdic heteropolyacid
Solution, it is intended to realize the tune garden sorrel formula in preparation process without outer acid adding, and remove most of sun during bipolar membrane electrodialysis
Ion, reduces the burden of ion exchange transition removal of impurities, and then overcomes the shortcomings of traditional handicraft, and acquisition is used to prepare high-quality phosphorus molybdenum
The phosphato-molybdic heteropolyacid solution of heteropoly acid product.
A method of molybdenum heteropolyacid solution being prepared, molybdate solution successively carries out first segment bipolar membrane electrodialysis, heating
Conversion and second segment bipolar membrane electrodialysis；Wherein, solution containing phosphate and/or first segment Bipolar Membrane electricity are incorporated in molybdate solution
It is incorporated in solution after dialysis in the solution during solution containing phosphate and/or thermal conversion and is incorporated solution containing phosphate；
The pH for controlling the solution of first segment bipolar membrane electrodialysis is 5.5~7.5；
The pH for controlling the solution of second segment bipolar membrane electrodialysis is 0.1~3.0；
Solution after second segment bipolar membrane electrodialysis is obtained into phosphato-molybdic heteropolyacid solution after ion exchange transition removal of impurities.
In the present invention, the solution containing phosphate can be in the solution of any operating procedure before second segment bipolar membrane electrodialysis
It is disposably added in system；Or it is added during different operation several times.For example, the solution containing phosphate can be added arbitrarily
In the solution after molybdate solution, the solution of first segment bipolar membrane electrodialysis and thermal conversion process.
In the present invention, preferable following embodiments: (1) being incorporated solution containing phosphate into molybdate solution, carries out first segment
Bipolar membrane electrodialysis, and the pH for controlling the solution of primary pole membrane electrodialysis is 5.5~7.5；Second is carried out after heated conversion again
Section bipolar membrane electrodialysis, and the pH for controlling the solution of second segment bipolar membrane electrodialysis is 0.1~3.0；(2) by molybdate solution into
Row first segment bipolar membrane electrodialysis, and the pH for controlling first segment bipolar membrane electrodialysis solution is 5.5~7.5, is then incorporated and contains again
Phosphorus solution, then heated conversion, second segment bipolar membrane electrodialysis again, and control the pH of the solution of second segment bipolar membrane electrodialysis
It is 0.1~3.0；(3) molybdate solution is subjected to first segment bipolar membrane electrodialysis, and controls first segment bipolar membrane electrodialysis solution
PH be 5.5~7.5, be incorporated solution containing phosphate after thermal conversion process, then carry out second segment bipolar membrane electrodialysis, control second segment
The pH of the solution of bipolar membrane electrodialysis is 0.1~3.0；By at least one second segment bipolar membrane electrodialysis in (1), (2), (3)
Solution uses highly acid H+Type cation exchange resin carries out ion exchange, obtains phosphato-molybdic heteropolyacid solution.
The molybdate solution is the aqueous solution of water-soluble molybdenum hydrochlorate.
Preferably, molybdate solution is at least one aqueous solution of sodium molybdate, ammonium molybdate, potassium molybdate, lithium molybdate.
Further preferably, molybdate solution is sodium molybdate aqueous solution.
Preferably, Mo concentration is 20~300g/L in the molybdate solution, pH value is greater than or equal to 8.
The solution containing phosphate is the oxyacid of phosphorus and/or the aqueous solution of oxysalt.
The solution containing phosphate is, for example, at least one aqueous solution of phosphoric acid, water-soluble phosphate, water-soluble phosphate
It can be known sodium ascorbyl phosphate, sylvite, ammonium salt, lithium salts etc..
Preferably, solution containing phosphate is the aqueous solutions such as phosphoric acid, sodium dihydrogen phosphate.
The additional amount of the solution containing phosphate is that the molar ratio of P/Mo in the mixed solution for control molybdenum and phosphorus is 1/9~1/12.
Preferably, the molar ratio of P/Mo is 1/9,1/11 or 1/12 in the mixed solution of control molybdenum and phosphorus.
The bipolar membrane electrodialysis system that the first segment bipolar membrane electrodialysis and second segment bipolar membrane electrodialysis use
Membrane stack is a kind of two Room bipolar membrane electrodialysis membrane stacks, by multiple films to forming；Anode is pressed to the direction of cathode, by partition, cavity block,
Bipolar Membrane and anode membrane are successively alternately arranged, including pole room (for the general name of anode chamber and cathode chamber), salt room and alkaline chamber.
