CN107098391A - A kind of method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis - Google Patents
A kind of method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis Download PDFInfo
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Abstract
The invention discloses a kind of method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis.The present invention is using ammonium tungstate solution as raw material, using a kind of bipolar membrane electrodialysis system with two Room bipolar membrane electrodialysis membrane stacks, in the presence of direct current field force, the removing of part ammonium ion and the reduction of pH value in ammonium tungstate solution are realized by bipolar membrane electrodialysis process, directly ammonium metatungstate solution is obtained in the acidifying room of bipolar membrane electrodialysis system.The present invention need not consume inorganic acid, not introduce impurity anions, short with flow, and direct yield is high, and power consumption is low, environment-friendly and be easily achieved industrialized advantage.
Description
Technical field
The present invention relates to a kind of preparation method of ammonium metatungstate solution, more particularly to one kind is adopted by raw material of ammonium tungstate solution
The method that ammonium metatungstate solution is prepared with bipolar membrane electrodialysis technology.
Background technology
Ammonium metatungstate (AMT), a kind of isopolyacid salt of tungsten, molecular formula is [(NH4)6(H2W12O40)]·nH2O.Ammonium metatungstate
It is a kind of important tungsten chemical product, is the important source material for preparing tungsten series hydrocatalyst in petrochemical industry.The method for producing AMT
It is more, it is different according to the method for producing AMT solution, it is broadly divided into solid phase transformation method and the big type of liquid phase conversion two.Secondary tungsten
Sour ammonium (APT, (NH4)10H2W12O42·nH2O thermal dissociation method) is a kind of typical solid phase transformation method, is industrial production at present
AMT main stream approach.This method is the temperature and time by controlling APT thermal dissociations, APT is removed the generation of part ammonium water-soluble
The big AMT of property, then dissolve through water, filter to obtain AMT solution, condensing crystallizing obtains AMT solids.The advantage of this method is product purity
Height, shortcoming be APT generation AMT conversion efficiency it is not high, normally only 80% or so, the direct yield of tungsten is not high, power consumption compared with
It is high that [Zhang Qixiu, Zhao Qinsheng are edited, and tungsten is metallurgical, metallurgical industry publishing house, 2005：158~159].
Liquid-phase conversion fado is with (NH4)2WO4(ammonium tungstate) solution is raw material, is neutralized, extracted using acid adding
[US3591331], ion exchange [US3857928, US3857929, US4557924], electrolysis with ion-exchange film [GB2073776,
CN85103826] etc. distinct methods reduce solution ph to OK range, obtain AMT solution, then obtained by condensing crystallizing
Solid AMT.The advantage of liquid phase conversion is directly to use ammonium tungstate solution for raw material, relative to APT thermal dissociation methods, eliminated
The process that ammonium tungstate solution produces APT, flow is short, and cost of material is low.But above-mentioned liquid phase conversion is inadequate, straight due to product purity
The reason such as yield is not high or technology is immature is in industrial production using less.
Making ammonium meta-tungstate process by continuous electrolysis disclosed in CN85103826 is one kind of liquid phase conversion, and this method is with tungsten
Acid ammonium solution is raw material, using cation-exchange membrane make barrier film by electrolytic cell be divided into one equipped with anode anode chamber and one
Cathode chamber equipped with negative electrode.Anode chamber is built with ammonium metatungstate solution, and cathode chamber is built with weak aqua ammonia or weak aqua ammonia and dust technology
Mixed liquor.The two poles of the earth lead to after direct current, are hybridly prepared into clear solution by ammonium tungstate solution and ammonium metatungstate solution and are continuously added to
Anode chamber, in the presence of electric field, the ammonium ion of anode chamber moves into cathode chamber through cation-exchange membrane, while anode reaction is produced
Raw H+Ion declines the pH value of anode chamber's solution, and continuous output ammonium metatungstate solution, a portion is used as circulating anode liquid
Mixed liquor is hybridly prepared into ammonium tungstate solution and is added to anode chamber's continuous electrolysis, and remaining is exported as product liquid.From anode
Room migrates into the NH of cathode chamber4 +The OH produced with cathode reaction-With reference to production NH4OH.The above method can realize continuous electrolyzing to make
Ammonium metatungstate solution technique is taken, short with flow, direct yield is high, the high and environment-friendly advantage of product purity, but there is electric energy
The problem of consumption is high and invests big, current this method not yet realizes industrialized production.
The content of the invention
For solve product purity that existing ammonium metatungstate preparation method is present not enough, direct yield it is not high and because inorganic acid disappears
The series of problems brought greatly and deficiency are consumed, bipolar membrane electrodialysis skill is used by raw material of ammonium tungstate solution the invention provides one kind
The method that art prepares ammonium metatungstate solution；The acid adjustment pattern without outer acid adding in preparation process is aimed at, the inclined of high-quality is obtained
Ammonium tungstate solution, and then overcome the shortcomings of that traditional handicraft invests the ammonium metatungstate that low, energy consumption is small, tungsten direct yield is high there is provided a kind of
Solution is interrupted or continuous production method.
