CN106975360A - A kind of method that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis - Google Patents
A kind of method that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis Download PDFInfo
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- CN106975360A CN106975360A CN201710259072.1A CN201710259072A CN106975360A CN 106975360 A CN106975360 A CN 106975360A CN 201710259072 A CN201710259072 A CN 201710259072A CN 106975360 A CN106975360 A CN 106975360A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
Abstract
The invention discloses a kind of method that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis.The present invention is using sodium molybdate 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 sodium ion and the reduction of pH value in sodium molybdate solution are realized by bipolar membrane electrodialysis process, directly many sodium molybdate solutions are 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 many sodium molybdate solutions, more particularly to one kind is adopted by raw material of sodium molybdate solution
The method that many sodium molybdate solutions are prepared with bipolar membrane electrodialysis technology.
Background technology
Sodium molybdate solution system is common solution system in molybdenum metallurgical process.The acid solution of thick sodium molybdate solution and molybdenum
It is the important source material liquid of making pure sodium molybdate solution and sodium molybdate series of products.Pure molybdic acid is being prepared by raw material of thick sodium molybdate
During sodium solution, it is sometimes desirable to adjust the pH value of sodium molybdate solution to acidity, during acidifying, molybdate will be sent out
Raw polymerization, generates many sodium molybdates.Relatively common many molybdic acid sodium salt such as sodium paramolybdates, are neutralized to pH value big by single sodium molybdate solution
When about 5, sodium paramolybdate is crystallized out, its solubility is 157g/100g (H at 30 DEG C2O).Nothing is added into sodium molybdate solution
Machine acid can realize the acidifying of sodium molybdate solution, but the introducing of a large amount of inorganic acids can increase the consumption of acid reagent for technique,
Substantial amounts of impurity anions will be brought into again for many sodium molybdate products, the quality of many sodium molybdate products is influenceed.
The content of the invention
For solve in existing many sodium molybdate preparation methods because inorganic acid consume the series of problems brought greatly or equipment investment it is big,
The deficiencies such as energy consumption height, many molybdic acids are prepared the invention provides one kind by raw material of sodium molybdate solution using bipolar membrane electrodialysis technology
The method of sodium solution；The acid adjustment pattern without outer acid adding in preparation process is aimed at, many sodium molybdate solutions of high-quality is obtained, enters
And overcome the shortcomings of traditional handicraft and invest many sodium molybdate solution interruptionizations or connect that low, energy consumption is small, molybdenum direct yield is high there is provided a kind of
Continuousization production method.
To overcome such technical barrier, the present inventor originally prepares many sodium molybdates using bipolar membrane electrodialysis technology
Solution.
A kind of method that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis, sodium molybdate solution is through bipolar membrane electrodialysis system
System processing, directly conversion obtain many sodium molybdate solutions；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 sodium molybdate or many sodium molybdates
Sodium molybdate 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 sodium ion and the reduction of pH value in sodium molybdate solution, directly in Bipolar Membrane electricity
The acidifying room of electrodialysis system obtains many sodium molybdate solutions.
Under electric field force effect, the water in Bipolar Membrane can be dissociated, and generate H+And OH-, moved respectively to Bipolar Membrane both sides
Move.H is produced using Bipolar Membrane dissociation water+And OH-, 1 membrane stack only needs to 1 pair of electrode, and the electric energy consumption of electrode reaction accounts for total hydrolytic dissociation
The percentage of power consumption is low, while the energy consumption for dissociating water using Bipolar Membrane 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 is designed by film stacking structure, alkali room and the selection of pole room solution, feed way design and processes parameter are selected
Etc. approach, Na in acidifying room sodium molybdate solution is realized+To the efficient migration of alkali room solution and removing, it ensure that Bipolar Membrane electric osmose
High efficiency, low energy consumption and the high molybdenum yield of analysis process；Alkali room solution and pole room solution are avoided to the acidifying many sodium molybdate solutions in room
Anions and canons pollution, obtain many sodium molybdate solutions of high-quality；And realize the interruption or serialization of many sodium molybdate solutions
Production.
