CN102877085B - 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 ion-exchange membrane electrolyzer for chlor-alkali production perfluorinated ion-exchange membrane method electrolysis vitriol synthesis persulphate, belongs to inorganic electrochemical synthesis field.
Background technology
Persulphate mainly comprises ammonium persulphate, Sodium Persulfate and Potassium Persulphate, is referred to as alkali metal persulphate, of many uses.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 emulsion polymerization in aqueous, the initiator that persulfide is formed as synthetic chloroprene rubber or emulsion polymerization body free radical.Can be used as initiator during tetrafluoroethylene polymerization, some water-soluble monomers such as the polymerizations such as acrylicacidandesters, acrylamide, vinyl acetate or copolymerization also make initiator with it.As oxygenant and SYNTHETIC OPTICAL WHITNER, be widely used in the Storage Battery Industry in China; It is also 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 used as flour and starch processing industry, oil prodution industry, as wheat modification agent, cereuisiae fermentum mould inhibitor; Photographic industry is used for remove hypo.
The production of persulphate has two kinds of methods, and one is electrolytic process, and two is anthraquinone.Anthraquinone have the little feature of energy consumption, but product purity is not high, and subsequent purification is more complicated; The feature of electrolytic process is that product purity is high, but power consumption is also higher.(development persulphate process for cleanly preparing [J] that Xiao Ke waits by force, Henan chemical industry, 06 phase in 2010,28-30) think that the current persulphate production technique of China is equivalent to the level of world's eighties in 20th century, be the continuity that Potassium Persulphate method produces hydrogen peroxide process, especially cell construction 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, about report comprises: (the research of Process for Electrosynthesis of Ammonium Persulfate such as Zhao Jianhong, Zhengzhou University's journal, 27th volume the 1st phase in 2006) to disclose with ammonium sulfate be raw material, in homemade box electrochemical reactor, adopt titanium base platinized electrode to be anode, lead antimony alloy electrode is negative electrode, Nafion427 cationic exchange membrane is barrier film, electrolytic preparation ammonium persulphate.With current efficiency and productive rate for optimization aim, investigate the impact of many factors on electrolytic reaction. the optimal conditions obtained is: in by product ammonium sulfate, p-aminophenol content is less than 0.05%, and starting point concentration is 36.5%, and anode additive is the ammonium polyphosphate of 0.06%, electrolysis temperature 15 DEG C.Turn on angle 72.48Ah, has carried out the repetition electrolytic experiment of 5 batches under this better condition, and current efficiency is all higher than 80%, and productive rate is all higher than 55%.Product, through crystallization, separation, drying, can obtain the ammonium persulphate product of massfraction more than 99.5%.(electrolysis dilute ammonium sulfate solution produces ammonium persulphate [J] to Cong Yufeng etc., Fusun PetroleumCollege's journal, phase calendar year 2001 04) produce the byproduct-dilute ammonium sulfate solution of vinyl cyanide for raw material with Fushun Petrochemical Company acrylic fiber chemical factory, adopt Process for Electrosynthesis of Ammonium Persulfate, under certain temperature, Pt is adopted to make anode, Pb makes negative electrode, tetrafluoroethylene cationic membrane is barrier film, adding a certain amount of self-control inhibitor is additive, electrolytic preparation ammonium persulphate, transformation efficiency can reach 95%, adopt crystallization process separated product, and by iodimetry,iodometry, product purity is measured, ammonium persulphate massfraction reaches 99%, investigated the kind of additive simultaneously, consumption, the kind of barrier film, current density, electrolysis time is on the impact of products collection efficiency.Experiment shows, produces ammonium persulphate product by this method, and technique is simple, processing ease, and production process is polluted little, and product is easily separated, and purity is high, is the best approach utilizing dilute ammonium sulfate solution to produce ammonium persulphate.Yellow Yongming (Production Status of Ammonium Persulfate by Electroynthesis [J], Guangdong chemical industry, 04 phase in 2007) summary thinks that electrolytic process prepares the cathode current density 0.5kA/m of ammonium persulphate
2, voltage 5-7V, temperature controls at 30 ~ 50 DEG C, and current efficiency is about 80%, and electrolytic power consumption 1.8-2.2kWh/t is carbon isotopes.The auspicious clear grade of model (electrolytic process prepares the applied research inorganic chemicals industry [J] of ammonium persulphate, 02 phase in 1997) electrolytic process preparation (NH
4)
2s
2o
8research air electrode replaces lead electrode, makes original bath voltage drop to 3.5V up to more than 5.8V; Research ionic membrane replaces ceramic membrane, can reduce bath voltage 0.65V, is studied by antianode promotor, makes current efficiency bring up to 83% by 62%.