In existing cationic membrane electrolytic preparation method, H is produced using electrode reaction+And OH-, 1 ionic membrane must match somebody with somebody
The precipitated oxygen and the reaction consumption electric energy of precipitation hydrogen occurred on standby 1 pair of electrode, anode and negative electrode is big, therefore equipment investment
Greatly, energy consumption is higher, and commercial Application is difficult.To overcome such technical barrier, the present inventor originally uses bipolar membrane electrodialysis
Technology prepares ammonium metatungstate solution；It is specific as follows：
A kind of method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis, ammonium tungstate solution is through bipolar membrane electrodialysis system
System processing, directly conversion obtain ammonium metatungstate solution；Described bipolar membrane electrodialysis system is two that Bipolar Membrane and anode membrane are constituted
Compartment cellular construction, two compartments include acidifying room and alkali room；The startup solution of described acidifying room is ammonium tungstate or ammonium metatungstate
Ammonium tungstate solution constantly can be supplemented into acidifying room during solution, bipolar membrane electrodialysis, in the presence of direct current field force, warp
Cross bipolar membrane electrodialysis process and realize the removing of part ammonium ion and the reduction of pH value in ammonium tungstate solution, directly in Bipolar Membrane electricity
The acidifying room of electrodialysis system obtains ammonium metatungstate solution.
In the present invention, by described bipolar membrane electrodialysis system, under electric field force effect, the water in Bipolar Membrane can occur
Dissociation, generates H+And OH-, migrated respectively to Bipolar Membrane both sides.H is produced using Bipolar Membrane dissociation water+And OH-, 1 membrane stack only needs
Want 1 pair of electrode, the percentage that the electric energy consumption of electrode reaction accounts for total hydrolytic dissociation power consumption is low, while utilizing Bipolar Membrane dissociation water
Energy consumption is low more than the energy consumption that water is dissociated using electrode reaction, therefore equipment investment and power consumption are relatively low.The present invention and then pass through film
The approach such as pile structure design, alkali room and the selection of pole room solution, the selection of feed way design and processes parameter, is solved by ammonium tungstate
Solution be acidified to be likely encountered during ammonium metatungstate solution hinder the problem of electric dialyzator is normally run because of Precipitation；
Realize NH in acidifying room ammonium tungstate solution4 +To the efficient migration of alkali room solution and removing, it ensure that bipolar membrane electrodialysis process
High efficiency, low energy consumption and high tungsten yield；Avoid the yin, yang of alkali room solution and pole room solution to acidifying room ammonium metatungstate solution
Ionic soil, obtains the ammonium metatungstate solution of high-quality；And realize the interruption or continuous production of ammonium metatungstate solution.
The film stacking structure of described bipolar membrane electrodialysis system is a kind of two compartments cellular construction, by the side of anode to negative electrode
To being followed successively by dividing plate, cavity block, dividing plate, some repeat units, Bipolar Membrane and dividing plate；Repeat unit by Bipolar Membrane, dividing plate, sun from
Proton exchange and dividing plate are alternately repeated arrangement and formed successively；Wherein, the lateral anode of the cavity block of Bipolar Membrane, the anode membrane of Bipolar Membrane is lateral
Negative electrode；Constitute anode chamber between cavity block on the outside of anode and membrane stack, the cavity block side of first Bipolar Membrane of cavity block and repeat unit
Between constitute between the anode membrane side of Bipolar Membrane in alkali room, repeat unit and cation-exchange membrane for acidifying room, cation-exchange membrane
It is alkali room between the cavity block side of Bipolar Membrane, cathode chamber is constituted between the anode membrane side of the Bipolar Membrane on the outside of membrane stack and negative electrode.
Described bipolar membrane electrodialysis system, including bipolar membrane electrodialysis device, acidifying room solution circulating slot, alkali room solution are followed
Annular groove, pole room solution circulating slot, acidifying room solution circulation conveying pump, alkali room solution circulation conveying pump, pole room solution circulation conveying
Pump；
Described bipolar membrane electrodialysis device by the anode chamber equipped with anode, the cathode chamber equipped with negative electrode, positioned at anode chamber and
Membrane stack between cathode chamber and the clamping device that above-mentioned each component is fixed together are constituted；
Described acidifying room solution circulating slot is connected by being acidified room solution circulation conveying pump with each acidifying room in membrane stack,
Described acidifying room is additionally provided with feed back to the circulation line for being acidified room solution circulating slot；
Described alkali room solution circulating slot is connected by alkali room solution circulation conveying pump with each alkali room in membrane stack, described
Alkali room is additionally provided with the circulation line of feed back to alkali room solution circulating slot；
Described pole room solution circulating slot is connected by the anode chamber in pole room solution circulation conveying pump and membrane stack and cathode chamber
Connect, described anode chamber and cathode chamber are also provided with feed back to the circulation line of pole room solution circulating slot.
