CN107344070A - A kind of continuous preparation system and preparation method of high basicity bodied ferric sulfate - Google Patents
A kind of continuous preparation system and preparation method of high basicity bodied ferric sulfate Download PDFInfo
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- CN107344070A CN107344070A CN201710455416.6A CN201710455416A CN107344070A CN 107344070 A CN107344070 A CN 107344070A CN 201710455416 A CN201710455416 A CN 201710455416A CN 107344070 A CN107344070 A CN 107344070A
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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
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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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- 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
- B01D61/52—Accessories; Auxiliary operation
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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
- B01D61/54—Controlling or regulating
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/12—Addition of chemical agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2684—Electrochemical processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/50—Specific extra tanks
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Abstract
The invention discloses a kind of continuous preparation system and preparation method of high basicity bodied ferric sulfate, wherein system includes membrane stack, positive electrode, negative electrode, electrolyte sampling device, acid solution generating means, PFS generating means, PFS storage devices, reaction solution storage device and power supply, and membrane stack has been internally formed cathode chamber, anode chamber, sour room, reative cell；During preparation, strong electrolytic solution is transported in anode chamber and cathode chamber by electrolyte sampling device, acid solution is transported in sour room by acid solution generating means, reaction solution is transported in reative cell by PFS generating means, the reaction solution in reaction solution storage device is continually transported in PFS generating means simultaneously so that the reaction solution in PFS generating means is overflowed in PFS storage devices；Power-on, Bipolar Membrane issue unboiled water dissociation, OH in electric field action‑PFS preparation process is participated in improve its basicity.Products obtained therefrom performance of the present invention is good, technique is simple, and is easily achieved continuous production.
Description
Technical field
The invention belongs to inorganic polymer flocculant production technical field, more particularly to a kind of high basicity bodied ferric sulfate
Continuous preparation system and preparation method.
Background technology
Bodied ferric sulfate (PFS, [Fe2(OH)n(SO4)3-n/2]m, n>2, m<10) it is a kind of new, high-quality, efficient molysite
Class inorganic polymer flocculant.Due to adsorption-flocculation is strong, dosage is few, without harmful substance such as aluminium and heavy metal ion etc.
Advantage, while decolourize, de-oiling, dehydration, degerming, deodorization, go COD, BOD and other effects notable, therefore, bodied ferric sulfate is used extensively
In industrial wastewater, municipal sewage, domestic water purified treatment.
The raw material for preparing bodied ferric sulfate is mainly ferrous sulfate and sulfuric acid, and preparation method includes direct oxidation method and catalysis
Oxidizing process.No matter which kind of method is used, and sulfuric acid and ferrous sulfate are required for through three peroxidating, hydrolysis and polymerization step (Hong Jin
The preparation chemical industry progress of moral water purification agent bodied ferric sulfates, 2001,3：33-35.)：
Oxidation：
Hydrolysis：
Polymerization：mFe2(OH)n(SO4)3-n/2→[Fe2(OH)n(SO4)3-n/2]m
PFS performance indications include pH (1%, Sol.), density, basicity (B, OH/Fe mol ratio), all iron content, also
Immunogenic substance content etc., wherein, basicity is then a relatively important index, shows the hydrolysis degree of iron ion, it is general and
Speech, the higher flocculating effect of B values is better, and (Xie Liping, Xu Xiangrong, once all bodied ferric sulfates basicities and flocculating property relation were ground
Study carefully Treatment of Industrial Water, 2001,21 (1)：26-28.).China national standard GB14591-2006 provides water treatment agent polyaluminum sulfate molysite
Base degree must reach more than 8%.
In addition, being searched for by domestic and foreign databases, it is found that existing PFS preparation process is usually batch mode of operation, deposit
Need to feed and the auxiliary operation such as discharging, product quality be not easy stabilization, complex operation, yield poorly the shortcomings of.
The content of the invention
In view of this, the invention provides a kind of continuous preparation system and method for high basicity bodied ferric sulfate,
The technical problem of solution is the product for preparing high basicity, while realizes continuous operation, and ensures that product quality is stable.
The present invention solves technical problem, adopts the following technical scheme that：
The continuous preparation system of the high basicity bodied ferric sulfate of the present invention, including：Membrane stack, positive electrode, negative electrode, electrolyte
Sampling device, acid solution generating means, PFS generating means, PFS storage devices, reaction solution storage device and power supply；
The negative electrode is connected with the negative pole of the power supply；The positive electrode is connected with the positive pole of the power supply；
The negative electrode and the positive electrode are respectively arranged at the both sides of the membrane stack；
The membrane stack has been internally formed four kinds of cathode chamber, anode chamber, sour room, reative cell compartments；
The outlet of the electrolyte sampling device is connected with anode chamber's charging aperture, the discharging opening of the anode chamber and institute
State cathode chamber charging aperture to be connected, the cathode chamber discharging opening is connected with the import of the electrolyte sampling device, forms electrolyte
Circulation loop；
The outlet of the acid solution generating means is connected with the sour room charging aperture, and the sour room discharging opening and the acid are molten
The import of liquid generating means is connected, and forms the circulation loop of acid solution；
The outlet of the PFS generating means is connected with the reative cell charging aperture, the reative cell discharging opening and the PFS
The import of generating means is connected, and forms PFS circulation loop；
The outlet of the reaction solution storage device is connected with the import of the PFS generating means；
The outlet of the PFS generating means is connected with the import of the PFS storage devices by overflow manner.
Preferably, the membrane stack is arranged by anion-exchange membrane, plastics filter, rubber sheet gasket, Bipolar Membrane successively alternate intervals
Row are formed, and close to positive electrode and negative electrode are anion-exchange membrane, between positive electrode and adjacent anion-exchange membrane
Anode chamber is formed, cathode chamber is formed between negative electrode and adjacent anion-exchange membrane；By handing between anode chamber and cathode chamber
Anion-exchange membrane and Bipolar Membrane for arrangement form the repeat unit of one or more sour rooms and reative cell.
