CN102877085A - Method for preparing high-purity peroxysulphate based on electrolytic oxidation through ion-exchange membrane electrolyzer for chlor-alkali production - Google Patents
Method for preparing high-purity peroxysulphate based on electrolytic oxidation through ion-exchange membrane electrolyzer for chlor-alkali production Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity peroxysulphate based on electrolytic oxidation through an ion-exchange membrane electrolyzer for chlor-alkali production. According to the method, a perfluorinated ion exchange membrane is arranged between electrodes, and the electrolyzer comprises an anode compartment, an anode, the perfluorinated ion exchange membrane, a cathode and a cathode compartment. The method comprises the following steps: an anolyte sulfate aqueous solution and a catholyte alkali solution are respectively supplied to the anode compartment and the cathode compartment of the electrolyzer to conduct electrochemical ion exchange, the electrolyzer is charged with direct current to conduct constant current electrolysis, sulphate ions in the sulphate solution are enriched in the anode compartment because of not passing through the ion-exchange membrane, and are migrated on the anode in the anode direction to discharge to generate sulfate radicals, the sulfate radicals are combined with M<+> to generate sulfate, and the anode out-of-electrolyzer solution is subjected to after treatment to obtain high-purity peroxysulphate. The method overcomes the defects that in the prior art, the energy consumption is high, and the current efficiency is low, is simple in process, achieves high current efficiency and low energy consumption, and is easy to realize industrial production.
Description
Technical field
The present invention relates to a kind of electrochemical method for synthesizing of persulphate, particularly a kind of method based on the synthetic persulphate of ion-exchange membrane electrolyzer for chlor-alkali production perfluorinated ion-exchange membrane method electrolysis vitriol belongs to inorganic electrochemical synthesis field.
Background technology
Persulphate mainly comprises ammonium persulphate, Sodium Persulfate and Potassium Persulphate, and the general designation alkali metal persulphate is of many uses.Such as ammonium persulphate ((NH
4)
2S
2O
8, have another name called ammonium peroxydisulfate, Ammonium peroxodisulphate, APS) and be the ammonium salt of peroxy-disulfuric acid.Peroxydisulfate contains peroxy, is strong oxidizer.The most important application of persulphate is exactly the emulsion polymerization in the aqueous solution, and persulfide is as the initiator of synthetic chloroprene rubber or the formation of emulsion polymerization body free radical.Initiator when can be used as tetrafluoroethylene polymerization, the polymerization such as some water-soluble monomers such as acrylicacidandesters, acrylamide, vinyl acetate or copolymerization are also made initiator with it.As oxygenant and SYNTHETIC OPTICAL WHITNER, be widely used in the Storage Battery Industry in China; It also is used as the desizing agent of fiber industry; And can be used as the etching agent of metal and semiconductor material surface treatment agent, printed wiring; Also be widely used in the formation fracturing of oil production; Food grade is as flour and starch processing industry, oil prodution industry, as wheat modification agent, cereuisiae fermentum mould inhibitor; Be used for removing hypo at photographic industry.
The production of persulphate has two kinds of methods, and the one, electrolytic process, the 2nd, anthraquinone.Anthraquinone have the little characteristics of energy consumption, but product purity is not high, and subsequent purification is complicated; The characteristics of electrolytic process are that product purity is high, but power consumption is also higher.Xiao Ke waits by force (development persulphate process for cleanly preparing [J], the Henan chemical industry, 06 phase in 2010,28-30) think that the present persulphate production technique of China is equivalent to world's level of the eighties in 20th century, continuity, the especially cell construction that is Potassium Persulphate method production hydrogen peroxide process is backward, power consumption is high, and current efficiency is low, postprocessing working procedures falls behind, and causes the drawbacks such as cost is high, raw material consumption is large.