The membrane stack film stacking structure of described bipolar membrane electrodialysis system is a kind of two compartments cellular construction, by anode to negative electrode
Direction, be followed successively by dividing plate, cavity block, dividing plate, some repeat units, Bipolar Membrane and dividing plate；Repeat unit by Bipolar Membrane, dividing plate,
Cation-exchange membrane 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
Lateral negative electrode；Constitute anode chamber between cavity block on the outside of anode and membrane stack, the moon of first Bipolar Membrane of cavity block and repeat unit
Constituted between film side in alkali room (1), repeat unit is acidifying room, cation between the anode membrane side of Bipolar Membrane and cation-exchange membrane
It is alkali room (2) between exchange membrane and the cavity block side of Bipolar Membrane, is constituted between the anode membrane side of the Bipolar Membrane on the outside of membrane stack and negative electrode cloudy
Pole room.
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 sodium molybdate or many sodium molybdate aqueous solutions；Alkali room, cathode chamber and anode chamber
It is electrolyte solution to start solution.
The present invention can realize the interruption of many sodium molybdate solutions by different modes of operation using sodium molybdate solution as raw material
Or continuous production.
During described bipolar membrane electrodialysis, it is sodium molybdate 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 Na in the solution of room+Alkali is migrated into through cation-exchange membrane
Room.Due to H+Move into and Na+Reduction, acidifying room in sodium molybdate solution pH value can continuous decrease, control acidifying room in solution
PH stable can obtain many sodium molybdate solutions in 2.0-4.5；So as to realize the interruption metaplasia production of many sodium molybdate solutions.
During described bipolar membrane electrodialysis, the startup solution for being acidified room is sodium molybdate, many sodium molybdates are 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 sodium molybdate solution, make sodium molybdate 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, and the H+ of generation is entered
It is acidified room, OH-Alkali room is entered, while being acidified the Na in the solution of room+Alkali room is migrated into through cation-exchange membrane.Due to H+
Move into and Na+Reduction, the sodium molybdate solution of the initial filling in acidifying room and the sodium molybdate solution pH value meeting that is continuously added to
Continuous decrease, controls solution ph in acidifying room stable in 2.0-4.5 by controlling the addition of sodium molybdate solution, can be in acid
Change interior and continuously generate many sodium molybdate solutions, many sodium molybdate solutions of generation import acidifying room circulating slot by being acidified room, from acidifying
It is interrupted in the circulating slot of room or continuously releases many sodium molybdate solutions；So as to realize the continuous production of many sodium molybdate solutions.
During bipolar membrane electrodialysis produces many sodium molybdate solutions, acidifying enters alkali room in room by cation-exchange membrane
In sodium ion sodium salt or NaOH are formed continuously in alkali room, Na ion concentrations in alkali room solution can be caused to gradually rise, sodium from
Sub- excessive concentration can cause bipolar membrane electrodialysis efficiency to decline, therefore by being continuously added to alkali room fluid infusion control into alkali room circulating slot
Na ion concentrations are in finite concentration scope in the circulating slot of alkaline room, and alkali room fluid infusion can be the low concentration with alkali room solution same composition
Electrolyte solution or pure water.The alkali room sodium salt mixed solution of bipolar membrane electrodialysis process generation can be between the extraction bypass of alkali room solution
Disconnected 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：7MoO4 2-+8H+=Mo7O24 6- (2)
Mo7O24 6-+H+=HMo7O24 5- (3)
HMo7O24 5-+H+=H2Mo7O24 4- (4)
H2Mo7O24 4-+H+=H3Mo7O24 3- (5)
8Mo7O24 6-+20H+=7Mo8O26 4-+10H2O (6)
In alkali room：Na++OH-→NaOH (7)
Preferably, during bipolar membrane electrodialysis, being acidified the Mo concentration of solution of room in below 250g/L.