Preferably, in addition to clamping device, the clamping device are used to fix the negative electrode, positive electrode and membrane stack；
Preferably, ion exchange is realized by interval of anion-exchange membrane between sour room and reative cell inside the membrane stack,
Using Bipolar Membrane as interval between the sour room of reative cell and next repeat unit adjacent thereto.
It is using above-mentioned continuous present invention also offers a kind of continuous preparation method of high basicity polymerization ferrous sulfate
Preparation system, comprise the following steps：
Strong electrolytic solution is transported in membrane stack anode chamber and cathode chamber by electrolyte sampling device；
Acid solution is transported in membrane stack sour room by acid solution generating means；
Reaction solution is transported in membrane stack reative cell by PFS generating means, while will be anti-in reaction solution storage device
Liquid is answered continually to be transported in PFS generating means with certain flow so that the PFS solution in PFS generating means overflows to PFS
In storage device；
Power-on, Bipolar Membrane issues unboiled water dissociation in electric field action, by H2O is dissociated into OH-And H+, OH-Participate in PFS's
Preparation process is to improve its basicity, H+Generation acid is combined with acid ion in sour room.
Preferably, the strong electrolytic solution is selected from sodium hydroxide, sodium sulphate, sodium nitrate, potassium sulfate, potassium nitrate and hydrogen-oxygen
Change the one or more in potassium solution, most preferably metabisulfite solution.
Preferably, the strong electrolytic solution concentration is 0.01~3mol/L.
Preferably, one or more of the acid solution in sulfuric acid, hydrochloric acid, salpeter solution, most preferably sulfuric acid are molten
Liquid.
Preferably, the acid solutions in the acid solution generating means are 0.005~6mol/L.
Preferably, the reaction solution is the mixed solution of ferrous sulfate, sulfuric acid and oxidant；In the reaction solution, institute
State ferrous sulfate concentration >=2mol/L, the amount ratio of the sulfuric acid and the material of the ferrous sulfate is 0.1~3；Described anti-
Answer in liquid, the amount for making the material of the oxidant is a, the amount of the material of ferrous sulfate is b, then a:b≥0.1.
Preferably, the oxidant is hydrogen peroxide, nitric acid, potassium chlorate, sodium hypochlorite, the one or more of sodium chlorate.
Compared with prior art, the invention provides a kind of continuous preparation system of high basicity bodied ferric sulfate and preparation
Method, water decomposition can occur in the presence of DC electric field using Bipolar Membrane, there is provided enough OH-Participate in PFS preparation
Journey is to improve its basicity；In addition, reaction solution storage device and PFS storage devices are introduced to ensure continually to input reaction solution
With obtain product PFS；Products obtained therefrom performance of the present invention is good, technological process is simple, it is easy to accomplish mechanization, automation and serialization
Production.
Brief description of the drawings
Fig. 1 is the structural representation of the continuous preparation system of high basicity bodied ferric sulfate provided in an embodiment of the present invention.
In figure, 1 is membrane stack, and 2 be dc source, and 3 be the negative pole of dc source, and 4 be the positive pole of dc source, and 5 be negative electrode, and 6 be sun
Electrode, 7 and 8 be clamping device, and 9 be electrodialysis plant, and 10 be reative cell discharging opening, and 11 be reative cell charging aperture, and 12 be sour room
Discharging opening, 13 be sour room charging aperture, and 14 be anode chamber's charging aperture, and 15 be cathode chamber discharging opening, and 16 be PFS immersible pumps, and 17 be acid
Room immersible pump, 18 be electrode chamber immersible pump, and 19 be reaction flow container, and 20 be acid solution tank, and 21 be electrode flow container, and 22 be PFS reaction solutions
Peristaltic pump, 23 be reaction solution storage tank, and 24 be PFS storage tanks.
Fig. 2 is that the membrane stack internal structure of the high continuous preparation system of basicity bodied ferric sulfate provided in an embodiment of the present invention is shown
It is intended to.In figure, 25 be anion-exchange membrane, and 26,27 form filters；28 be Bipolar Membrane, and 29 be filter.30th, 31,32,33 difference
It is that signal solution enters outgoing direction.
Fig. 3 is the membrane stack voltage versus time curve figure of 1- of embodiment of the present invention embodiments 3.
Fig. 4 is the sour room concentration versus time curve figure of 1- of embodiment of the present invention embodiments 3.
Embodiment
The continuous preparation system of high basicity bodied ferric sulfate provided by the invention, including：Membrane stack, positive electrode, negative electrode,
Electrolyte sampling device, acid solution generating means, PFS generating means, PFS storage devices, reaction solution storage device and power supply；
The negative electrode is connected with the negative pole of the power supply；The positive electrode is connected with the positive pole of the power supply；
The negative electrode and the positive electrode are respectively arranged at the both sides of the membrane stack；
The membrane stack is internally formed four cathode chamber, anode chamber, sour room, reative cell compartments；
The outlet of the electrolyte sampling device is connected with anode chamber's charging aperture, anode chamber's discharging opening with it is described
Cathode chamber charging aperture is connected, and the cathode chamber discharging opening is connected with the import of the electrolyte sampling device, forms electrolyte
Circulation loop；
The outlet of the acid solution generating means is connected with the sour room charging aperture, and the sour room discharging opening and the acid are molten
The import of liquid generating means is connected, and forms the circulation loop of acid solution；
The outlet of the PFS generating means is connected with the reative cell charging aperture, the reative cell discharging opening and the PFS
The import of generating means is connected, and forms PFS circulation loop；
The outlet of the reaction solution storage device is connected with the import of the PFS generating means；
The outlet of the PFS generating means is connected with the import of the PFS storage devices by overflow manner.