In the present invention, described bipolar membrane electrodialysis system：
Described acidifying room solution circulating slot is provided with acidifying room solution fluid infusion, acidifying room solution loop head, acidifying
Room solution loop exit and acidifying room solution extraction bypass, wherein, acidifying room solution loop exit is circulated by being acidified room solution
Delivery pump be connected with being acidified room solution inlet in membrane stack, be acidified in described membrane stack room taphole by acid cycle pipeline and
It is acidified the connection of room solution loop head.
Described alkali room solution circulating slot is provided with alkali room solution fluid infusion, alkali room solution loop head, alkali room solution and followed
Ring is exported and alkali room solution produces bypass, wherein, alkali room solution loop exit passes through in alkali room solution circulation conveying pump and membrane stack
Alkali room solution inlet is connected, and alkali room taphole is connected by alkali room circulation line and alkali room solution loop head in described membrane stack
Connect.
Described pole room solution circulating slot is provided with pole room solution fluid infusion, pole room solution loop head, pole room solution and followed
Ring is exported and pole room solution produces bypass, wherein, pole room solution loop exit passes through in pole room solution circulation conveying pump and membrane stack
In pole room (for anode chamber and cathode chamber) solution inlet connection, described membrane stack pole room taphole by pole liquid circulation line with
Pole room solution loop head is connected.
During described bipolar membrane electrodialysis, alkali room solution is circulated between alkali room and alkali room solution circulating slot；
Pole room solution is circulated between pole room and pole room solution circulating slot；Room solution is acidified in acidifying room and acidifying room solution circulation
Circulated between groove.
The startup solution of described acidifying room is ammonium tungstate or ammonium metatungstate aqueous solution；Alkali room, cathode chamber and anode chamber
It is electrolyte solution to start solution.
The present invention can realize the interruption of ammonium metatungstate solution by different modes of operation using ammonium tungstate solution as raw material
Or continuous production.
During described bipolar membrane electrodialysis, it is ammonium tungstate solution, alkali room, cathode chamber and anode that acidifying room, which starts solution,
The startup solution of room is electrolyte solution.First start circulating pump, treat that solution is put in each room and each outdoor between solution circulating slot
Start the cycle over after flowing, direct current is led in cathode and anode, in the presence of electric field, water is dissociated in Bipolar Membrane, generation
H+Enter acidifying room, OH-Alkali room is entered, while being acidified the NH in the solution of room4 +Alkali is migrated into through cation-exchange membrane
Room.Due to H+Move into and NH4 +Reduction, acidifying room in ammonium tungstate solution pH value can continuous decrease, control acidifying room in it is molten
Liquid pH stable can obtain ammonium metatungstate solution in 2.0-4.0；So as to realize the interruption metaplasia production of ammonium metatungstate solution.
During described bipolar membrane electrodialysis, the startup solution for being acidified room is ammonium tungstate, ammonium metatungstate is at least one
The aqueous solution；Alkali room, cathode chamber and the startup of anode chamber solution are electrolyte solution.First start circulating pump, treat solution in each room
Started the cycle between putting solution circulating slot with each outdoor after flowing, direct current is led in cathode and anode, into acidifying room inlet pipeline
Or acidifying room solution circulating slot in be continuously added to ammonium tungstate solution, make ammonium tungstate solution with acidifying room circulating slot solution mix simultaneously one
Rise and enter acidifying room, be continuously added to alkali room fluid infusion into alkali room inlet pipeline or alkali room circulating slot, alkali room fluid infusion is followed with alkali room
Annular groove solution mixes and enters alkali room together.In the presence of electric field, water is dissociated in Bipolar Membrane, the H of generation+Enter
It is acidified room, OH-Alkali room is entered, while being acidified the NH in the solution of room4 +Alkali room is migrated into through cation-exchange membrane.Due to H+
Move into and NH4 +Reduction, the ammonium tungstate solution of the initial filling in acidifying room and the ammonium tungstate solution pH value meeting that is continuously added to
Continuous decrease, controls solution ph in acidifying room stable in 2.0-4.0 by controlling the addition of ammonium tungstate solution, can be in acid
Change interior and continuously generate ammonium metatungstate solution, the ammonium metatungstate solution of generation imports acidifying room circulating slot by being acidified room, from acidifying
It is interrupted in the circulating slot of room or continuously releases ammonium metatungstate solution；So as to realize the continuous production of ammonium metatungstate solution.
It is ammonium tungstate solution and WO to be acidified room to start solution3When concentration is higher than 50g/L, during acidifying, work as acidifying
Solution ph drops to 7-8 in the circulating slot of room, and acidifying room is likely to occur precipitation, with the progress of bipolar membrane electrodialysis, works as acidifying
Solution ph continues to drop to 4 or so in the circulating slot of room, and precipitation can dissolve again, obtains limpid ammonium metatungstate solution；Acidifying
It is ammonium metatungstate solution that room, which starts solution, during bipolar membrane electrodialysis into acidifying room inlet pipeline or acidifying room solution circulation
Ammonium tungstate solution is continuously added in groove, it is the beginning in 2.0-4.0, acidifying room solution circulating slot to control acidifying room circulating slot solution ph
Produced eventually without precipitation, continuously obtain limpid transparent ammonium metatungstate solution.