Preferably, the membrane stack of bipolar membrane electrodialysis system presses anode to the direction of cathode, be followed successively by partition, cavity block, every
Plate, several repetitive units, Bipolar Membrane and partition；Repetitive unit is successively replaced by Bipolar Membrane, partition, cation-exchange membrane and partition
Repeated arrangement forms；The wherein lateral anode of the cavity block of Bipolar Membrane, the lateral cathode of the anode membrane of Bipolar Membrane；Yin on the outside of anode and membrane stack
Anode chamber is constituted between film, cavity block and repetitive unit first, which are opened, constitutes alkaline chamber (1) between the cavity block side of Bipolar Membrane, in repetitive unit
It is salt room between the anode membrane side of Bipolar Membrane and cation-exchange membrane, is alkaline chamber between cation-exchange membrane and the cavity block side of Bipolar Membrane
(2), cathode chamber is constituted between the anode membrane side and cathode of the Bipolar Membrane on the outside of membrane stack.
In the present invention, the bipolar membrane electrodialysis system of first segment bipolar membrane electrodialysis and the use of second segment bipolar membrane electrodialysis
Salt room starting solution be molybdate solution, or with the molybdenum after phosphorus-phosphorus mixed solution；Alkaline chamber, cathode chamber and anode chamber are opened
Dynamic solution is electrolyte solution.
The molybdenum-phosphorus mixed solution is the mixed liquor or first segment Bipolar Membrane electric osmose of molybdate solution and solution containing phosphate
The mixed liquor of the mixed liquor of solution and solution containing phosphate after analysis or solution and solution containing phosphate after thermal conversion process.
The electrolyte solution is sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium nitrate, ammonium hydroxide, ammonium hydrogen carbonate, carbonic acid
Ammonium, ammonium nitrate, potassium hydroxide, saleratus, potassium carbonate, potassium nitrate, lithium hydroxide, lithium carbonate, lithium nitrate etc. it is single or mixed
Heshui solution.
Preferably, electrolyte molar concentration is 0.05~1.0mol/L in the electrolyte solution.
The electrolyte molar concentration is that the integral molar quantity of electrolyte in electrolyte solution is removed in electrolyte solution volume.
Preferably, alkaline chamber and pole room starting solution are the electrolyte solution with cation identical as salt room solution.
In bipolar membrane electrodialysis system, salt room solution circulates between salt room and salt room solution circulating slot；Alkaline chamber is molten
Liquid circulates between alkaline chamber and alkaline chamber solution circulating slot；Pole room solution (solution of anode chamber and cathode chamber) is in pole room and pole
It is circulated between the solution circulating slot of room.
The pH for controlling the solution of first segment bipolar membrane electrodialysis is 5.5~7.5；Control the molten of second segment bipolar membrane electrodialysis
The pH of liquid is 0.1~3.0.
Preferably, the pH of the solution of control first segment bipolar membrane electrodialysis is 6.0~7.0；Control second segment Bipolar Membrane
The pH of electrodialytic solution is 0.5~2.0.
Preferably, the current density of first segment bipolar membrane electrodialysis and second segment bipolar membrane electrodialysis be alone 500~
750A/m2。
The thermal conversion temperature is 70~100 DEG C, and the time is 4~48h.
In the present invention, by the solution of second segment bipolar membrane electrodialysis through highly acid H+Type cation exchange resin carries out ion
Exchange transition removal of impurities, is made the phosphato-molybdic heteropolyacid solution.
Existing conventional membrane material can be selected in cavity block, Bipolar Membrane, cation-exchange membrane of bipolar membrane electrodialysis system etc..
The highly acid H+Type cation exchange resin is preferably macroporous type highly acid H+Type cation exchange resin, into
One step is preferably D001 resin.