It is domestic that to prepare the research of ammonium persulphate about electrolytic process a lot, relevant report comprises: (the research of Process for Electrosynthesis of Ammonium Persulfate such as Zhao Jianhong, Zhengzhou University's journal, the 1st phase of the 27th volume in 2006) announced take ammonium sulfate as raw material, in homemade box electrochemical reactor, adopting titanium base platinized electrode is anode, and the lead antimony alloy electrode is negative electrode, the Nafion427 cationic exchange membrane is barrier film, the electrolytic preparation ammonium persulphate.Take current efficiency and productive rate as optimization aim, investigated the impact of many factors on electrolytic reaction. resulting optimal conditions is: p-aminophenol content is less than 0.05% in the by product ammonium sulfate, and starting point concentration is 36.5%, and anode additive is 0.06% ammonium polyphosphate, 15 ℃ of electrolysis temperatures.Energising amount 72.48Ah has carried out 5 batches repetition electrolytic experiment under this better condition, current efficiency all is higher than 80%, and productive rate all is higher than 55%.Product can obtain the ammonium persulphate product of massfraction more than 99.5% through crystallization, separation, drying.(the electrolysis dilute ammonium sulfate solution is produced ammonium persulphate [J] to Cong Yufeng etc., Fusun PetroleumCollege's journal, 04 phase of calendar year 2001) produces the byproduct-dilute ammonium sulfate solution of vinyl cyanide as raw material take Fushun Petrochemical Company acrylic fiber chemical factory, adopt Process for Electrosynthesis of Ammonium Persulfate, under the certain temperature, adopt Pt to make anode, Pb makes negative electrode, and the tetrafluoroethylene cationic membrane is barrier film, and adding a certain amount of self-control inhibitor is additive, the electrolytic preparation ammonium persulphate, transformation efficiency can reach 95%, adopts the crystallization process separated product, and with iodimetry,iodometry product purity is measured, the ammonium persulphate massfraction reaches 99%, investigated simultaneously the kind of additive, consumption, the kind of barrier film, current density, electrolysis time is on the impact of products collection efficiency.Experiment shows, produces the ammonium persulphate product with this method, and technique is simple, processing ease, and production process is polluted little, and product is easily separated, and purity is high, is to utilize dilute ammonium sulfate solution to produce the best approach of ammonium persulphate.Yellow Yongming (Production Status of Ammonium Persulfate by Electroynthesis [J], Guangdong chemical industry, 04 phase in 2007) is summed up and is thought that electrolytic process prepares the cathode current density 0.5kA/m of ammonium persulphate
2, voltage 5-7V, temperature is controlled at 30～50 ℃, and current efficiency is about 80%, and electrolytic power consumption 1.8-2.2kWh/t is the highly energy-consuming product.The auspicious clear grade of model (electrolytic process prepares the applied research inorganic chemicals industry [J] of ammonium persulphate, 02 phase in 1997) prepares (NH with electrolytic process
4)
2S
2O
8The research air electrode replaces lead electrode, makes original bath voltage up to dropping to 3.5V more than the 5.8V; Research replaces ceramic membrane with ionic membrane, can reduce bath voltage 0.65V, studies by antianode promotor, makes current efficiency bring up to 83% by 62%.
But it is still on the low side that electrolytic process prepares the current efficiency of persulphate, causes power consumption too high, do not meet the requirement of present low carbon development till now.
The selective ion-exchange membrane that sees through characteristic of ion is begun to be applied in the chlor-alkali electrolytic cells in eighties of last century the fifties.Du pont company has been developed the ion-exchange membrane of perfluorinated sulfonic resin the sixties.The skeleton structure ion-exchange membrane of this perfluoro has extraordinary stability, is adapted at most using in the severe rugged environment of chlor-alkali electrolytic cells.Japan AGC company and Japanese Asahi Kasei Corporation have also been developed the similar perfluorinated ion-exchange membrane of structure in succession.Japanese Asahi Kasei Corporation had replaced the perfluoro sulfonic acid membrane of E.I.Du Pont Company with the perfluorocarboxylic acid film in 1976, and had developed carboxylic acid-sulfonic acid composite membrane.Beginning Shandong Dongyue Polymer Material Co., Ltd. researched and developed successfully domestic Membrane Used In Chlor-alkali Cell (being perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane) in 2009, and took the lead in dropping into Lanxing (Beijing) Chemical Machinery Co., Ltd. at the experimental installation (2.7m of Huanghua chlor-alkali company limited of Cangzhou Dahua Group company limited
2The NBH electrolyzer) trial run obtains initial success.Subsequently again at ten thousand tons of devices of Dongyue Fluorine-Silicon Material Co., Ltd., Shandong's chlor-alkali plant, the middle salt Changzhou chemical industry chlor-alkali plant F of limited-liability company
2The successful Application such as device.