During bipolar membrane electrodialysis production ammonium metatungstate solution, acidifying enters alkali room in room by cation-exchange membrane
In ammonium ion ammonium salt or ammoniacal liquor are formed continuously in alkali room, ammonium concentration in alkali room solution can be caused to gradually rise, alkali room
The NH between acidifying room4 +Concentration difference increase, the NH from alkali room to acidifying room under concentration gradient effect4 +Reverse migration make
With enhancing, so as to cause current efficiency to decline, direct current consumption increases.It is continuously added into alkali room inlet pipeline or alkali room circulating slot
Ammonium salt solution is simultaneously interrupted from alkali room circulating slot or continuously releases ammonium salt solution it is possible to prevente effectively from this phenomenon.Alkali room fluid infusion can be
With the low concentration electrolyte solution or pure water of alkali room solution same composition.Such as, when selection ammonium bicarbonate soln is used as initial filling
During the ammonium salt aqueous solution being continuously added to the ammonium salt solution in alkali room circulating slot and into alkali room inlet tube, generated in alkali room
NH4OH can partly or entirely and NH4HCO3Generation neutralization reaction generates (NH4)2CO3.The alkali room of bipolar membrane electrodialysis process generation
Ammonium salt mixed solution can be by alkali room solution extraction bypass interruption or continuous releasing.
The main chemical reactions that above-mentioned bipolar membrane electrodialysis process occurs are as follows：
In Bipolar Membrane：H2O→H++OH- (1)
Acidifying is indoor：18H++12WO4 2-→H2W12O40 6-+8H2O (2)
In alkali room：NH4 ++OH-→NH4OH (3)
Preferably, during bipolar membrane electrodialysis, being acidified the WO of the solution of room3Concentration is in below 400g/L.
, can be by regulating and controlling solution W O in acidifying room circulating slot in actual production process3WO in concentration regulation and control acidifying room3Concentration.
It that is to say, solution W O in control acidifying room circulating slot during bipolar membrane electrodialysis3Concentration is in below 400g/L.It is acidified room solution
WO3Excessive concentration can cause solution density big, and acidifying room increases with alkali room solution pressure difference, is unfavorable for bipolar membrane electrodialysis process
Stable operation, as optimization, solution W O in control acidifying room circulating slot3Concentration is further optimized for control in below 350g/L
Solution W O in the circulating slot of relieving haperacidity room3Concentration is in 50-350g/L.
It that is to say, the ammonium tungstate solution WO supplemented into acidifying room3Concentration is in below 350g/L.Preferably, to acidifying
The ammonium tungstate solution WO supplemented in room3Concentration is in 50-350g/L.
Preferably, the pH value that the solution of room is acidified during controlling bipolar membrane electrodialysis is 2.0-4.0.
, can be by controlling the pH value of solution in acidifying room circulating slot during bipolar membrane electrodialysis to be in actual production process
2.0-4.0。
Described alkali room solution is the single or mixed aqueous solution of ammoniacal liquor, ammonium hydrogen carbonate, ammonium carbonate or ammonium nitrate, and alkali room is molten
Ammonium concentration in liquid is more than 0.1mol/L.
The selection of alkali room solution is ammonium salt solution, can avoid the cation transport pair caused by homo-ion infiltration or concentration difference diffusion
The pollution of ammonium metatungstate solution；Ammonium concentration is too high or too low, can cause the decline of current efficiency and the increasing of direct current consumption
Plus, ammonium concentration requirement is more than 0.1mol/L, preferably, selection is 0.1~3mol/L, in the range of the ammonium concentration
Under, that is, good electric conductivity is can guarantee that, preferable current efficiency is can guarantee that again.Further preferably, described alkali room solution is
Ammonium concentration in ammonium bicarbonate soln, alkali room solution is 0.5~2mol/L.
Described pole room solution is the single or mixed aqueous solution of ammoniacal liquor, ammonium hydrogen carbonate, ammonium carbonate or ammonium nitrate.
Anode material may be selected platinum, titanium according to different electrode chamber solution and apply ruthenium, nickel etc., and cathode material is according to different electricity
Nickel, stainless steel, platinum etc. may be selected in pole room solution.
Cavity block, Bipolar Membrane, cation-exchange membrane of bipolar membrane electrodialysis system etc. can select existing conventional membrane material.
In membrane stack in electrodialysis system of the present invention, Bipolar Membrane, cation-exchange membrane are a film pair；The film of described membrane stack
Quantity is not specially required, can be adjusted according to processing capacity.