Thinking and technical principle of the invention is as follows:
In alkaline solution, Mo is with single molybdate MoO4 2-Form exists, in the presence of having P in solution, with the drop of pH
Low, Mo gradually occurs hybrid polymer with P and reacts, and generates phosphato-molybdic heteropolyacid root in acid condition.With molybdate or molybdenum and phosphorus
Mixed solution is raw material, and the process for preparing phosphato-molybdic heteropolyacid through bipolar membrane electrodialysis and ion exchange is as shown in Figure 1.Bipolar Membrane electricity
Dialysis is a kind of emerging membrane technology, bipolar membrane electrodialysis device film when being acidified molybdate solution using bipolar membrane electrodialysis technology
The structure and working principle of heap are as shown in Fig. 2.Under the action of electric field force, H in Bipolar Membrane2O is dissociated, and generates H respectively+
And OH-, the acidification of solution can be realized under the premise of being added without inorganic acid.In the present invention, first start circulating pump, to solution each
Room and each outdoor are set start the cycle over flowing between solution circulating slot after, in cathode and anode lead to direct current, in the effect of electric field force
Under, the cation permeables cation-exchange membrane such as sodium ion, ammonium ion, potassium ion or lithium ion in the solution of salt room moves into alkaline chamber,
Salt room solution ph constantly reduces, from entered in salt room by cation-exchange membrane alkalization room in sodium ion, ammonium ion, potassium from
The cation such as son or lithium ion is formed continuously sodium hydroxide, ammonium hydroxide, potassium hydroxide or lithium hydroxide in alkaline chamber.Hydrogen-oxygen in alkaline chamber
Change sodium, ammonium hydroxide, potassium hydroxide or lithium hydroxide concentration reach recyclable after certain value.In first segment bipolar membrane electrodialysis mistake
Cheng Zhong, control solution ph are 5.5-7.5, and molybdenum is gradually polymerized to para-molybdic acid root and more molybdates.Pyrolytic conversion process is conducive to
Be conducive to push the progress of molybdenum and phosphaization reaction.After second segment bipolar membrane electrodialysis, obtained phosphorus and molybdenum mixed solution pH value
For 0.1~3 (preferably 1~2), the cation such as Na of wherein most+、NH4 +、K+And Li+Deng in bipolar membrane electrodialysis mistake
It is migrated in journey to alkaline chamber.Therefore, bipolar membrane electrodialysis process can not only realize the acidification of solution, moreover it is possible to pass through the migration of cation
It realizes most of from phosphato-molybdic heteropolyacid salt to the transition of phosphato-molybdic heteropolyacid.
Select macroporous type highly acid H+Type cation exchange resin further makes the transition to second segment bipolar membrane electrodialysis solution
And removal of impurities, following reaction occurs on ion exchange column, and (M indicates Na, NH4, K or Li et al.):
Resin after absorption can be recycled after inorganic acid such as HCl desorption, and desorption reaction is as follows:
Phosphato-molybdic heteropolyacid solution is obtained after ion exchange transition removal of impurities, the phosphato-molybdic heteropolyacid that can be used for preparing high-quality produces
Product.PH value by the P/Mo in control solution than, phosphato-molybdic heteropolyacid solution and change operating parameter in product preparation process,
It can get the phosphato-molybdic heteropolyacid product of different structure.
A kind of method preparing phosphato-molybdic heteropolyacid solution proposed by the present invention has following excellent compared with traditional handicraft
Gesture:
(1) mixed solution containing molybdenum solution or molybdenum and phosphorus is acidified using bipolar membrane electrodialysis method, in acidization
Without using inorganic acid, impurity anions are not introduced, low to equipment corrosion, environmental pollution is small, theoretically has heteropoly acid yield
High, the advantages that quality is good；
(2) bipolar membrane electrodialysis is not only able to achieve the acidification to feed liquid, moreover it is possible to pass through cation permeable in acidization
The selective migration of film removes most of cation, to realize most of turn from phosphato-molybdic heteropolyacid salt to phosphato-molybdic heteropolyacid
Type, and the burden of subsequent ion exchange process is greatly reduced, improve the processing capacity and impurity-eliminating effect of ion-exchange process；
(3) compared with conventional electrodialysis acidification technique, new method is avoided that corrosion of the heteropoly acid to anode material, has energy
Consume low, high-efficient advantage.New method is avoided that the use of organic solvent, without using inorganic acid tune acid, avoids impurity yin
The introducing of ion reduces the burden of ion-exchange process, improves the production capacity of ion exchange, operational safety is high, ring
Border is friendly, and the solution purity of acquisition is high, and quality is good, is the new cleanproduction process of a green non-pollution.