Referring to Fig. 1, Fig. 1 is the structure of the continuous preparation system of high basicity bodied ferric sulfate provided in an embodiment of the present invention
Schematic diagram.Wherein, 1 is membrane stack, and 2 be dc source, and 3 be the negative pole of dc source, and 4 be the positive pole of dc source, and 5 be negative electricity
Pole, 6 be positive electrode, and 7 and 8 be clamping device, and 9 be electrodialysis plant, and 10 be reative cell discharging opening, and 11 be reative cell charging aperture,
12 be sour room discharging opening, and 13 be sour room charging aperture, and 14 be anode chamber's charging aperture, and 15 be cathode chamber discharging opening, and 16 be that PFS dives under water
Pump, 17 be sour room immersible pump, and 18 be electrode chamber immersible pump, and 19 be reaction flow container, and 20 be acid solution tank, and 21 be electrode flow container, and 22 are
PFS reaction solution peristaltic pumps, 23 be reaction solution storage tank, and 24 be PFS storage tanks.
In the present invention, the continuous preparation system of high basicity bodied ferric sulfate includes membrane stack.Membrane stack includes anion exchange
Film, Bipolar Membrane and filter, the filter is between anion-exchange membrane and Bipolar Membrane.The present invention is to the anion-exchange membrane
There is no special limitation with Bipolar Membrane, using anion-exchange membrane well known to those skilled in the art and Bipolar Membrane, purchased by market
Buy acquisition.In an embodiment of the present invention, the anion-exchange membrane, Bipolar Membrane every effective area can be 5~
400cm2；In a further embodiment, the anion-exchange membrane, every effective area of Bipolar Membrane are alternatively 10~200cm2；
In other examples, the anion-exchange membrane, every effective area of Bipolar Membrane can also be 20cm2.The present invention can
With using the BP-I Bipolar Membranes and AMX anion-exchange membranes of Japanese astom companies.
In the present invention, the anion-exchange membrane, filter, Bipolar Membrane, filter, anion-exchange membrane order laminate rear structure
Into repeat unit, the positive electrode and negative electrode are close to anion-exchange membrane.In an embodiment of the present invention, the membrane stack can
With including 1~20 repeat unit；In a further embodiment, the membrane stack can also include 2~15 repeat units；At it
In his embodiment, the membrane stack can also include 2 repeat units.
In the present invention, the repeat unit preferably also includes sealing gasket, and the sealing gasket is arranged at the anion and handed over
Change between film and the positive electricity pole plate, between the anion-exchange membrane and the negative electricity pole plate.
In the present invention, the edge of the filter preferably includes aperture, and the aperture includes sealed aperture and apertured orifice,
The sealed aperture is used to cause liquid flowing；The opening direction of the apertured orifice is preferably filter middle part so that liquid can
On the one hand to carry out ion exchange at middle part, on the other hand continued to flow out according to aperture direction, can be used for controlling outlet port.
Preferably also include aperture on the anion-exchange membrane and Bipolar Membrane, aperture is closed pores, and is located at film edge.By upper
State film composition and aperture be set so that independent room each between can carry out ion exchange, and independent room
Between each self-forming circulation loop and export controllable.
In the present invention, the position relationship of the filter, anion-exchange membrane, Bipolar Membrane and aperture is as shown in Fig. 2 be this
What inventive embodiments provided continuously prepares high basicity bodied ferric sulfate device membrane stack internal structure schematic diagram, wherein 25 for it is cloudy from
Proton exchange, 26,27 composition filters；28 be Bipolar Membrane, and 29 be filter.30th, 31,32,33 be that signal solution enters outgoing direction respectively.
In the present invention, the negative electrode and the positive electrode are respectively placed in the both sides of the membrane stack.The present invention is to described
Negative electrode and positive electrode do not have special limitation, using the negative electrode used in electrodialysis plant well known to those skilled in the art and
Positive electrode, meet practical operation condition.In the present invention, the negative electrode is connected by wire with the negative pole of power supply；Institute
Positive electrode is stated by wire with the positive pole of power supply to be connected.In the embodiment of the present invention, the power supply is and the negative electrode
The supporting power supply with the positive electrode；The power supply can be dc source.
In the present invention, the clamping device is used to fix the negative electrode, positive electrode and membrane stack.The present invention is to the folder
Tight device does not have special limitation, meets practical operation condition.In an embodiment of the present invention, the clamping device can be with
Iron plate is clamped by two pieces and bolt forms, and two pieces of clamping iron plates are respectively arranged to the both sides of the membrane stack, blending bolt fastening.
In the present invention, the membrane stack is internally formed four kinds of cathode chamber, anode chamber, sour room and reative cell compartments.The electricity
The outlet of solution liquid sampling device is connected with anode chamber's charging aperture, the charging of the discharging opening of the anode chamber and the cathode chamber
Mouth is connected, and the discharging opening of the cathode chamber is connected with the import of electrolyte sampling device.In the present invention, the cathode chamber charging
Mouth is arranged on the position different from anode chamber's charging aperture, sour room charging aperture and reative cell charging aperture；The cathode chamber discharging opening is set
Put in the position different from anode chamber's discharging opening, sour room discharging opening and reative cell discharging opening.In the present invention, the anode chamber is entered
Material mouth is arranged on the position different from cathode chamber charging aperture, sour room charging aperture and reative cell charging aperture；Anode chamber's discharging opening
It is arranged on the position different from cathode chamber discharging opening, sour room discharging opening and reative cell discharging opening.In the present invention, the electrolyte enters
The import of sampling device can be identical with the outlet of the electrolyte sampling device, can also be different.The present invention is by by the electricity
The outlet of solution liquid sampling device is connected with anode chamber's charging aperture, anode chamber's discharging opening and the cathode chamber charging aperture phase
Even, the cathode chamber discharging opening is connected with the import of electrolyte sampling device, makes electrolyte sampling device, anode chamber and cathode chamber
Between form circulation loop.