Present business-like chlorine industry is perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane with perfluorinated ion-exchange membrane (Membrane Used In Chlor-alkali Cell), and the anode side of composite membrane was that perfluorinated sulfonic acid layer, cathode side are the perfluorocarboxylic acid layer when perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane was used for electrolyzer.The preparation method is referring to CN101811359A.Sulphonic layer has higher ion and sees through ability, and is that lower bath voltage is arranged in 20%～30% at alkali concn, thereby can save significantly power consumption; And carboxylic layer can stop OH
-The infiltration migration of ion anode guarantees higher current efficiency.Because of its distinctive negatively charged ion blocking effect, chlorine industry except being applied to chlor-alkali, can also be widely used in other electrochemical synthesis fields with perfluorinated ion-exchange membrane, prepares highly purified fine chemicals.
Chinese patent file CN1233585A(CN99104507.6) a kind of method that adopts the electrolytic preparation ammonium persulphate is disclosed, adopt the aluminum oxide diaphragm cell, comprise that electrolysis is used as the sulphate-containing ion of anode material and the aqueous solution of ammonium ion, the crystallization electrolysate, from mother liquor, isolate crystal, described raw material for anode is comprised of ammonium sulfate solution, and wherein the amount of ammonium ion is at least 1 equivalent (2 times of moles) by sulfate ion.The method of the electrolytic preparation vitriol that this patent document is used still has weak point: 1. current efficiency is still lower, from its all embodiment in general current efficiency 80.3%-87.2% is only arranged; 2. the caustic soda that generates is consumed, but not is to produce separately as product widely as a kind of, causes product single, and production efficiency is low.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method that a kind of electrolytic oxidation based on ion-exchange membrane electrolyzer for chlor-alkali production prepares the high purity persulphate, the present invention adopts ion-exchange membrane electrolysis electrolysis sulfate liquor to prepare the electrochemical method for synthesizing of high purity persulphate with high conversion.
Technical scheme of the present invention is as follows:
A kind of electrolytic oxidation based on ion-exchange membrane electrolyzer for chlor-alkali production prepares the method for persulphate, by use the electrolyzer that perfluorinated ion-exchange membrane is set and is mainly consisted of by anolyte compartment, anode, perfluorinated ion-exchange membrane, negative electrode, cathode compartment between electrode, carry out according to the following steps:
(1) anolyte and catholyte are supplied to respectively in the anolyte compartment and cathode compartment of this electrolyzer, carry out the electrochemical ion exchange; Wherein, described anolyte is the aqueous solution (M of vitriol
2SO
4), catholyte is the alkaline solution (MOH) corresponding with positively charged ion in the described vitriol;
The vitriol general formula is M
2SO
4, wherein M=K, Na, NH
4
(2) carry out constant-current electrolysis to the logical direct current of electrolyzer, under electric field action, positively charged ion (M in the sulfate liquor in the anolyte compartment
+) to cathode direction migration and see through perfluorinated ion-exchange membrane and enter cathode compartment, water molecules is decomposed into hydrogen and hydroxide ion at negative electrode in the cathode compartment, hydroxide ion with see through positively charged ion (M in the sulfate liquor that the perfluorinated ion-exchange membrane migration comes
+) in conjunction with generating alkali (MOH), i.e. alkaline solution;
Water molecules in the anolyte compartment is decomposed into oxygen and hydrogen ion at anode, and sulfate ion can't and be enriched in the anolyte compartment through ion-exchange membrane in the sulfate liquor, and the migration of anode direction generates persulfate in the anode discharge; With M
+In conjunction with generating persulphate;
(3) collect the tank liquor that goes out that persulphate is rich in the anolyte compartment, can obtain the high purity persulphate through concentrated, crystallization treatment.Described concentrated, crystallization treatment gets final product by techniques well known.
The alkali of collecting the cathode compartment enrichment goes out tank liquor and can carry out recycle.Get final product by techniques well known.
Cathode and anode generates during electrolysis hydrogen and oxygen both can be used as by product and had collected use, also can be directly emptying, and environmentally safe, toxicological harmless.