In actual production process, Mo concentration in room can be acidified by regulating and controlling solution Mo concentration regulation and control in acidifying room circulating slot.
That is to say, during bipolar membrane electrodialysis control acidifying room circulating slot in solution Mo concentration in below 250g/L.It is acidified room solution
Mo excessive concentrations 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 Mo concentration is further optimized for control in below 200g/L in control acidifying room circulating slot
Solution Mo concentration is in 20-150g/L in acidifying room circulating slot.
The sodium molybdate solution Mo concentration supplemented into acidifying room is in below 200g/L.Preferably, being supplemented into acidifying room
Sodium molybdate solution Mo concentration in 20-150g/L.
Preferably, the pH value that the solution of room is acidified during controlling bipolar membrane electrodialysis is 2.0-4.5.
, can be by controlling the pH value of solution in acidifying room circulating slot during bipolar membrane electrodialysis to be in actual production process
2.0-4.5.Solution ph is too low in acidifying room circulating slot stability of solution is deteriorated, and many sodium molybdates are separated out with precipitation form,
Influence the stable operation of bipolar membrane electrodialysis process.Preferably, during control bipolar membrane electrodialysis in acidifying room circulating slot
The pH value of solution is 3.0-4.0.
Described alkali room solution is the aqueous solution of soluble sodium salt, preferably sodium hydroxide, sodium acid carbonate or sodium carbonate
Na ion concentration in single or mixed aqueous solution, alkali room solution is more than 0.1mol/L.
The selection of alkali room solution is sodium salt solution, can avoid the cation transport pair caused by homo-ion infiltration or concentration difference diffusion
The pollution of many sodium molybdate solutions；Na ion concentration is too high or too low, can cause the decline of current efficiency and the increasing of direct current consumption
Plus, Na ion concentration requirement is more than 0.1mol/L, preferably, selection is 0.1~5mol/L, in the range of the Na ion concentration
Under, that is, good electric conductivity is can guarantee that, preferable current efficiency is can guarantee that again.Further preferably, the sodium in alkali room solution from
Sub- concentration is 0.1~2mol/L.
Described pole room solution is the single or mixed aqueous solution of ammoniacal liquor, sodium acid carbonate, sodium carbonate or sodium 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 sodium ion efficiently moving to alkali room solution in acidifying room sodium molybdate solution
Move high efficiency, low energy consumption and the high molybdenum yield with removing, guarantee bipolar membrane electrodialysis process；Avoid alkali room solution and pole room solution
Cation contamination to being acidified many sodium molybdate solutions in room, obtains many sodium molybdate solutions of high-quality；And realize many sodium molybdate solutions
Interruption or continuous production.
It is molten that one kind proposed by the present invention prepares many sodium molybdates by raw material of sodium molybdate solution using bipolar membrane electrodialysis technology
The method of liquid is compared with inorganic acid acid adjustment method, without using inorganic acid acid adjustment, does not introduce impurity anions, superior product quality, examination
Agent consumption is small.