In an embodiment of the present invention, circulating for the ease of electrolyte, the outlet of the electrolyte sampling device
The first attachment means can be provided between anode chamber's charging aperture；Anode chamber's discharging opening is fed with the cathode chamber
The second attachment means can be provided between mouthful；Can between the import of the cathode chamber discharging opening and the electrolyte sampling device
To be provided with the 3rd attachment means.The present invention is not special to the first attachment means, the second attachment means and the 3rd attachment means
Limitation, meet practical operation condition；In an embodiment of the present invention, first attachment means can be emulsion tube；
Second attachment means can be emulsion tube；3rd attachment means can be emulsion tube.
In the present invention, the electrolyte sampling device preferably includes electrolyte container and electrolyte conveying device.
In the present invention, the import of the electrolyte container is connected with the cathode chamber discharging opening；The electrolyte conveying device
It is arranged inside the electrolyte container.In an embodiment of the present invention, the import of the electrolyte container and institute
Cathode chamber discharging opening is stated using the 3rd attachment means described in above-mentioned technical proposal to be connected；The outlet of the electrolyte conveying device
It is connected using the first attachment means described in above-mentioned technical proposal with anode chamber's charging aperture；Anode chamber's discharging opening uses
The second attachment means are connected with the import of the cathode chamber described in above-mentioned technical proposal.
In the present invention, the electrolyte container is used to hold electrolyte.In the present invention, the electrolyte is preferred
For strong electrolytic solution, more preferably strong electrolytic solution be selected from sodium hydroxide, sodium sulphate, sodium nitrate, potassium sulfate, potassium nitrate and
One or more in potassium hydroxide solution, most preferably metabisulfite solution.In the present invention, the molar concentration of the electrolyte
Preferably 0.01mol/L~3mol/L, more preferably 0.03mol/L~2mol/L, most preferably 0.06mol/L~1.2mol/
L, preferably the most 0.08mol/L~1mol/L.The volume of the electrolyte is preferably the electricity flooded in electrolyte container
Solve liquid conveying device.The present invention does not have special limitation to shape, the material and size of the electrolyte container, meets real
Border operating condition；In an embodiment of the present invention, electrolyte container can be electrode solution tank 21.
In the present invention, the electrolyte conveying device is used to the electrolyte in the electrolyte container being delivered to
In the anode chamber, electrolyte is delivered to the negative electrode by the anode chamber and the second attachment means of the cathode chamber again
Room, electrolyte are delivered to the electrolyte by the 3rd attachment means of the cathode chamber and the electrolyte container again and contained
Put in container, form circulation loop.In an embodiment of the present invention, electrolyte conveying device can be electrode solution immersible pump 18.
In the present invention, the outlet of the acid solution generating means is connected with the sour room charging aperture, the acid solution life
Import into device is connected with the sour room discharging opening.In the present invention, the sour room charging aperture is arranged on feeds with cathode chamber
Mouth, anode chamber's charging aperture position different with reative cell charging aperture；The sour room discharging opening is arranged on cathode chamber discharging opening, anode
The room discharging opening position different with reative cell discharging opening.In the present invention, the imports of the acid solution generating means can with it is described
The outlet of acid solution generating means is identical, can also be different.The present invention is by by the outlet of the acid solution sampling device and institute
State sour room charging aperture to be connected, the sour room discharging opening is connected with the import of the acid solution sampling device so that acid solution sample introduction
Circulation loop is formed between device and sour room.
In an embodiment of the present invention, circulating for the ease of acid solution, the outlet of the acid solution generating means
The 4th attachment means can be provided between the sour room charging aperture；The import of the acid solution generating means and the sour room
The 5th attachment means can be provided between discharging opening.The present invention does not have to the 4th described attachment means and the 5th attachment means
Special limitation, meet practical operation condition；In the present invention, the 4th attachment means and the 5th attachment means can be with
It is identical with the first attachment means described in above-mentioned technical proposal, can also be different.In an embodiment of the present invention, the described 4th connects
Connection device can be emulsion tube；5th attachment means can be emulsion tube.
In the present invention, the acid solution generating means preferably include acid solution container and acid solution conveying device.
In the present invention, the import of the acid solution container is connected with the sour room discharging opening；The acid solution conveying device is set
It is placed in inside the acid solution container；In an embodiment of the present invention, the import of the acid solution container with it is described
Sour room discharging opening is connected using the 5th attachment means described in above-mentioned technical proposal；The outlet of the acid solution conveying device uses
The 4th attachment means described in above-mentioned technical proposal are connected with the sour room charging aperture.
In the present invention, the acid solution container is used to hold acid solution.In the present invention, the acid solution is preferred
For strong acid solution, the more preferably one or more in sulfuric acid, hydrochloric acid, salpeter solution, most preferably sulfuric acid solution.In the present invention
In, the molar concentration of the acid solution is preferably 0.005mol/L~6mol/L, more preferably 0.05mol/L~5mol/L, most
Preferably 0.1mol/L~4mol/L, preferably the most 0.15mol/L~3mol/L.The volume of the acid solution is preferably to flood
Acid solution conveying device in acid solution container.Shape, material and size of the present invention to the acid solution container
There is no special limitation, meet practical operation condition；In an embodiment of the present invention, the acid solution container can be with
For acid solution tank 20.
In the present invention, the acid solution conveying device is used to the acid solution in the acid solution container being delivered to institute
State in sour room.In an embodiment of the present invention, the acid solution conveying device can be sour room immersible pump 17.