Beneficial effect
In the present invention, using the described alkali room of two described Room film stacking structures, cooperation and pole room solution composition and concentration, choosing
Select suitable feed way and technological parameter, it is possible to achieve ammonium ion efficiently moving to alkali room solution in acidifying room ammonium tungstate solution
Move high efficiency, low energy consumption and the high tungsten yield with removing, guarantee bipolar membrane electrodialysis process；Avoid alkali room solution and pole room solution
Cation contamination to being acidified room ammonium metatungstate solution, obtains the ammonium metatungstate solution of high-quality；And realize ammonium metatungstate solution
Interruption or continuous production.
A kind of method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis technology proposed by the present invention, with it is industrial often
Ammonium paratungstate thermal dissociation is produced ammonium metatungstate technology and compared, and directly uses ammonium tungstate solution for raw material, eliminates ammonium tungstate
The process that solution produces APT, flow is short, and cost of material is low, and direct yield is high；Compared with inorganic acid acid adjustment method, without using inorganic
Sour acid adjustment, does not introduce impurity anions, and superior product quality, reagent consumption is small；Compared with ion-exchange, water consumption and wastewater flow rate
Discharge is small, and production capacity is big, and production efficiency is high；Compared with cationic membrane electrolysis, aquatic products is dissociated using Bipolar Membrane in the present invention
Raw H+ and OH-, 1 cation-exchange membrane and 1 Bipolar Membrane component film pair, several films are only needed to composition membrane stack, a membrane stack
Want 1 pair of electrode, the percentage that the electric energy consumption of electrode reaction accounts for total hydrolytic dissociation power consumption is low, while utilizing Bipolar Membrane dissociation water
Energy consumption is low more than the energy consumption that water is dissociated using electrode reaction, therefore equipment investment and power consumption are relatively low.
It is molten that one kind proposed by the present invention prepares ammonium metatungstate by raw material of ammonium tungstate solution using bipolar membrane electrodialysis technology
The method of liquid compared with traditional ammonium metatungstate solution preparation method, with flow is short, high income, environmentally safe, raw material into
Sheet is low, be easy to the advantages such as industrialization.
Brief description of the drawings：
The schematic diagram that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis that Fig. 1 uses for the present invention.
Fig. 2 is the connection of bipolar membrane electrodialysis system equipment and solution flow line schematic diagram.
Embodiment
The implementation of the present invention is illustrated with embodiment with reference to the accompanying drawings.Below implement be intended to illustrate invention without
It is limitation of the invention further.
The bipolar membrane electrodialysis system and the schematic diagram of membrane stack arrangement mode that the present invention is selected are shown in Fig. 1,2.
Described bipolar membrane electrodialysis system, including bipolar membrane electrodialysis device, acidifying room solution circulating slot, alkali room solution are followed
Annular groove, pole room solution circulating slot, acidifying room solution circulation conveying pump, alkali room solution circulation conveying pump, pole room solution circulation conveying
Pump；
Described bipolar membrane electrodialysis device by the anode chamber equipped with anode, the cathode chamber equipped with negative electrode, positioned at anode chamber and
Membrane stack between cathode chamber and the clamping device that above-mentioned each component is fixed together are constituted；
Described bipolar membrane electrodialysis device film stacking structure is a kind of two compartments cellular construction, by the direction of anode to negative electrode,
It is followed successively by dividing plate, cavity block, dividing plate, some repeat units, Bipolar Membrane and dividing plate；Repeat unit is handed over by Bipolar Membrane, dividing plate, cation
Change film and dividing plate and be alternately repeated arrangement successively and form；Wherein, the lateral anode of the cavity block of Bipolar Membrane, the anode membrane of Bipolar Membrane is laterally cloudy
Pole；Constitute anode chamber between cavity block on the outside of anode and membrane stack, the cavity block side of first Bipolar Membrane of cavity block and repeat unit it
Between constitute alkali room (1), between the anode membrane side of Bipolar Membrane and cation-exchange membrane be acidifying room, cation-exchange membrane in repeat unit
It is alkali room (2) between the cavity block side of Bipolar Membrane, cathode chamber is constituted between the anode membrane side of the Bipolar Membrane on the outside of membrane stack and negative electrode.
Described acidifying room solution circulating slot is connected by being acidified room solution circulation conveying pump with each acidifying room in membrane stack,
Described acidifying room is additionally provided with feed back to the circulation line for being acidified room solution circulating slot；
Described alkali room solution circulating slot is connected by alkali room solution circulation conveying pump with each alkali room in membrane stack, described
Alkali room is additionally provided with the circulation line of feed back to alkali room solution circulating slot；
Described pole room solution circulating slot is connected by the anode chamber in pole room solution circulation conveying pump and membrane stack and cathode chamber
Connect, described anode chamber and cathode chamber are also provided with feed back to the circulation line of pole room solution circulating slot.