Preferred according to the present invention, described persulphate is Sodium Persulfate, Potassium Persulphate or ammonium persulphate.Anolyte vitriol is sodium sulfate, vitriolate of tartar or ammonium sulfate, and described catholyte is corresponding sodium hydroxide, potassium hydroxide or ammoniacal liquor.
Preferred according to the present invention, the anolyte compartment goes out tank liquor persulphate concentration in mass concentration 20%～35%.
The method of electrolytic preparation persulphate according to the present invention, preferred following electrolytic condition:
Described electrolysis temperature is 20 ℃～55 ℃, and further preferred, electrolysis temperature is 35 ℃～45 ℃, with 40 ℃ for most preferably.
Preferably, when electrolysis temperature was higher than room temperature, described anolyte and catholyte stock liquid can be preheating to first when being lower than 5～10 ℃ of electrolysis temperatures and pass in the electrolyzer.
The current density of described constant-current electrolysis is 1-6kA/m
2, 3-4.5kA/m preferably
2
Preferred according to the present invention, in the electrolytic process, keep certain pressure between cathode compartment and anolyte compartment, the cathode compartment gaseous pressure is higher than the anolyte compartment, and anode and cathode pressure reduction is controlled at 0.1-5kPa, and preferably this anode and cathode pressure reduction is 2 ~ 4kPa.
When carrying out constant-current electrolysis to the logical direct current of electrolyzer, control anolyte and catholyte into and out of groove concentration: make described anolyte advance groove vitriol mass concentration and be controlled at 25～42wt%, preferably advancing groove vitriol mass concentration is 30-40%; Catholyte (alkaline solution) advances groove mass concentration 15%～28%, goes out accordingly groove mass concentration 20%～32%, goes out the groove mass concentration and exceeds into groove mass concentration 2 ~ 5%.Described catholyte goes out groove concentration can be by adding pure water control.
According to the present invention, anode material flow quantity Q(L/h wherein) be calculated as follows acquisition:
I is the dc electrolysis electric current in the formula, the A of unit; Mn is the molecular weight for vitriol in the anolyte feedstock solution; X is for advancing groove vitriol mass percent concentration; F is Faraday's number, 96485C/mol.
Anode of the present invention, perfluorinated ion-exchange membrane, negative electrode are the chlorine industry common technology.Wherein preferred perfluorinated ion-exchange membrane is chlor-alkali perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane, can buy by market, perhaps by the prior art preparation, the preparation method is referring to CN101811359A, and is concrete such as its specification sheets embodiment 1, embodiment 2, embodiment 3 or embodiment 4.
Described cathode electrode is the mesh electrode of stainless steel or nickel-base strip activated coating, the mesh electrode of preferred stainless steel or nickel-base strip activated coating; Anode electrode is titanium base net shape electrode.By prior art, market is bought.
Described ion-exchange membrane electrolyzer can be single cell electrolyzer (Fig. 1), also can a plurality of unit electrolytic bath series connection form bipolar cell (Fig. 2).
The below is take the ammonium sulfate electrolysis as example illustrates principle of the present invention: the ammonium sulfate solution in the electrolyzer anode chamber is under the effect of electrical forces, and the sulfate ion anode direction migration in the solution is until in the anode discharge and generate persulfate.Simultaneously, owing to the selection perviousness of ionic membrane, sulfate ion can't spread through ion-exchange membrane, only has ammonium ion could select to see through and enter cathode compartment, and is enriched in wherein.Water molecules is decomposed into hydrogen and hydroxide ion at negative electrode in the electric tank cathode chamber.The latter is combined into ammonium hydroxide with the ammonium ion that is come by anolyte compartment's migration just.
Ammonium sulfate ((NH
4)
2SO
4) electrolytic preparation ammonium persulphate electrode reaction is as follows:
2SO
4 2-－2e→S
2O
8 2-↑
The electrochemical cathode reaction is:
2H
2O+2e→2OH
-+H
2↑
Total reaction is:
2(NH
4)
2SO
4+2H
2O→(NH
4)
2S
2O
8+2NH
4OH+H
2↑
Compared with prior art, excellent results of the present invention is as follows:
The shortcomings such as 1, electrolysis process of the present invention avoids in the existing method power consumption high, and current efficiency is low, present method is simple, easily realizes industrial amplification production.