In the present invention, the outlet of the PFS generating means is connected with the reative cell charging aperture, the PFS generations dress
The import put is connected with the reative cell discharging opening.In the present invention, the reative cell charging aperture is arranged on feeds with cathode chamber
Mouth, anode chamber's charging aperture position different with sour room charging aperture；The reative cell discharging opening is arranged on and cathode chamber discharging opening, sun
The pole room discharging opening position different with sour room discharging opening.In the present invention, the import of the PFS generating means can be with the PFS
The outlet of generating means is identical, can also be different.The present invention is by the way that the outlet of the PFS generating means is entered with the reative cell
Material mouth is connected, and the reative cell discharging opening is connected with the import of the PFS sampling devices so that PFS generating means and reative cell
Between form circulation loop.
In an embodiment of the present invention, circulating for the ease of PFS reaction solutions, the outlet of the PFS generating means
The 6th attachment means can be provided between the reative cell charging aperture；The import of the PFS generating means and the reaction
The 7th attachment means can be provided between the discharging opening of room.The present invention does not have to the 6th described attachment means and the 7th attachment means
There is special limitation, meet practical operation condition；In the present invention, the 6th attachment means and the 7th attachment means can
, can also be different with identical with the first attachment means described in above-mentioned technical proposal.In an embodiment of the present invention, the described 6th
Attachment means can be emulsion tube；7th attachment means can be emulsion tube.
In the present invention, the PFS generating means preferably include PFS reaction solutions container and PFS reaction solutions conveying dress
Put.In the present invention, the import of the PFS reaction solutions container is connected with the reative cell discharging opening；The PFS reaction solutions
Conveying device is arranged inside the PFS reaction solutions container.In an embodiment of the present invention, the PFS reaction solutions are held
The import of container is connected with the reative cell discharging opening using the 7th attachment means described in above-mentioned technical proposal；The PFS is anti-
The outlet of liquid container is answered to be connected with the reative cell charging aperture using the 6th attachment means described in above-mentioned technical proposal.
In the present invention, the PFS reaction solutions container is used to hold PFS reaction solutions.In the present invention, the PFS
Reaction solution is preferably the mixed solution of ferrous sulfate, sulfuric acid and oxidant.In the present invention, the ferrous sulfate preferably in reaction solution is dense
Degree >=2mol/L, more preferably 2~10mol/L, it is further preferably 2~8mol/L, is further preferably 2~6mol/L, most preferably 2~
4mol/L.In the present invention, the amount ratio of the material of sulfuric acid and ferrous sulfate preferably in reaction solution is 0.1~3, more preferably
0.2~2, most preferably 0.25~0.6.In the present invention, oxidant is preferably strong oxidizer, more preferably hydrogen peroxide, nitric acid, chlorine
Sour potassium, sodium hypochlorite, the most preferably one or more of sodium chlorate, potassium chlorate.Preferably, strong oxidizer in the reaction solution is made
Material amount be a, the amount of the material of ferrous sulfate be b, then a:b≥0.1.The volume of the PFS reaction solutions is preferably to fill
PFS reaction solution containers.The present invention does not have special limit to shape, the material and size of the PFS reaction solutions container
System, meets practical operation condition；In an embodiment of the present invention, the PFS reaction solutions container can be reaction solution
Tank 19.
In the present invention, the PFS reaction solutions conveying device is used to the PFS reaction solutions being delivered to inside the membrane stack
Reative cell in.In an embodiment of the present invention, the PFS reaction solutions conveying device can be PFS immersible pumps 16.
In the present invention, the outlet of the reaction solution storage device is connected with the import of the PFS reaction solutions container,
The outlet of the PFS reaction solutions container is connected with the import of PFS storage devices by overflow manner.
In an embodiment of the present invention, to be passed into PFS reaction solutions container for the ease of reaction solution then successive
Product PFS is prepared, the outlet of the reaction solution storage device can be provided with the 8th with the import of the PFS generating means and be connected
Device and the first PFS reaction solution conveying devices；The present invention does not have special limitation to the 8th attachment means, meets actual behaviour
Make condition；In the present invention, the 8th attachment means can be with the first attachment means phase described in above-mentioned technical proposal
Together, can also be different.In an embodiment of the present invention, the 8th attachment means can be emulsion tube.
In the present invention, the reaction solution storage device is used to hold PFS reaction solutions.In the present invention, the reaction solution
The reaction solution composition and concentration that storage device is held with PFS reaction solution containers are consistent.The present invention is to the reaction solution
Shape, the material and size of storage container do not have special limitation, meet practical operation condition；In embodiments of the invention
In, the reaction solution container can be reaction solution storage tank 23.
In the present invention, the PFS storage devices are used to hold the PFS overflowed from PFS reaction solution containers
Solution.The present invention does not have special limitation to shape, the material and size of PFS storage devices, meets practical operation condition.
In an embodiment of the present invention, PFS storage devices can be PFS storage tanks 24.
In the present invention, it is preferred to constant current or constant voltage operation are carried out to said apparatus using dc source 1.
Present invention also offers a kind of high basicity PFS continuous preparation method, using above-mentioned system, including following step
Suddenly：
Strong electrolytic solution is transported in membrane stack anode chamber and cathode chamber by electrolyte sampling device；
Acid solution is transported in the sour room of membrane stack by acid solution generating means；
Reaction solution is transported in the reative cell of membrane stack by PFS generating means, while by reaction solution storage device
Reaction solution is continually transported in PFS generating means with certain flow so that the PFS solution of PFS generating means overflows to PFS
In storage device.
Dc source is opened, the Bipolar Membrane in the membrane stack issues unboiled water dissociation in electric field action, by H2O is dissociated into OH-With
H+, OH-It is incorporated in reaction solution in membrane stack internal-response room and obtains high basicity PFS, H+With anion binding in membrane stack internal acid
Acid solution is obtained in room.