Detailed description of the invention
Fig. 1 is a kind of flow chart for preparing phosphato-molybdic heteropolyacid solution methods proposed by the present invention；
Fig. 2 is bipolar membrane electrodialysis acidification molybdate solution or molybdenum and phosphorus mixed solution schematic diagram.
Specific embodiment
Illustrate embodiments of the present invention below by embodiment, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Following embodiment is used to be implemented by flow chart described in Fig. 1.
The bipolar membrane electrodialysis that the first segment bipolar membrane electrodialysis and second segment bipolar membrane electrodialysis of following embodiment use
The membrane stack of system is a kind of two Room bipolar membrane electrodialysis membrane stacks, by multiple films to forming；Anode is pressed to the direction of cathode, by every
Plate, cavity block, Bipolar Membrane and anode membrane are successively alternately arranged, including pole room, salt room (feed compartment) and alkaline chamber.
The membrane stack of bipolar membrane electrodialysis system presses anode to the direction of cathode, if being followed successively by partition, cavity block, partition, dry weight
Multiple unit, Bipolar Membrane and partition；Repetitive unit is successively alternately repeated arrangement by Bipolar Membrane, partition, cation-exchange membrane and partition
It forms；The wherein lateral anode of the cavity block of Bipolar Membrane, the lateral cathode of the anode membrane of Bipolar Membrane；Structure between cavity block on the outside of anode and membrane stack
At anode chamber, cavity block and repetitive unit first are opened and constitute alkaline chamber (1) between the cavity block side of Bipolar Membrane, Bipolar Membrane in repetitive unit
It is salt room between anode membrane side and cation-exchange membrane, is alkaline chamber (2), membrane stack between cation-exchange membrane and the cavity block side of Bipolar Membrane
Cathode chamber is constituted between the anode membrane side of the Bipolar Membrane in outside and cathode.
Following embodiment carries out first segment Bipolar Membrane electric osmose using the bipolar membrane electrodialysis system as shown in Fig. 2 schematic diagram
Analysis and second segment bipolar membrane electrodialysis.
In bipolar membrane electrodialysis system, salt room solution circulates between salt room and salt room solution circulating slot；Alkaline chamber is molten
Liquid circulates between alkaline chamber and alkaline chamber solution circulating slot；Pole room solution (solution of anode chamber and cathode chamber) is in pole room and pole
It is circulated between the solution circulating slot of room.
In the present invention, bipolar membrane electrodialysis equipment and cavity block, Bipolar Membrane, cation-exchange membrane type are not important to
It asks, existing conventional membrane material can be selected.Existing conventional equipment also can be selected in bipolar membrane electrodialysis device.
For example, the bipolar membrane electrodialysis device that following embodiment is selected is the ACILYZER-02 type of ASTOM company, Japan production
Electric dialyzator.20 films pair are shared in electrodialysis membrane stack.The effective area of single film is 0.02m2, compartment thickness 1mm.It is bipolar
Film, cation-exchange membrane and anion-exchange membrane be respectively ASTOM company, Japan produce NEOSEPTABP-1, CMB and AHA from
Proton exchange.
Embodiment 1:
First segment bipolar membrane electrodialysis: feed compartment (salt room) is the sodium molybdate solution of the 80.13g/L containing Mo, and initial pH value is
12.91；Alkaline chamber solution is 0.05mol/L NaOH solution；Pole room solution is 0.1mol/LNaOH solution；The first initial body of three Room solution
Product is 4L.First segment bipolar membrane electrodialysis current density is 500A/m2, electrolysis time 40min, obtaining pH value is 6.78 to contain
Molybdenum sodium salt solution, Mo concentration are 95.63g/L；
Conversion: solution boils 4h and is converted after first segment bipolar membrane electrodialysis；It is dilute that appropriate pure water can be added in liquid after conversion
It releases, is 1/12 addition sodium dihydrogen phosphate by P/Mo molal weight ratio, obtains the mixed solution that concentration containing Mo is 65.16g/L, pH value
It is 7.89；
Second segment bipolar membrane electrodialysis: taking the 3.46L mixed solution to carry out second segment bipolar membrane electrodialysis, (current density is
500A/m2), finally obtained two sections of electrodialysis liquor capacities are 2.74L, wherein concentration containing Mo is 82.25g/L, pH value is
0.15.Na during bipolar membrane electrodialysis+Removal efficiency reach 95.8%, Mo yield be 99.96%.