In the present invention, described bipolar membrane electrodialysis system：
Described acidifying room solution circulating slot is provided with acidifying room solution fluid infusion, acidifying room solution loop head, acidifying
Room solution loop exit and acidifying room solution extraction bypass, wherein, acidifying room solution loop exit is circulated by being acidified room solution
Delivery pump be connected with being acidified room solution inlet in membrane stack, be acidified in described membrane stack room taphole by acid cycle pipeline and
It is acidified the connection of room solution loop head.
Described alkali room solution circulating slot is provided with alkali room solution fluid infusion, alkali room solution loop head, alkali room solution and followed
Ring is exported and alkali room solution produces bypass, wherein, alkali room solution loop exit passes through in alkali room solution circulation conveying pump and membrane stack
Alkali room solution inlet is connected, and alkali room taphole is connected by alkali room circulation line and alkali room solution loop head in described membrane stack
Connect.
Described pole room solution circulating slot is provided with pole room solution fluid infusion, pole room solution loop head, pole room solution and followed
Ring is exported and pole room solution produces bypass, wherein, pole room solution loop exit passes through in pole room solution circulation conveying pump and membrane stack
In pole room (for anode chamber and cathode chamber) solution inlet connection, described membrane stack pole room taphole by pole liquid circulation line with
Pole room solution loop head is connected.
During described bipolar membrane electrodialysis, alkali room solution is circulated between alkali room and alkali room solution circulating slot；
Pole room solution is circulated between pole room and pole room solution circulating slot；Room solution is acidified in acidifying room and acidifying room solution circulation
Circulated between groove.
In the present invention, bipolar membrane electrodialysis equipment and cavity block, Bipolar Membrane, cation-exchange membrane species are not important to
Ask, can select existing conventional membrane material.Bipolar membrane electrodialysis device also can select existing conventional equipment.
The bipolar membrane electrodialysis device that following examples are selected is the ACILYZER-02 type electric osmoses that ASTOM companies of Japan produce
Parser.20 films pair are had in electrodialysis membrane stack.The effective area of single film is 0.02m2, compartment thickness is 1mm.Bipolar Membrane,
Cation-exchange membrane and anion-exchange membrane are respectively NEOSEPTABP-1, CMB and AHA ion of Japanese ASTOM companies production
Exchange membrane.
Embodiment 1
Using basic structure electrodialysis system as shown in Figure 2, the membrane stack of wherein electric dialyzator includes 20 two Room lists
Member, the effective area of single film is 0.02m2, Bipolar Membrane is NEOSEPTA BP-1, and cation-exchange membrane is NEOSEPTA CMB,
Anode and the equal titanium nickel plating plate electrode of negative electrode, film stacking structure are as shown in Figure 1.Ammonium tungstate solution contains WO3250g/L.Initially filling
It is ammonium metatungstate solution to the solution in acidifying room circulating slot, wherein WO3300.0g/L, pH value 3.0 or so, volume 6.0L.Most
The solution being just filled into alkali room circulating slot is NH4HCO3Solution, concentration is 1.0mol/L, and volume is 5L.It is added continuously to alkali room
Solution be 1.0mol/L NH4HCO3Solution.The solution being initially filled into pole room circulating slot is NH4OH solution, and concentration is
1.0mol/L, volume is 4L.After power-on servicing starts, ammonium tungstate solution is added continuously to be acidified room inlet pipeline, NH4HCO3It is molten
Liquid is added continuously to alkali room inlet pipeline, using constant current operation, and operation electric current is 18A, by adjusting ammonium tungstate solution
The pH value of charging rate control acidifying room circulating slot solution is 2.0 or so, when the liquid level of acidifying room reaches that acidifying room circulating slot overflows
At head piece, ammonium metatungstate solution is flowed continually out at acidifying room circulating slot overfall.Continued electrolysis 3 hours, tank voltage stabilization exists
42V or so, the ammonium metatungstate solution of acquisition is as clear as crystal.Operate the ammonium metatungstate solution flowed continually out and acidifying room after terminating
Ammonium metatungstate solution mixing in circulating slot, obtains ammonium metatungstate solution 11.8L, wherein WO altogether3329.0g/L, pH value 2.0.
When the liquid level of alkali room is reached at alkali room circulating slot overfall in operating process, solution is continuous at alkali room circulating slot overfall in groove
Outflow.Operation mixes the solution in the solution and alkali room circulating slot that are flowed continually out from alkali room circulating slot after terminating, and is contained altogether
Ammonium salt solution 11.5L, wherein WO30.11g/L, it follows that process WO3Direct yield close to 100%.
Embodiment 2
Using basic structure electrodialysis system as shown in Figure 2, the membrane stack of wherein electric dialyzator is same as Example 1.Tungsten
Acid ammonium solution contains WO3151.2g/L,.The solution being initially filled into acidifying room circulating slot is the metatungstic acid prepared with embodiment 1
What ammonium salt solution diluted and obtained through deionized water, wherein WO3150.0g/L, pH value 2.0 or so, volume 6.0L.