In the present invention, strong electrolytic solution is transported to electrodialysis membrane stack anode chamber by electrolyte sampling device first
In cathode chamber；The strong electrolytic solution is selected from sodium hydroxide, sodium sulphate, sodium nitrate, potassium sulfate, potassium nitrate and potassium hydroxide
One or more in solution, most preferably metabisulfite solution.In the present invention, the molar concentration of the electrolyte is preferably
0.01mol/L~3mol/L, more preferably 0.03mol/L~2mol/L, most preferably 0.06mol/L~1.2mol/L, the most
Preferably 0.08mol/L~1mol/L.The present invention has been clearly described for said apparatus and mode of movement, herein not
Repeat again.
In the present invention, above-mentioned electrolyte sampling device be used to providing power supply from electrolyte, have the chamber of circulation.
Position relationship with remaining salt room can be without limiting.
In the present invention, the acid solution in acid solution container is transported to electrodialytic membranes by acid solution conveying device
In the sour room of heap；The volume of the acid solution is preferably the acid solution conveying device flooded in acid solution container.In this hair
In bright, the molar concentration of acid solution is preferably 0.005mol/L~6mol/L, and more preferably 0.05mol/L~5mol/L is optimal
Elect 0.1mol/L~4mol/L as, the most preferably 0.15mol/L~3mol/L.
In the present invention, the PFS reaction solutions in PFS reaction solution containers are conveyed by PFS reaction solutions conveying device
Into the reative cell of electrodialysis membrane stack；The volume of the PFS reaction solutions is preferably to fill PFS reaction solution containers.The present invention
In, ferrous sulfate concentration >=2mol/L, more preferably 2~10mol/L preferably in reaction solution, is further preferably 2~8mol/L, then
Preferably 2~6mol/L, most preferably 2~4mol/L.In the present invention, the material of sulfuric acid and ferrous sulfate preferably in reaction solution
Amount ratio be 0.1~3, more preferably 0.2~2, most preferably 0.25~0.6.In the present invention, oxidant is preferably Strong oxdiative
Agent, more preferably hydrogen peroxide, nitric acid, potassium chlorate, sodium hypochlorite, the most preferably one or more of sodium chlorate, potassium chlorate.It is preferred that
, the amount for making the material of strong oxidizer in the reaction solution is a, the amount of the material of ferrous sulfate is b, then a:b≥0.1.
In the present invention, the Bipolar Membrane in the membrane stack issues unboiled water dissociation in electric field action, and OH- is incorporated in reaction solution
High basicity PFS is obtained in membrane stack internal-response room, H+ obtains acid solution with anion binding in sour room inside membrane stack.
In the present invention, it is preferred that before running gear so that solution circulation flow moves discharger inner air；Treat sky
After gas discharge, dc source, running gear are opened.It is furthermore preferred that it is specially to open immersible pump that the solution circulation flow is dynamic so that
Anode chamber and the solution of cathode chamber, sour room, reative cell each flow according to circulation loop.
To further appreciate that the present invention, with reference to continuous preparation of the embodiment to high basicity PFS provided by the invention
System and method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
Assemble preparation system：Specifically, electrodialysis plant 9 adds stream after alternately being laminated by anion-exchange membrane and Bipolar Membrane
The auxiliary material such as road filter and sealing gasket, which is formed, has 2 pairs of anion-exchange membranes and cation-exchange membrane repeat unit to form membrane stack 1,
Every effective area is 20cm2, and the negative electrode 5 at membrane stack both ends, positive electrode 6 are separately positioned on, and it is placed in electrode both ends
Clamping device 7,8 is formed clamps what is formed by bolt.Repeat unit puts in order composition by materials described below：Filter, anion
Exchange membrane, filter, Bipolar Membrane, filter, anion-exchange membrane；Anion-exchange membrane in repeat unit close to positive electrode, it is cloudy from
Proton exchange is close to negative electrode；Clamping device includes battery lead plate, bolt, nut and pad.Assembling electrodialysis membrane stack only needs will be upper
Part is stated by Fig. 2 laminated structures, then loads onto electrodialysis membrane stack clamping device 7,8, then screw up with a wrench.
Anode chamber's charging aperture 14, the cathode chamber discharging opening 15 of electrodialysis plant 9, sour room charging aperture 13, sour room discharging opening 12,
Reative cell charging aperture 11, reative cell discharging opening 10 respectively by flexible rubber hose be connected to corresponding to electrode flow container 21, acid solution tank 20, anti-
The inside of flow container 19 is answered, reaction solution storage tank 23 is connected to the inside of reaction flow container 19 by emulsion tube.Electrode flow container 21, acid solution
Electricity connected with the charging aperture emulsion tube of corresponding electrode chamber, sour room and reative cell respectively is equipped with inside tank 20, reaction flow container 19
Pole room immersible pump 18, sour room immersible pump 17 and PFS immersible pumps 16, form three electrode chamber, sour room and reative cell independent circulations
Loop；Reaction solution in reaction solution storage tank 23 is pumped into reaction flow container 19 by PFS reaction solutions peristaltic pump 22；Flow container will be reacted
19 are placed in PFS storage tanks 24；The positive electrode 6 of electrodialytic membranes stack device 9 and negative electrode 5 are passed through into wire and supporting direct current respectively
The positive pole 3 of power supply 2 is connected with negative pole 4.
High basicity PFS is prepared using above-mentioned shown continuous preparation system, comprised the following steps；
The potassium sulfate solution that 200mL molar concentrations are 0.3mol/L, the volume of potassium sulfate solution are poured into electrode flow container 21
Account for the 50% of the volume of electrode flow container 21.
The sulfuric acid solution that 200mL molar concentrations are 0.2mol/L is poured into acid solution tank 20, the volume of sulfuric acid solution accounts for acid solution
The 40% of the volume of tank 20.
100mL reaction solutions (4.65mol/L ferrous sulfate, 1.20mol/L sulfuric acid, 0.80mol/L are poured into reaction flow container 19
Potassium chlorate), the volume of reaction solution accounts for the 100% of reative cell tank 19.