Ion exchange transition and removal of impurities: depth is carried out using D001 resin and removes Na+, adsorb time of contact 70min, liquid after friendship
For phosphato-molybdic heteropolyacid solution, Na in liquid after the friendship of ion exchange resin 8 times of resin volume feed liquids of absorption+Concentration is 0.085g/L,
The needs of preparation high-quality phosphato-molybdic heteropolyacid product can be met.Resin is parsed using 1mol/L HCl solution after absorption, is solved
Time of contact 70min is analysed, the resin after desorption can be recycled after pure water.
Embodiment 2:
First segment bipolar membrane electrodialysis: feed compartment is the ammonium molybdate solution of the 20g/L containing Mo, is by P/Mo molal weight ratio
1/9 is added phosphoric acid, initial pH value 9.50, and alkaline chamber solution is 1.0mol/LNH4HCO3Solution；Pole room solution is 0.5mol/L
NH4OH solution；Three Room solution initial volumes are 5L.First segment bipolar membrane electrodialysis current density is 750A/m2, electrolysis time
25min, obtains the mixed solution of molybdenum and phosphorus that pH value is 7.5, and Mo concentration is 25.5g/L；
Conversion: solution converts 48h at 90 DEG C after first segment bipolar membrane electrodialysis；Obtaining concentration containing Mo is 26.7g/L's
Mixed solution, pH value 7.25；
Second segment bipolar membrane electrodialysis: taking the 4.1L mixed solution to carry out second segment bipolar membrane electrodialysis, (current density is
750A/m2), finally obtained two sections of electrodialysis liquor capacities are 3.2L, wherein concentration containing Mo is 34.1g/L, pH value 2.01；
NH during bipolar membrane electrodialysis4 +Removal efficiency reach 85%, Mo yield be 99.7%.
Ion exchange transition and removal of impurities: depth is carried out using D001 resin and removes NH4 +, adsorb time of contact 80min, liquid after friendship
For phosphato-molybdic heteropolyacid solution, NH in liquid after the friendship of ion exchange resin 6 times of resin volume feed liquids of absorption4 +Concentration is 0.05g/L, can
Meet the needs of preparation high-quality phosphato-molybdic heteropolyacid product.Resin is parsed using 1mol/L HCl solution after absorption, is parsed
Time of contact 70min, the resin after desorption can be recycled after pure water.
Embodiment 3:
First segment bipolar membrane electrodialysis: feed compartment is the sodium molybdate solution of the 300.0g/L containing Mo, initial pH value 13.5；
Alkaline chamber solution is 1.0mol/L NaHCO3Solution；Pole room solution is 1.0mol/L NaOH solution；Three Room solution initial volumes are equal
For 4L.First segment bipolar membrane electrodialysis current density is 600A/m2, electrolysis time 45min, obtain pH value be 5.50 sodium containing molybdenum
Salting liquid, Mo concentration are 375g/L；
Conversion: solution is 1/11 addition sodium dihydrogen phosphate by P/Mo molal weight ratio after first segment bipolar membrane electrodialysis, is boiled
Boiling 12h is converted；Appropriate pure water dilution can be added in liquid after conversion, obtain the mixed solution that concentration containing Mo is 200.5g/L, pH
Value is 8.02；
Second segment bipolar membrane electrodialysis: taking the 4L mixed solution to carry out second segment bipolar membrane electrodialysis, (current density is
600A/m2), finally obtained two sections of electrodialysis liquor capacities are 3.4L, wherein concentration containing Mo is 235.8g/L, pH value is
1.50.Na during bipolar membrane electrodialysis+Removal efficiency reach 90.2%, Mo yield be 99.97%.
Ion exchange transition and removal of impurities: depth is carried out using D001 resin and removes Na+, adsorb time of contact 70min, liquid after friendship
For phosphato-molybdic heteropolyacid solution, Na in liquid after the friendship of ion exchange resin 6 times of resin volume feed liquids of absorption+Concentration is 0.06g/L, can
Meet the needs of preparation high-quality phosphato-molybdic heteropolyacid product.Resin is parsed using 1mol/L HCl solution after absorption, is parsed
Time of contact 60min, the resin after desorption can be recycled after pure water.