But till now, the current efficiency that electrolytic process prepares persulphate is still on the low side, causes power consumption too high, does not meet the requirement of current low carbon development.
Start to be applied in chlor-alkali electrolytic cells the fifties in eighties of last century to the selective ion-exchange membrane through characteristic of ion.Du pont company develops 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 also develop the perfluorinated ion-exchange membrane of similar in succession.Within 1976, Japanese Asahi Kasei Corporation instead of the perfluoro sulfonic acid membrane of E.I.Du Pont Company with perfluorocarboxylic acid film, and develops carboxylic acid-sulfonic acid composite membrane.Within 2009, start Shandong Dongyue Polymer Material Co., Ltd. and research and develop successfully domestic Membrane Used In Chlor-alkali Cell (i.e. perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane), and take the lead in dropping into the experimental installation (2.7m of Lanxing (Beijing) Chemical Machinery Co., Ltd. in Huanghua chlor-alkali company limited of Cangzhou Dahua Group company limited
2nBH electrolyzer) trial run, obtain initial success.Subsequently again at Dongyue Fluorine-Silicon Material Co., Ltd., Shandong's chlor-alkali plant ten thousand tons of devices, Zhong Yan Changzhou chemical industry limited-liability company chlor-alkali plant F
2the successful Application such as device.
Current business-like chlorine industry perfluorinated ion-exchange membrane (Membrane Used In Chlor-alkali Cell) is perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane, and when perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane is used for electrolyzer, the anode side of composite membrane is perfluorinated sulfonic acid layer, cathode side is perfluorocarboxylic acid layer.Preparation method is see CN101811359A.Sulphonic layer has higher ion permeable ability, and is have lower bath voltage in 20% ~ 30% at alkali concn, thus can save power consumption significantly; And carboxylic layer can stop OH
-the infiltration migration of ion anode, ensures higher current efficiency.Because of its distinctive negatively charged ion blocking effect, chlorine industry perfluorinated ion-exchange membrane, except being applied to chlor-alkali, can also being widely used in other electrochemical synthesis fields, preparing highly purified fine chemicals.
Chinese patent document CN1233585A(CN99104507.6) disclose a kind of method adopting electrolytic preparation ammonium persulphate, adopt aluminum oxide diaphragm cell, comprise electrolysis and be used as the sulphate-containing ion of anode material and the aqueous solution of ammonium ion, crystallization electrolysate, crystal is isolated from mother liquor, the described raw material for anode is made up of ammonium sulfate solution, and wherein the amount of ammonium ion is at least 1 equivalent (2 times 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 only have 80.3%-87.2%; 2. the caustic soda generated is consumed, but not is be used as product widely as one to produce separately, and cause product single, production efficiency is low.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that electrolytic oxidation based on ion-exchange membrane electrolyzer for chlor-alkali production prepares high purity persulphate, the present invention is the electrochemical method for synthesizing adopting ion-exchange membrane electrolysis electrolysis sulfate liquor to prepare 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 being used between electrode, perfluorinated ion-exchange membrane being set and the electrolyzer formed primarily of anolyte compartment, anode, perfluorinated ion-exchange membrane, negative electrode, cathode compartment, carrying out according to the following steps:
(1), in anolyte compartment anolyte and catholyte being supplied to this electrolyzer respectively and cathode compartment, electrochemical ion exchange is carried out; Wherein, described anolyte is the aqueous solution (M of vitriol
2sO
4), catholyte is the alkaline solution (MOH) corresponding with the positively charged ion in described vitriol;
Vitriol general formula is M
2sO
4, wherein M=K, Na, NH
4;
(2) lead to direct current to electrolyzer and carry out constant-current electrolysis, under electric field action, the sulfate liquor cationic (M in anolyte compartment
+) to cathode direction migration and enter cathode compartment through perfluorinated ion-exchange membrane, in cathode compartment, water molecules is decomposed into hydrogen and hydroxide ion on negative electrode, hydroxide ion with move through perfluorinated ion-exchange membrane the sulfate liquor cationic (M come
+) combine generation alkali (MOH), i.e. alkaline solution;
Water molecules in anolyte compartment is decomposed into oxygen and hydrogen ion on anode, in sulfate liquor sulfate ion cannot through ion-exchange membrane enrichment in the anode compartment, and anode direction migration on anode electric discharge generate persulfate; With M
+in conjunction with generation persulphate;
(3) that collects that anolyte compartment is rich in persulphate goes out tank liquor, can obtain high purity persulphate through concentrated, crystallization treatment.Described concentrated, crystallization treatment press techniques well known.