In the present invention H is produced using Bipolar Membrane dissociation water+And OH-, 1 cation-exchange membrane and 1 Bipolar Membrane component film
Right, several films only need to 1 pair of electrode to composition membrane stack, a membrane stack, and the electric energy consumption of electrode reaction accounts for total hydrolytic dissociation electric energy and disappeared
The percentage of consumption is low, while the energy consumption for dissociating water using Bipolar Membrane 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 many sodium molybdates by raw material of sodium molybdate solution using bipolar membrane electrodialysis technology
The method of liquid compared with traditional many sodium molybdate solution preparation methods, 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 many sodium molybdate solutions are 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.Sodium molybdate solution 102.58g/L containing Mo.Initially fill out
The solution being charged in sour room circulating slot is many sodium molybdate solutions, wherein Mo 150.0g/L, pH value 3.0 or so, volume 6.0L.Most
The solution being just filled into alkali room circulating slot is NaHCO3Solution, concentration is 1.0mol/L, and volume is 5L.It is added continuously to alkali room
Solution be 1.0mol/L NaHCO3Solution.The solution being initially filled into pole room circulating slot is NaOH solution, and concentration is
1.0mol/L, volume is 4L.After power-on servicing starts, sodium molybdate solution is added continuously to sour room inlet pipeline, NaHCO3Solution
Alkali room inlet pipeline is added continuously to, using constant current operation, operation electric current is 18A, by adjusting adding for sodium molybdate solution
The pH value of speed control sour room circulating slot solution is expected 2.0 or so, it is many when the liquid level of sour room is reached at sour room circulating slot overfall
Sodium molybdate solution is flowed continually out at sour room circulating slot overfall.Continued electrolysis 3 hours, tank voltage is stable in 42V or so, obtains
Many sodium molybdate solutions it is as clear as crystal.Operate many molybdenums in many sodium molybdate solutions and sour room circulating slot that flow continually out after terminating
Acid sodium solution is mixed, and many sodium molybdate solution 11.8L, wherein Mo 154.4g/L, pH value 2.0 are obtained altogether.Work as alkali room in operating process
Liquid level reach at alkali room circulating slot overfall that solution is flowed continually out at alkali room circulating slot overfall in groove.After operation terminates
Solution in the solution and alkali room circulating slot that are flowed continually out from alkali room circulating slot is mixed, 12.5L containing sodium solution is obtained altogether, wherein
Mo 0.04g/L, it follows that process Mo direct yield is 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.Molybdenum
Acid sodium solution 50.5g/L containing Mo,.The solution being initially filled into sour room circulating slot is molten with many sodium molybdates of the preparation of embodiment 1
What liquid diluted and obtained through deionized water, wherein Mo 61.8g/L, pH value 2.0 or so, volume 6.0L.
The solution being initially filled into alkali room circulating slot is Na2CO3Solution, concentration is 0.1mol/L, and volume is 5L.Prepare
The solution for being added continuously to alkali room is also the Na that concentration is 0.1mol/L2CO3Solution.Initially it is filled into molten in pole room circulating slot
Liquid is NaOH solution, and concentration is 1.0mol/L, and volume is 5L.After power-on servicing starts, sodium molybdate solution is added continuously to acidifying
In liquid circulating slot, Na2CO3Solution is added continuously in alkali lye circulating slot, using constant current operation, and operation electric current is 16A, is led to
The pH value of charging rate control sour room circulating slot solution of sodium molybdate solution is overregulated 3.0 or so, when the liquid level of sour room reaches
At sour room circulating slot overfall, many sodium molybdate solutions are flowed continually out at sour room circulating slot overfall.Continue power-on servicing 4 small
When, tank voltage is stable in 39V or so, and many sodium molybdate solutions of acquisition are as clear as crystal.Operate many molybdenums flowed continually out after terminating
Many sodium molybdate solutions mixing in acid sodium solution and sour room circulating slot, obtains many sodium molybdate solution 16.5L, wherein Mo altogether
68.9g/L, pH value 4.0.When the liquid level of alkali room reaches at alkali room circulating slot overfall that solution is followed from alkali room in groove in electrolytic process
Flowed continually out at annular groove overfall.Operate the solution in the solution and alkali room circulating slot for terminating will to be flowed continually out from alkali room circulating slot
Mixing, obtains 13.4L containing sodium solution, wherein Mo 0.05g/L altogether, it follows that process Mo 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.Sodium molybdate is molten
Liquid 150.2g/L containing Mo.The solution being initially filled into sour room circulating slot is many sodium molybdate solutions prepared with embodiment 2 through going
Ionized water dilution is obtained, wherein Mo 15.5g/L, pH value 4.0 or so, volume 6.0L.Initially it is filled into molten in alkali room circulating slot
Liquid is NaOH solution, and 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
NaOH solution.The solution being initially filled into pole room circulating slot is NaOH solution, and concentration is 1.0mol/L, and volume is 5L.Electricity
After dialysis operation starts, sodium molybdate solution is added continuously to sour room inlet pipeline, and NaOH solution is added continuously to alkali room inlet tube
Road, using constant current operation, operation electric current is 10A, and sour room circulating slot is controlled by the charging rate for adjusting sodium molybdate solution
The pH value of solution sour room circulating slot and alkali room circulating slot liquid level in 2.0 or so, electrolytic process constantly increase, every 1 small time-division
Part solution is not taken out from sour room circulating slot and alkali room circulating slot, so as to ensure the liquid level of sour room circulating slot and alkali room circulating slot
Will not be too high.Continue power-on servicing 3.5 hours, tank voltage is stable in 31V or so, and many sodium molybdate solutions of acquisition are as clear as crystal.