The solution being initially filled into alkali room circulating slot is (NH4)2CO3Solution, concentration is 0.1mol/L, and volume is 5L.It is accurate
The standby solution for being added continuously to alkali room is also (NH that concentration is 0.1mol/L4)2CO3Solution.Initially it is filled into pole room circulating slot
Solution be NH4OH solution, concentration is 1.0mol/L, and volume is 5L.After power-on servicing starts, ammonium tungstate solution is added continuously to
In acidifying solution circulating slot, (NH4)2CO3Solution is added continuously in alkali lye circulating slot, and using constant current operation, operation electric current is
16A, controls to be acidified the pH value of room circulating slot solution 3.0 or so, when acidifying room by adjusting the charging rate of ammonium tungstate solution
Liquid level reach acidifying room circulating slot overfall at, ammonium metatungstate solution from acidifying room circulating slot overfall at flow continually out.Hold
Continuous power-on servicing 4 hours, tank voltage is stable in 40V or so, and the ammonium metatungstate solution of acquisition is as clear as crystal.Operation will even after terminating
The ammonium metatungstate solution mixing in ammonium metatungstate solution and acidifying room circulating slot that afterflow goes out, obtains ammonium metatungstate solution altogether
16.1L, wherein WO3174.2g/L, pH value 4.0.When the liquid level of alkali room is reached at alkali room circulating slot overfall in electrolytic process,
Solution is flowed continually out at alkali room circulating slot overfall in groove.Operation terminates the solution and alkali that will be flowed continually out from alkali room circulating slot
Solution mixing in the circulating slot of room, obtains 13.6L containing ammonium salt solution, wherein WO altogether30.08g/L, it follows that process WO3's
Direct yield is close to 100%.
Embodiment 3
The equipment of use is same as Example 1, and difference is that cathode and anode is titanium platinum plating plate electrode.Ammonium tungstate is molten
Liquid contains WO3100.0g/L.The solution being initially filled into acidifying room circulating slot is the ammonium metatungstate solution prepared with embodiment 2
Dilute and obtain through deionized water, wherein WO350.0g/L, pH value 4.0 or so, volume 6.0L.Initially it is filled into alkali room circulating slot
Interior solution is NH4NO3Solution, concentration is 0.5mol/L, and volume is 5L.The solution for preparing to be added continuously to alkali room is that concentration is
0.5mol/L NH4NO3Solution.The solution being initially filled into pole room circulating slot is NH4NO3Solution, concentration is 1.0mol/L,
Volume is 5L.After electrodialysis operation starts, ammonium tungstate solution is added continuously to be acidified room inlet pipeline, NH4NO3Solution continuously adds
Enter to alkali room inlet pipeline, using constant current operation, operation electric current is 10A, by the charging rate for adjusting ammonium tungstate solution
The pH value of control acidifying room circulating slot solution is acidified room circulating slot and alkali room circulating slot liquid level not in 2.0 or so, electrolytic process
It is disconnected to increase, part solution was taken out from acidifying room circulating slot and alkali room circulating slot respectively every 1 hour, so as to ensure that acidifying room is followed
The liquid level of annular groove and alkali room circulating slot will not be too high.Continue power-on servicing 4 hours, tank voltage is stable in 32V or so, acquisition it is inclined
Ammonium tungstate solution is as clear as crystal.The metatungstic acid that operation will be interrupted in the ammonium metatungstate solution taken out and acidifying room circulating slot after terminating
Ammonium salt solution is mixed, and ammonium metatungstate solution 19.3L, wherein WO are obtained altogether396.3g/L, pH value 2.0.It will be interrupted from alkali room circulating slot
The solution of taking-up and operation terminate the solution mixing in rear alkali room circulating slot, and 13.5L containing ammonium salt solution, wherein WO are obtained altogether3
0.04g/L, it follows that process WO3Direct yield close to 100%.
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 embodiment of the present invention 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 that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis, it is characterised in that：Ammonium tungstate solution is through bipolar
The processing of EDBM system, directly conversion obtain ammonium metatungstate solution；The membrane stack of described bipolar membrane electrodialysis system is bipolar
Two compartment cellular constructions of film and anode membrane composition, two compartments include acidifying room and alkali room；The startup solution of described acidifying room is
Ammonium tungstate solution constantly is supplemented into acidifying room during ammonium tungstate or ammonium metatungstate solution, bipolar membrane electrodialysis, in direct current
In the presence of field force, the drop of the removing of part ammonium ion and pH value in ammonium tungstate solution is realized by bipolar membrane electrodialysis process
It is low, directly obtain ammonium metatungstate solution in the acidifying room of bipolar membrane electrodialysis system.