The alkali collecting cathode compartment enrichment goes out tank liquor and can carry out recycle.By techniques well known.
The hydrogen that during electrolysis, cathode and anode generates and oxygen, both can collect as by product and use, also can be directly emptying, 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, potassium sulfate or ammonium sulfate, and described catholyte is corresponding sodium hydroxide, potassium hydroxide or ammoniacal liquor.
Preferred according to the present invention, anolyte compartment goes out tank liquor persulphate concentration in mass concentration 20% ~ 35%.
According to the method for electrolytic preparation persulphate of the present invention, preferred following electrolytic condition:
Described electrolysis temperature is 20 DEG C ~ 55 DEG C, and further preferably, electrolysis temperature is 35 DEG C ~ 45 DEG C, is most preferably with 40 DEG C.
Preferably, when electrolysis temperature is higher than room temperature, described anolyte and catholyte stock liquid first can be preheating to and pass in electrolyzer lower than during electrolysis temperature 5 ~ 10 DEG C again.
The current density of described constant-current electrolysis is 1-6kA/m
2, preferably 3-4.5kA/m
2.
Preferred according to the present invention, in electrolytic process, keep certain pressure between cathode compartment and anolyte compartment, cathode compartment gaseous pressure is higher than anolyte compartment, and anode and cathode pressure reduction controls at 0.1-5kPa, and preferably this anode and cathode pressure reduction is 2 ~ 4kPa.
When leading to direct current to electrolyzer and carrying out constant-current electrolysis, control anolyte and catholyte into and out of groove concentration: make described anolyte enter groove vitriol mass concentration and control at 25 ~ 42wt%, preferably entering groove vitriol mass concentration is 30-40%; Catholyte (alkaline solution) enters groove mass concentration 15% ~ 28%, goes out groove mass concentration 20% ~ 32% accordingly, goes out groove mass concentration and exceeds into groove mass concentration 2 ~ 5%.Described catholyte goes out groove concentration and can control by adding pure water.
According to the present invention, wherein anode material flow quantity Q(L/h) be calculated as follows acquisition:
In formula, I is DC electrolysis electric current, unit A; Mn is the molecular weight of vitriol in anolyte feedstock solution; X is for entering groove vitriol mass percent concentration; F is Faraday's number, 96485C/mol.
Anode of the present invention, perfluorinated ion-exchange membrane, negative electrode are chlorine industry common technology.Wherein preferred perfluorinated ion-exchange membrane is chlor-alkali perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane, buy by market, or by prior art preparation, preparation method is see CN101811359A, concrete as its specification sheets embodiment 1, embodiment 2, embodiment 3 or embodiment 4.
Described cathode electrode is the mesh electrode of the mesh electrode of stainless steel or nickel-base strip activated coating, preferred stainless steel or nickel-base strip activated coating; Anode electrode is titanium base mesh electrode.By prior art, market is bought.
Described ion-exchange membrane electrolyzer can be single cell electrolyzer (Fig. 1), also multiple unit electrolytic bath series connection can form bipolar cell (Fig. 2).
For ammonium sulfate electrolysis, principle of the present invention is described below: the ammonium sulfate solution in electrolyzer anode chamber is under the effect of electrical forces, and the sulfate ion anode direction migration in solution until discharge and generate persulfate on anode.Meanwhile, due to the selective penetrated property of ionic membrane, sulfate ion cannot diffuse transmission ion-exchange membrane, only has ammonium ion could select through and enter cathode compartment, and is enriched in wherein.In electric tank cathode room, water molecules is decomposed into hydrogen and hydroxide ion on negative electrode.The latter is combined into ammonium hydroxide with being moved the ammonium ion come by anolyte compartment just.
Ammonium sulfate ((NH
4)
2sO
4) electrolytic preparation ammonium persulphate electrode reaction is as follows:
2SO
4 2-－2e→S
2O
8 2-↑
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:
1, electrolysis process of the present invention avoids power consumption in existing method high, the shortcomings such as current efficiency is low, and present method is simple, easily realizes industrial amplification production.
2, the cation selective of negative electrode is moved to negative electrode by electrolysis by method of the present invention, avoids 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 utilizes chlor-alkali ion groove electrolyzer, has both played the speciality that fluoro-containing macromolecule material electrochemical corrosion resistant is strong, negatively charged ion can be stoped again 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 described, but the present invention is not limited only to following examples.
The perfluorinated ion-exchange membrane used in embodiment is commercial goods film, DF988 type, DF2801 type chlor-alkali perfluorocarboxylic acid-perfluorinated sulfonic acid composite ionic membrane, and Shandong Dongyue Polymer Material Co., Ltd. produces, and N966 type ionic membrane E.I.Du Pont Company produces.