Operation mixes many sodium molybdate solutions being interrupted in many sodium molybdate solutions and sour room circulating slot taken out after terminating, and many molybdenums are obtained altogether
Acid sodium solution 19.5L, wherein Mo 130.5g/L, pH value 2.0.The solution taken out from alkali room circulating slot will be interrupted and operation terminates
The solution mixing in alkali room circulating slot, obtains 15.4L containing sodium solution, wherein Mo 0.06g/L, it follows that process Mo altogether afterwards
Direct 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 many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis, it is characterised in that：Sodium molybdate solution is through bipolar
The processing of EDBM system, directly conversion obtain many sodium molybdate solutions；Described bipolar membrane electrodialysis system is Bipolar Membrane and sun
Two compartment cellular constructions of film composition, two compartments include acidifying room and alkali room；The startup solution of described acidifying room is sodium molybdate
Or many sodium molybdate solutions, constantly sodium molybdate solution is supplemented into acidifying room during bipolar membrane electrodialysis, in direct current field force
Under effect, the removing of part sodium ion and the reduction of pH value in sodium molybdate solution are realized by bipolar membrane electrodialysis process, directly
Many sodium molybdate solutions are obtained in the acidifying room of bipolar membrane electrodialysis system.
2. the method as claimed in claim 1 that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis, it is characterised in that：It is bipolar
The membrane stack of EDBM system is a kind of two Room bipolar membrane electrodialysis membrane stack, by multiple films to constituting；Anode is pressed to the side of 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 alkali room (1), between the anode membrane side of Bipolar Membrane and cation-exchange membrane be acidifying room, cation exchange in repeat unit
It is alkali room (2) between film and 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.
3. the method as claimed in claim 1 or 2 that many sodium molybdate solutions are 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 many sodium molybdate solutions are 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 many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis as described in any one of Claims 1 to 4, its feature
It is：During bipolar membrane electrodialysis, the Mo concentration of solution of room is acidified in below 250g/L.
6. the method that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis as described in claim 1 or 5, it is characterised in that：
The sodium molybdate solution Mo concentration supplemented into acidifying room is in below 200g/L.
7. the method that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis as described in claim any one of 1-6, its feature
It is：The pH value for controlling the solution for being acidified room during bipolar membrane electrodialysis is 2.0-4.5.
8. the method that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis as described in claim any one of 1-7, its feature
It is：Described alkali room solution is the single or mixed aqueous solution of sodium hydroxide, sodium acid carbonate or sodium carbonate, in alkali room solution
Na ion concentration is more than 0.1mol/L.
9. the method as claimed in claim 3 that many sodium molybdate solutions are prepared based on bipolar membrane electrodialysis, it is characterised in that：It is bipolar
During EDBM, during bipolar membrane electrodialysis control acidifying room circulating slot in solution Mo concentration in below 250g/L；Control
The pH value that solution in the circulating slot of room is acidified during bipolar membrane electrodialysis processed is 2.0-4.5.
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