2. the method as claimed in claim 1 that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis, it is characterised in that：It is bipolar
The membrane stack of EDBM device system is a kind of two Room bipolar membrane electrodialysis membrane stack, by multiple films to constituting；Anode is pressed to negative electrode
Direction, is followed successively by dividing plate, cavity block, dividing plate, some repeat units, Bipolar Membrane and dividing plate；Repeat unit is by Bipolar Membrane, dividing plate, sun
Amberplex and dividing plate are alternately repeated arrangement and formed successively；Wherein, the lateral anode of the cavity block of Bipolar Membrane, the anode membrane side of Bipolar Membrane
To negative electrode；Constitute anode chamber between cavity block on the outside of anode and membrane stack, the cavity block of first Bipolar Membrane of cavity block and repeat unit
It is acidifying room between the anode membrane side of Bipolar Membrane and cation-exchange membrane to be constituted between side in alkali room (1), repeat unit, and cation is handed over
It is alkali room (2) to change between film and the cavity block side of Bipolar Membrane, and negative electrode is constituted between the anode membrane side of the Bipolar Membrane on the outside of membrane stack and negative electrode
Room.
3. the method as claimed in claim 1 or 2 that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis, it is characterised in that：
Described bipolar membrane electrodialysis system, including bipolar membrane electrodialysis device, acidifying room solution circulating slot, alkali room solution circulating slot, pole
Room solution circulating slot, acidifying room solution circulation conveying pump, alkali room solution circulation conveying pump, pole room solution circulation conveying pump；
Described bipolar membrane electrodialysis device is by the anode chamber equipped with anode, the cathode chamber equipped with negative electrode, positioned at anode chamber and negative electrode
Membrane stack between room and the clamping device that above-mentioned each component is fixed together are constituted；
Described acidifying room solution circulating slot is connected by being acidified room solution circulation conveying pump with each acidifying room in membrane stack, described
Acidifying room be additionally provided with by feed back to be acidified room solution circulating slot circulation line；
Described alkali room solution circulating slot is connected by alkali room solution circulation conveying pump with each alkali room in membrane stack, described alkali room
It is additionally provided with the circulation line of feed back to alkali room solution circulating slot；
Described pole room solution circulating slot is connected by pole room solution circulation conveying pump with the anode chamber in membrane stack and cathode chamber, institute
The anode chamber stated and cathode chamber are also provided with feed back to the circulation line of pole room solution circulating slot.
4. the method as claimed in claim 3 that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis, it is characterised in that：It is described
Bipolar membrane electrodialysis during, alkali room solution is circulated between alkali room and alkali room solution circulating slot；Pole room solution is in pole
Circulated between room and pole room solution circulating slot；It is acidified room solution recycle stream between acidifying room and acidifying room solution circulating slot
It is dynamic.
5. the method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis as described in any one of Claims 1 to 4, its feature
It is：The WO of room solution is acidified during bipolar membrane electrodialysis3Concentration is in below 400g/L.
6. the method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis as described in claim 1 or 5, it is characterised in that：
The ammonium tungstate solution WO supplemented into acidifying room3Concentration is in below 350g/L.
7. the method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis as described in claim any one of 1-6, its feature
It is：Control to be acidified the pH value of room solution during bipolar membrane electrodialysis for 2.0-4.0.
8. the method that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis as described in claim any one of 1-7, its feature
It is：The solution of described alkali room is the single or mixed aqueous solution of ammoniacal liquor, ammonium hydrogen carbonate, ammonium carbonate or ammonium nitrate, alkali room
Ammonium concentration in solution is more than 0.1mol/L.
9. the method as claimed in claim 3 that ammonium metatungstate solution is prepared based on bipolar membrane electrodialysis, it is characterised in that：It is bipolar
Solution W O in the solution circulating slot of room is acidified during EDBM3Concentration is in below 400g/L；Control bipolar membrane electrodialysis process
The pH value of solution is 2.0-4.0 in middle acidifying room solution circulating slot.
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Cited By (3)
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| CN110563039A (en) * | 2019-09-11 | 2019-12-13 | 赣州市海龙钨钼有限公司 | Method for preparing ammonium paratungstate |
| CN114162870A (en) * | 2021-12-01 | 2022-03-11 | 中国科学院过程工程研究所 | Ammonium paratungstate, preparation method thereof and bipolar membrane electrolysis device |
| CN114368806A (en) * | 2022-02-16 | 2022-04-19 | 中领水净科技(深圳)有限公司 | Alkaline electrolysis ionized water preparation system |
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| CN110563039A (en) * | 2019-09-11 | 2019-12-13 | 赣州市海龙钨钼有限公司 | Method for preparing ammonium paratungstate |
| CN114162870A (en) * | 2021-12-01 | 2022-03-11 | 中国科学院过程工程研究所 | Ammonium paratungstate, preparation method thereof and bipolar membrane electrolysis device |
| CN114162870B (en) * | 2021-12-01 | 2022-09-30 | 中国科学院过程工程研究所 | Ammonium paratungstate, preparation method thereof and bipolar membrane electrolysis device |
| CN114368806A (en) * | 2022-02-16 | 2022-04-19 | 中领水净科技(深圳)有限公司 | Alkaline electrolysis ionized water preparation system |
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