2, method of the present invention by electrolysis with the cation selective of negative electrode move to negative electrode, avoid introducing other impurity, can obtain the alkali byproducts such as highly purified sodium hydroxide.Products obtained therefrom persulphate purity is higher than 99.6%.
3, method of the present invention is utilized chlor-alkali ion groove electrolyzer, has both brought into play the strong speciality of fluoro-containing macromolecule material electrochemical corrosion resistant, can stop again negatively charged ion from the infiltration of negative electrode anode, can realize high current efficiency and low power consumption.Technological process current efficiency is more than 98%.
Embodiment
By the following examples the present invention is further specified, but the present invention is not limited only to following examples.
The perfluorinated ion-exchange membrane that uses among the embodiment is the commercial goods film, and DF988 type, DF2801 type chlor-alkali are produced with perfluorocarboxylic acid-perfluorinated sulfonic acid composite ionic membrane, Shandong Dongyue Polymer Material Co., Ltd., and N966 type ionic membrane E.I.Du Pont Company produces.
With the Ni-based mesh electrode of activated coating, be the conventional products that chlorine industry is used with stainless steel-based mesh electrode, the titanium base net shape electrode of activated coating, chemical industry equipment company limited of Zibo Golden Bridge provides among the embodiment.
Data processing:
The purity testing of product persulphate is measured according to GB/T 23939-2009 method among A, the embodiment.
B, the inventive method can use formula (I) to calculate the cathode efficiency η (%) of electrolytic process in for some time:
In the formula, take sodium hydroxide as cathode materials liquid as example:
η---current efficiency, %;
F---Faraday's number (96485C/mol);
M---for some time inner cathode is collected the quality of product sodium hydroxide solution, g in the electrolytic process;
The massfraction of the sodium hydroxide solution that c---negative electrode is collected, %;
N---pass through the electric weight (Amin) of electrolyzer in the electrolytic process in for some time, can obtain by the product of electric current and time;
The molecular weight of M---sodium hydroxide, 40g/mol.
C, the inventive method can use formula (II) to calculate the ton product power consumption of electrolytic process in for some time:
In the formula:
Electrolysis direct current power consumption in Θ---the report period, unit is kilowatt-hour (kWh);
Product day output in M---the report period, unit is tpd (t/d);
The time of t---report period (being generally 72 hours), unit is hour (h).
Annotate: calculated by 24 hours runtime every day.
Embodiment 1:
A kind of method of electrolytic preparation high purity persulphate, by use the electrolyzer that perfluorinated ion-exchange membrane 3 is set and is mainly consisted of by anolyte compartment 4, anode 1, perfluorinated ion-exchange membrane 3, negative electrode 2, cathode compartment 5 between electrode, carry out according to the following steps:
(1) in ion-exchange membrane electrolyzer as shown in Figure 1, carries out the electrochemical ion exchange, cathode electrode is the Ni-based mesh electrode with activated coating, anode electrode is titanium base net shape electrode, fluorine ion exchange membrane 3 is DF988 type chlor-alkali perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane ionic membrane, useful area 50cm
2
(2) the anolyte raw material is the aqueous solution of 30% mass concentration ammonium sulfate, and the catholyte raw material is 28% mass concentration solution of ammonium hydroxide; With pump anode material liquid and cathode materials liquid are squeezed in the anolyte compartment of electrolyzer and the cathode compartment respectively and circulated;
(3) under 35 ℃, carry out constant-current electrolysis, current density 1.5kA/m to the logical direct current of electrolyzer
2, advance groove anolyte ammonium sulfate concentrations and be controlled at 30%, flow velocity 0.086L/h; The catholyte solution of ammonium hydroxide advances groove mass concentration 28%, goes out groove mass concentration 30%; Anode and cathode pressure reduction is controlled at 2kPa.Ammonium persulphate concentration adopts national standard (GB/T 23939-2009 industry ammonium persulphate) to measure.
(4) anode that step (3) is obtained go out tank liquor after filtration, freezing, crystallization, centrifugation, drying namely gets the high purity ammonium persulphate again.Recycling Mother Solution is used.
Through Data Management Analysis, this technological process current efficiency is 98.33%, and power consumption is 2170kWh/t, the purity of product ammonium persulphate＞99.69%.