To reaction solution storage tank 23 pour into 200mL reaction solutions (4.65mol/L ferrous sulfate, 1.20mol/L sulfuric acid,
0.80mol/L potassium chlorate), the volume of reaction solution accounts for the 60% of reative cell tank 19.
Electrode chamber immersible pump 18, sour room immersible pump 17, PFS immersible pumps 16 are opened, makes electrode flow container 21, acid solution tank 20, anti-
Answer the solution circulation flow in flow container 19 dynamic with the bubble in remover；After flowing 10min to be recycled, dc source operation is opened
Electrodialysis plant, PFS reaction solutions peristaltic pump 22 is opened, setting flow is 1mL/min, is operated in the present embodiment using constant current,
Setting electric current density size is 10mA/cm2。
The present embodiment tests electrodialysis plant voltage during high basicity PFS is prepared and sour room acid solution is dense
Degree, as shown in Figure 3 and Figure 4, Fig. 3 is the electrodialysis plant voltage of 1~embodiment of the embodiment of the present invention 3 with the time to test result
Change curve, Fig. 4 are the sour room acid solutions versus time curve figure of 1~embodiment of the embodiment of the present invention 3.
The properties of product that the present embodiment is determined in PFS storage tanks change with time, and test result is as shown in table 1.
The polyaluminum sulfate ferrum property of the embodiment of the present invention 1 of table 1 measure
| Time (minute) | All iron content (%) | Basicity (%) | pH | Density (g/mL) |
| 60 | 10.89 | 6.92 | 2.17 | 1.53 |
| 120 | 11.50 | 8.64 | 2.22 | 1.56 |
| 180 | 11.14 | 11.60 | 2.23 | 1.57 |
Embodiment 2
Potassium nitrate is prepared using the continuous preparation system shown in embodiment 1, comprised the following steps：
The potassium hydroxide solution that 400mL molar concentrations are 0.3mol/L is poured into electrode flow container 21, potassium hydroxide solution
Volume accounts for the 80% of the volume of electrode flow container 21.
The sulfuric acid solution that 200mL molar concentrations are 0.2mol/L is poured into acid solution tank 20, the volume of sulfuric acid solution accounts for acid solution
The 40% of the volume of tank 20.
100mL reaction solutions (4.65mol/L ferrous sulfate, 1.20mol/L sulfuric acid, 0.80mol/L are poured into reaction flow container 19
Potassium chlorate), the volume of reaction solution accounts for the 100% of reative cell tank 19.
To reaction solution storage tank 23 pour into 200mL reaction solutions (4.65mol/L ferrous sulfate, 1.20mol/L sulfuric acid,
0.80mol/L potassium chlorate), the volume of reaction solution accounts for the 60% of reative cell tank 19.
Electrode chamber immersible pump 18, sour room immersible pump 17, PFS immersible pumps 16 are opened, makes electrode flow container 21, acid solution tank 20, anti-
Answer the solution circulation flow in flow container 19 dynamic with the bubble in remover；After flowing 10min to be recycled, dc source operation is opened
Electrodialytic membranes stack device, PFS reaction solutions peristaltic pump 22 is opened, setting flow is 1mL/min, is grasped in the present embodiment using constant current
Make, setting electric current density size is 20mA/cm2。
The present embodiment tests electrodialysis plant voltage during high basicity PFS is prepared and sour room acid solution is dense
Degree, as shown in Figure 3 and Figure 4, Fig. 3 is the electrodialysis plant voltage of 1~embodiment of the embodiment of the present invention 3 with the time to test result
Change curve, Fig. 4 are the sour room acid solutions versus time curve figure of 1~embodiment of the embodiment of the present invention 3.
The properties of product that the present embodiment is determined in PFS storage tanks change with time, and test result is as shown in table 2.
The polyaluminum sulfate ferrum property of the embodiment of the present invention 2 of table 2 measure
| Time (minute) | All iron content (%) | Basicity (%) | pH | Density (g/mL) |
| 60 | 11.01 | 6.15 | 2.17 | 1.53 |
| 120 | 11.65 | 8.65 | 2.22 | 1.54 |
| 180 | 11.88 | 10.18 | 2.23 | 1.55 |
Embodiment 3
Potassium nitrate is prepared using the continuous preparation system shown in embodiment 1, comprised the following steps：
The potassium hydroxide solution that 200mL molar concentrations are 0.3mol/L is poured into electrode flow container 21, potassium hydroxide solution
Volume accounts for the 50% of the volume of electrode flow container 21.
The sulfuric acid solution that 200mL molar concentrations are 0.2mol/L is poured into acid solution tank 20, the volume of sulfuric acid solution accounts for acid solution
The 40% of the volume of tank 20.
100mL reaction solutions (4.65mol/L ferrous sulfate, 2.40mol/L sulfuric acid, 0.80mol/L are poured into reaction flow container 19
Potassium chlorate), the volume of reaction solution accounts for the 100% of reative cell tank 19.
To reaction solution storage tank 23 pour into 200mL reaction solutions (4.65mol/L ferrous sulfate, 1.20mol/L sulfuric acid,
0.80mol/L potassium chlorate), the volume of reaction solution accounts for the 60% of reative cell tank 19.
Electrode chamber immersible pump 18, sour room immersible pump 17, PFS immersible pumps 16 are opened, makes electrode flow container 21, acid solution tank 20, anti-
Answer the solution circulation flow in flow container 19 dynamic with the bubble in remover；After flowing 10min to be recycled, dc source operation is opened
Electrodialytic membranes stack device, PFS reaction solutions peristaltic pump 22 is opened, setting flow is 2mL/min, is grasped in the present embodiment using constant current
Make, setting electric current density size is 10mA/cm2。
The present embodiment tests electrodialysis plant voltage during high basicity PFS is prepared and sour room acid solution is dense
Degree, as shown in Figure 3 and Figure 4, Fig. 3 is the electrodialysis plant voltage of 1~embodiment of the embodiment of the present invention 3 with the time to test result
Change curve, Fig. 4 are the sour room acid solutions versus time curve figure of 1~embodiment of the embodiment of the present invention 3.