The stainless steel-based mesh electrode of the Ni-based mesh electrode with activated coating in embodiment, band activated coating, titanium base mesh electrode are the conventional products of chlorine industry, and Zibo Chemical Equipment Co., Ltd. of Golden Bridge provides.
Data processing:
In A, embodiment, the purity testing of product persulphate measures according to GB/T 23939-2009 method.
B, the inventive method can calculate the cathode efficiency η (%) of for some time Inner electrolysis process with formula (I):
In formula, for sodium hydroxide as cathode materials liquid:
η---current efficiency, %;
F---Faraday's number (96485C/mol);
M---in electrolytic process, for some time inner cathode collects the quality of product sodium hydroxide solution, g;
The massfraction of the sodium hydroxide solution of c---cathode collector, %;
N---the electricity (Amin) by electrolyzer in for some time in electrolytic process, the product by electric current and time obtains;
The molecular weight of M---sodium hydroxide, 40g/mol.
C, the inventive method can calculate the ton product power consumption of for some time Inner electrolysis process with formula (II):
In formula:
Θ---report period Inner electrolysis direct current consumption, unit is kilowatt-hour (kWh);
M---product day output in the report period, unit is tpd (t/d);
The time (being generally 72 hours) of t---report period, unit is hour (h).
Note: runtime every day calculated by 24 hours.
Embodiment 1:
A method for electrolytic preparation high purity persulphate, arranging perfluorinated ion-exchange membrane 3 and the electrolyzer formed primarily of anolyte compartment 4, anode 1, perfluorinated ion-exchange membrane 3, negative electrode 2, cathode compartment 5 by being used between electrode, carrying out according to the following steps:
(1) in ion-exchange membrane electrolyzer as shown in Figure 1, electrochemical ion exchange is carried out, cathode electrode is the Ni-based mesh electrode of band activated coating, anode electrode is titanium base mesh 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) anolyte raw material is the aqueous solution of 30% mass concentration ammonium sulfate, and catholyte raw material is 28% mass concentration solution of ammonium hydroxide; Anode material liquid and cathode materials liquid squeezed in the anolyte compartment of electrolyzer and cathode compartment with pump respectively and circulate;
(3) at 35 DEG C, lead to direct current to electrolyzer and carry out constant-current electrolysis, current density 1.5kA/m
2, enter groove anolyte ammonium sulfate concentrations and control 30%, flow velocity 0.086L/h; Catholyte solution of ammonium hydroxide enters groove mass concentration 28%, goes out groove mass concentration 30%; Anode and cathode pressure reduction controls at 2kPa.Ammonium persulfate concentrations adopts national standard (GB/T 23939-2009 industry ammonium persulphate) to measure.
(4) the anode that step (3) obtains go out tank liquor after filtration, freezing, crystallization, centrifugation, then drying, obtains high purity ammonium persulphate.Recycling Mother Solution uses.
Through Data Management Analysis, this technological process current efficiency is 98.33%, and power consumption is 2170kWh/t, the purity > 99.69% of product ammonium persulphate.
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, electrochemical ion exchange is carried out, cathode electrode is the stainless steel-based mesh electrode of band activated coating, anode electrode is titanium base mesh 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; First by anolyte and catholyte raw material preheating to 35 DEG C, then in anolyte compartment anolyte and catholyte being squeezed into electrolyzer with pump respectively and cathode compartment;
(3) at 45 DEG C, lead to direct current to electrolyzer and carry out constant-current electrolysis, current density 3.5kA/m
2, anolyte enters groove vitriol mass concentration and controls 40%, flow velocity 9.66L/h; Catholyte enters groove mass concentration 29%, goes out groove mass concentration 31%; Anode and cathode pressure reduction controls at 4kPa.
(4) the anode that step (3) obtains go out tank liquor after filtration, freezing, crystallization, centrifugation, then drying, obtains high purity persulphate.Recycling Mother Solution uses.
Through data processing, this technological process current efficiency is 98.33%, and power consumption is 2060kWh/t, the purity > 99.69% of product Sodium Persulfate.
Embodiment 3:
With embodiment 1, difference is that in step (3), current density is 3.5kA/m
2.
Through data processing, this technological process current efficiency is 98.47%, and power consumption is 2210kWh/t, the purity > 99.72% of product ammonium persulphate.
Embodiment 4:
With embodiment 1, difference is that step (3) Anodic liquid enters groove ammonium sulfate mass concentration and controls 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 > 99.76% of product ammonium persulphate.