Collection cathode compartment solution of ammonium hydroxide goes out tank liquor and carries out recycle.
Embodiment 2:
(1) in ion-exchange membrane electrolyzer as shown in Figure 1, carries out the electrochemical ion exchange, cathode electrode is the stainless steel-based mesh electrode with activated coating, anode electrode is titanium base net shape electrode, perfluorinated ion-exchange membrane 3 is DF2801 type chlor-alkali perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane ionic membrane, useful area 50dm
2
(2) anolyte is the aqueous solution of sodium sulfate, and catholyte is sodium hydroxide solution; With anolyte and catholyte raw material preheating to 35 ℃, with pump anolyte and catholyte are squeezed in the anolyte compartment and cathode compartment of electrolyzer respectively more first;
(3) under 45 ℃, carry out constant-current electrolysis, current density 3.5kA/m to the logical direct current of electrolyzer
2, anolyte advances groove vitriol mass concentration and is controlled at 40%, flow velocity 9.66L/h; Catholyte advances groove mass concentration 29%, goes out groove mass concentration 31%; Anode and cathode pressure reduction is controlled at 4kPa.
(4) anode that step (3) is obtained go out tank liquor after filtration, freezing, crystallization, centrifugation, drying namely gets the high purity persulphate again.Recycling Mother Solution is used.
Through data processing, this technological process current efficiency is 98.33%, and power consumption is 2060kWh/t, the purity of product Sodium Persulfate＞99.69%.
Embodiment 3:
With embodiment 1, difference is that current density is 3.5kA/m in the step (3)
2
Through data processing, this technological process current efficiency is 98.47%, and power consumption is 2210kWh/t, the purity of product ammonium persulphate＞99.72%.
Embodiment 4:
With embodiment 1, difference is that step (3) Anodic liquid advances groove ammonium sulfate mass concentration and is controlled at about 36% flow velocity 0.072L/h.
Through data processing, this technological process current efficiency is 98.55%, and power consumption is 2215kWh/t, the purity of product ammonium persulphate＞99.76%.
Embodiment 5:
With embodiment 1, difference is that catholyte ammonium hydroxide advances groove mass concentration 30% in the step (3), goes out groove mass concentration 32%.
Through data processing, this technological process current efficiency is 98.58%, and power consumption is 2223kWh/t, the purity of product ammonium persulphate＞99.87%.
Embodiment 6:
With embodiment 2, difference is that perfluorinated ion-exchange membrane 3 is N966 type chlor-alkali perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane ionic membrane in the step (1).
Through data processing, this technological process current efficiency is 98.37%, and power consumption is 2260kWh/t, the purity of product Sodium Persulfate＞99.79%.
Embodiment 7:
With embodiment 2, difference is that difference is that current density is 5.5kA/m in the step (3)
2, anolyte advances groove sodium sulfate flow velocity 14.76L/h.
Through data processing, this technological process current efficiency is 98.54%, and power consumption is 2120kWh/t, the purity of product Sodium Persulfate＞99.79%.
Claims (10)
1. the electrolytic oxidation based on ion-exchange membrane electrolyzer for chlor-alkali production prepares the method for persulphate, by use the electrolyzer that perfluorinated ion-exchange membrane is set and is mainly consisted of by anolyte compartment, anode, perfluorinated ion-exchange membrane, negative electrode, cathode compartment between electrode, carry out according to the following steps:
(1) anolyte and catholyte are supplied to respectively in the anolyte compartment and cathode compartment of this electrolyzer, carry out the electrochemical ion exchange; Wherein, described anolyte is the aqueous solution (M of vitriol
2SO
4), catholyte is the alkaline solution (MOH) corresponding with positively charged ion in the described vitriol; The vitriol general formula is M
2SO
4, wherein M=K, Na, NH
4
(2) carry out constant-current electrolysis to the logical direct current of electrolyzer, under electric field action, positively charged ion (M in the sulfate liquor in the anolyte compartment
+) to cathode direction migration and see through perfluorinated ion-exchange membrane and enter cathode compartment, water molecules is decomposed into hydrogen and hydroxide ion at negative electrode in the cathode compartment, hydroxide ion with see through positively charged ion (M in the sulfate liquor that the perfluorinated ion-exchange membrane migration comes
+) in conjunction with generating alkali (MOH), i.e. alkaline solution;
Water molecules in the anolyte compartment is decomposed into oxygen and hydrogen ion at anode, and sulfate ion can't and be enriched in the anolyte compartment through ion-exchange membrane in the sulfate liquor, and the migration of anode direction generates persulfate in the anode discharge; With M
+In conjunction with generating persulphate;
(3) collect the tank liquor that goes out that persulphate is rich in the anolyte compartment, can obtain the high purity persulphate through concentrated, crystallization treatment.
2. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that described persulphate is Sodium Persulfate, Potassium Persulphate or ammonium persulphate; Vitriol is sodium sulfate, vitriolate of tartar or ammonium sulfate, and described catholyte is corresponding sodium hydroxide, potassium hydroxide or ammoniacal liquor.
3. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that described electrolysis temperature is 20 ℃～55 ℃.
4. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that electrolysis temperature is 35 ℃～45 ℃; Preferred 40 ℃.
5. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that when electrolysis temperature is higher than room temperature, and described anolyte and catholyte stock liquid are preheating to first when being lower than 5～10 ℃ of electrolysis temperatures and pass in the electrolyzer.
6. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, and the current density that it is characterized in that described constant-current electrolysis is 1-6kA/m
2, preferred 3-4.5kA/m
2
7. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that in the electrolytic process, keeps certain pressure between cathode compartment and anolyte compartment, and the cathode compartment gaseous pressure is higher than the anolyte compartment, and anode and cathode pressure reduction is controlled at 0.1-5kPa; Preferred this anode and cathode pressure reduction is 2 ~ 4kPa.
8. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that the control anolyte advances the groove sulfate concentration at 25～40wt% when carrying out constant-current electrolysis to the logical direct current of electrolyzer; Catholyte advances groove mass concentration 15%～28%, goes out groove mass concentration 20%～32%, goes out the groove mass concentration and exceeds into groove mass concentration 2 ~ 5%.
9. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that described perfluorinated ion-exchange membrane is chlor-alkali perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane; Described negative electrode is stainless steel or Ni-based mesh electrode, and anode electrode is titanium base net shape electrode.
10. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that described electrolyzer is the single cell electrolyzer, or a plurality of unit electrolytic bath serial or parallel connection forms the combined electrolysis groove.
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| CN108707921A (en) * | 2018-05-28 | 2018-10-26 | 华南理工大学 | A kind of device and method for being electrolysed while generating persulfate and its activator ferrous ion |
| CN110073036A (en) * | 2017-01-13 | 2019-07-30 | 东丽株式会社 | The manufacturing method of ammonium persulfate |
| CN111020623A (en) * | 2019-12-31 | 2020-04-17 | 河北中科同创科技发展有限公司 | Closed electrolytic tank |
| CN111472016A (en) * | 2020-04-15 | 2020-07-31 | 中南大学 | Method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid |
| CN111547902A (en) * | 2020-05-07 | 2020-08-18 | 中南大学 | Device for removing pollutants by in-situ generation of persulfate and hydrogen peroxide and treatment method |
| CN113174604A (en) * | 2021-04-13 | 2021-07-27 | 浙江工业大学 | Method for preparing sodium persulfate through direct electrooxidation |
| CN113881952A (en) * | 2021-10-28 | 2022-01-04 | 浙江工业大学 | Electrolytic synthesis method of high sodium sulfate |
| CN116641071A (en) * | 2023-05-31 | 2023-08-25 | 亚泰电化有限公司 | Preparation method of high-purity potassium persulfate |
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| CN110073036A (en) * | 2017-01-13 | 2019-07-30 | 东丽株式会社 | The manufacturing method of ammonium persulfate |
| TWI736732B (en) * | 2017-01-13 | 2021-08-21 | 日商東麗股份有限公司 | Manufacturing method of ammonium persulfate |
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| CN113174604A (en) * | 2021-04-13 | 2021-07-27 | 浙江工业大学 | Method for preparing sodium persulfate through direct electrooxidation |
| CN113881952A (en) * | 2021-10-28 | 2022-01-04 | 浙江工业大学 | Electrolytic synthesis method of high sodium sulfate |
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