The present embodiment is only the preferred embodiments of the invention in summary, is not to be construed as to the scope of the present invention
Restriction, for the field technical work personnel according to the present invention the present embodiment done without departing from technical solution of the present invention
Adjustment and change, it should think to be within the scope of the present invention.
Claims (9)
1. a kind of method for preparing phosphato-molybdic heteropolyacid solution, which is characterized in that molybdate solution successively carries out first segment Bipolar Membrane
Electrodialysis, thermal conversion and second segment bipolar membrane electrodialysis；Wherein, solution containing phosphate and/or first are incorporated in molybdate solution
Solution containing phosphate is incorporated in solution after being incorporated solution containing phosphate and/or thermal conversion in solution after section bipolar membrane electrodialysis；It is described
Solution containing phosphate be phosphorus oxyacid and/or oxysalt aqueous solution；
The pH for controlling the solution of first segment bipolar membrane electrodialysis is 5.5 ~ 7.5；
The pH for controlling the solution of second segment bipolar membrane electrodialysis is 0.1 ~ 3.0；
Solution after second segment bipolar membrane electrodialysis is obtained into phosphato-molybdic heteropolyacid solution after ion exchange transition removal of impurities.
2. the method for preparing phosphato-molybdic heteropolyacid solution as described in claim 1, which is characterized in that the molybdate solution is
Sodium molybdate, ammonium molybdate, potassium molybdate, lithium molybdate at least one aqueous solution.
3. the method for preparing phosphato-molybdic heteropolyacid solution as claimed in claim 2, which is characterized in that in the molybdate solution
Mo concentration is 20 ~ 300g/L, and pH value is greater than or equal to 8.
4. the method for preparing phosphato-molybdic heteropolyacid solution as described in claim 1, which is characterized in that the addition of the solution containing phosphate
Amount is that the molar ratio of P/Mo in the mixed solution for control molybdenum and phosphorus is 1/9 ~ 1/12.
5. such as the described in any item methods for preparing phosphato-molybdic heteropolyacid solution of claim 1 ~ 4, which is characterized in that first segment is bipolar
The membrane stack for the bipolar membrane electrodialysis system that membrane electrodialysis and second segment bipolar membrane electrodialysis use presses anode to the direction of cathode, according to
Secondary is partition, cavity block, partition, several repetitive units, Bipolar Membrane and partition；Repetitive unit is exchanged by Bipolar Membrane, partition, cation
Film and partition, which are successively alternately repeated, to be arranged；The wherein lateral anode of the cavity block of Bipolar Membrane, the lateral cathode of the anode membrane of Bipolar Membrane；Sun
Constitute anode chamber between cavity block on the outside of pole and membrane stack, cavity block and repetitive unit first, which are opened, constitutes alkali between the cavity block side of Bipolar Membrane
Room is salt room, the yin of cation-exchange membrane and Bipolar Membrane between the anode membrane side and cation-exchange membrane of Bipolar Membrane in repetitive unit
It is alkaline chamber between film side, constitutes cathode chamber between the anode membrane side and cathode of the Bipolar Membrane on the outside of membrane stack.
6. the method for preparing phosphato-molybdic heteropolyacid solution as claimed in claim 5, which is characterized in that bipolar membrane electrodialysis system
It is molybdate solution that salt room, which starts solution, or with the molybdenum after phosphorus-phosphorus mixed solution；Alkaline chamber, cathode chamber and the starting of anode chamber
Solution is electrolyte solution.
7. the method for preparing phosphato-molybdic heteropolyacid solution as claimed in claim 6, which is characterized in that the electrolyte solution is
Sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium nitrate, ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrate, potassium hydroxide, bicarbonate
Potassium, potassium carbonate, potassium nitrate, lithium hydroxide, lithium bicarbonate, lithium carbonate, the single or mixed aqueous solution in lithium nitrate；Electrolyte rubs
Your concentration is 0.05 ~ 1.0mol/L.
8. the method for preparing phosphato-molybdic heteropolyacid solution as described in claim 1, which is characterized in that the thermal conversion temperature
It is 70 ~ 100 DEG C, the time is 4 ~ 48h.
9. the method for preparing phosphato-molybdic heteropolyacid solution as described in claim 1, which is characterized in that the ion exchange uses
Resin be highly acid H+Type cation exchange resin.
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