Embodiment 5:
With embodiment 1, difference is that in step (3), catholyte ammonium hydroxide enters groove mass concentration 30%, 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 > 99.87% of product ammonium persulphate.
Embodiment 6:
With embodiment 2, difference is that in step (1), perfluorinated ion-exchange membrane 3 is N966 type chlor-alkali perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane ionic membrane.
Through data processing, this technological process current efficiency is 98.37%, and power consumption is 2260kWh/t, the purity > 99.79% of product Sodium Persulfate.
Embodiment 7:
With embodiment 2, difference is difference is that in step (3), current density is 5.5kA/m
2, anolyte enters 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 > 99.79% of product Sodium Persulfate.
Claims (11)
1. the electrolytic oxidation based on ion-exchange membrane electrolyzer for chlor-alkali production prepares the method for persulphate, arrange perfluorinated ion-exchange membrane and the electrolyzer formed primarily of anolyte compartment, anode, perfluorinated ion-exchange membrane, negative electrode, cathode compartment by being used between electrode, described perfluorinated ion-exchange membrane is chlor-alkali perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane; Carry out according to the following steps:
(1), in anolyte compartment anolyte and catholyte being supplied to this electrolyzer respectively and cathode compartment, electrochemical ion exchange is carried out; Wherein, described anolyte is the aqueous solution (M of vitriol
2sO
4), catholyte is the alkaline solution (MOH) corresponding with the positively charged ion in described vitriol; Vitriol general formula is M
2sO
4, wherein M=K, Na, NH
4;
When leading to direct current to electrolyzer and carrying out constant-current electrolysis, control anolyte and enter groove sulfate concentration at 25 ~ 40wt%; Catholyte enters groove mass concentration 15% ~ 28%, goes out groove mass concentration 20% ~ 32%, goes out groove mass concentration and exceeds into groove mass concentration 2 ~ 5%;
(2) lead to direct current to electrolyzer and carry out constant-current electrolysis, the current density of described constant-current electrolysis is 1-6kA/m
2, under electric field action, the sulfate liquor cationic (M in anolyte compartment
+) to cathode direction migration and enter cathode compartment through perfluorinated ion-exchange membrane, in cathode compartment, water molecules is decomposed into hydrogen and hydroxide ion on negative electrode, hydroxide ion with move through perfluorinated ion-exchange membrane the sulfate liquor cationic (M come
+) combine generation alkali (MOH), i.e. alkaline solution;
Water molecules in anolyte compartment is decomposed into oxygen and hydrogen ion on anode, in sulfate liquor sulfate ion cannot through ion-exchange membrane enrichment in the anode compartment, and anode direction migration on anode electric discharge generate persulfate; With M
+in conjunction with generation persulphate;
(3) that collects that anolyte compartment is rich in persulphate goes out tank liquor, obtains high purity persulphate through concentrated, crystallization treatment;
The alkali collecting cathode compartment enrichment goes out tank liquor and carries out recycle.
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, potassium sulfate 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 DEG C ~ 55 DEG C.
4. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that electrolysis temperature is 35 DEG C ~ 45 DEG C.
5. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that electrolysis temperature is 40 DEG C.
6. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, and it is characterized in that when electrolysis temperature is higher than room temperature, described anolyte and catholyte stock liquid are first preheating to and pass in electrolyzer lower than during electrolysis temperature 5 ~ 10 DEG C again.
7. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, it is characterized in that the current density of described constant-current electrolysis is 3-4.5kA/m
2.
8. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, and it is characterized in that, in electrolytic process, keeping certain pressure between cathode compartment and anolyte compartment, cathode compartment gaseous pressure is higher than anolyte compartment, and anode and cathode pressure reduction controls at 0.1-5kPa.
9. electrolytic oxidation as claimed in claim 8 prepares the method for persulphate, it is characterized in that described anode and cathode pressure reduction is 2 ~ 4 kPa.
10. electrolytic oxidation as claimed in claim 1 prepares the method for persulphate, and it is characterized in that described negative electrode is stainless steel or Ni-based mesh electrode, anode electrode is titanium base mesh electrode.
11. electrolytic oxidations as claimed in claim 1 prepare the method for persulphate, it is characterized in that described electrolyzer is single cell electrolyzer, or multiple unit electrolytic bath serial or parallel connection forms combined electrolysis groove.
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| CN113174604B (en) * | 2021-04-13 | 2022-12-06 | 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 |
| CN116641071B (en) * | 2023-05-31 | 2023-11-03 | 亚泰电化有限公司 | Preparation method of high-purity potassium persulfate |
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