The properties of product that the present embodiment is determined in PFS storage tanks change with time, and test result is as shown in table 3.
The polyaluminum sulfate ferrum property of the embodiment of the present invention 3 of table 3 measure
| Time (minute) | All iron content (%) | Basicity (%) | pH | Density (g/mL) |
| 60 | 11.01 | 6.55 | 2.19 | 1.55 |
| 120 | 11.65 | 8.35 | 2.25 | 1.58 |
| 180 | 11.88 | 10.68 | 2.28 | 1.57 |
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For one of ordinary skill in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out some
Improve and modification, these improvement and modification are also fallen into the protection domain of the claims in the present invention.To the disclosed embodiments
Described above, the special technical staff in this area is realized or using the present invention, a variety of modifications to these embodiments are to ability
It will be apparent for the professional and technical personnel of domain.Generic principles defined herein can not depart from the essence of the present invention
In the case of refreshing or scope, realize in other embodiments.Therefore, the present invention is not intended to be limited to these realities shown in this article
Example is applied, and is to fit to the most wide scope consistent with principles disclosed herein and novel features.
Claims (9)
- A kind of 1. continuous preparation system of high basicity bodied ferric sulfate, it is characterised in that including：Membrane stack, positive electrode, negative electricity Pole, electrolyte sampling device, acid solution generating means, PFS generating means, PFS storage devices, reaction solution storage device and electricity Source；The negative electrode is connected with the negative pole of the power supply；The positive electrode is connected with the positive pole of the power supply；The negative electrode and the positive electrode are respectively arranged at the both sides of the membrane stack；The membrane stack has been internally formed four kinds of cathode chamber, anode chamber, sour room, reative cell compartments；The outlet of the electrolyte sampling device is connected with anode chamber's charging aperture, anode chamber's discharging opening and the negative electrode Room charging aperture is connected, and the cathode chamber discharging opening is connected with the import of the electrolyte sampling device, forms the circulation of electrolyte Loop；The outlet of the acid solution generating means is connected with the sour room charging aperture, and the sour room discharging opening is given birth to the acid solution Import into device is connected, and forms the circulation loop of acid solution；The outlet of the PFS generating means is connected with the reative cell charging aperture, and the reative cell discharging opening generates with the PFS The import of device is connected, and forms PFS circulation loop；The outlet of the reaction solution storage device is connected with the import of the PFS generating means；The outlet of the PFS generating means is connected with the import of the PFS storage devices by overflow manner.
- 2. the continuous preparation system of high basicity bodied ferric sulfate according to claim 1, it is characterised in that：The membrane stack By anion-exchange membrane, plastics filter, rubber sheet gasket, Bipolar Membrane, alternate intervals are arranged to make up successively, and close to positive electrode and the moon Electrode is anion-exchange membrane, forms anode chamber between positive electrode and adjacent anion-exchange membrane, negative electrode with it is adjacent Anion-exchange membrane between form cathode chamber；By the anion-exchange membrane that is alternately arranged and double between anode chamber and cathode chamber Pole film forms the repeat unit of one or more sour rooms and reative cell.
- 3. the continuous preparation system of high basicity bodied ferric sulfate according to claim 2, it is characterised in that：Also include folder Tight device, the clamping device are used to fix the negative electrode, positive electrode and membrane stack.
- 4. the continuous preparation system of high basicity bodied ferric sulfate according to claim 2, it is characterised in that：The membrane stack Ion exchange is realized using anion-exchange membrane as interval, reative cell and adjacent thereto next between internal sour room and reative cell Using Bipolar Membrane as interval between the sour room of repeat unit.
- A kind of 5. system using the high basicity bodied ferric sulfate of continuous preparation system described in any one in Claims 1 to 44 Preparation Method, it is characterised in that：Comprise the following steps：Strong electrolytic solution is transported in membrane stack anode chamber and cathode chamber by electrolyte sampling device；Acid solution is transported in membrane stack sour room by acid solution generating means；Reaction solution is transported in membrane stack reative cell by PFS generating means, while by the reaction solution in reaction solution storage device Continually it is transported in PFS generating means so that the reaction solution in PFS generating means is overflowed in PFS storage devices；Power-on, Bipolar Membrane issues unboiled water dissociation in electric field action, by H2O is dissociated into OH-And H+, OH-Participate in PFS preparation Journey is to improve its basicity, H+Generation acid is combined with acid ion in sour room.
- 6. preparation method according to claim 5, it is characterised in that：The strong electrolytic solution is selected from sodium hydroxide, sulphur One or more in sour sodium, sodium nitrate, potassium sulfate, potassium nitrate and potassium hydroxide solution；The strong electrolytic solution concentration is 0.01~3mol/L.
- 7. preparation method according to claim 5, it is characterised in that：The acid solution is selected from sulfuric acid, hydrochloric acid, salpeter solution In one or more；Acid solutions in the acid solution generating means are 0.005~6mol/L.
- 8. preparation method according to claim 5, it is characterised in that：The reaction solution is the mixed solution of ferrous sulfate, sulfuric acid and oxidant；In the reaction solution, the ferrous sulfate concentration >=2mol/L, the amount of the sulfuric acid and the material of the ferrous sulfate Ratio is 0.1~3；In the reaction solution, the amount that makes the material of the oxidant is a, the amount of the material of ferrous sulfate is b, then a:b≥ 0.1。
- 9. preparation method according to claim 8, it is characterised in that：The oxidant be hydrogen peroxide, nitric acid, potassium chlorate, The one or more of sodium hypochlorite, sodium chlorate.
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| CN110282715A (en) * | 2019-07-16 | 2019-09-27 | 闽江学院 | A kind of preparation and application of polyquaternium In-situ reaction improved PFS |
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