CN103518007A - Apparatus for electrolyzing sulfuric acid and method for electrolyzing sulfuric acid - Google Patents

Apparatus for electrolyzing sulfuric acid and method for electrolyzing sulfuric acid Download PDF

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Publication number
CN103518007A
CN103518007A CN201280022515.0A CN201280022515A CN103518007A CN 103518007 A CN103518007 A CN 103518007A CN 201280022515 A CN201280022515 A CN 201280022515A CN 103518007 A CN103518007 A CN 103518007A
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Prior art keywords
sulfuric acid
electrolysis
anode side
loop
concentration
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CN201280022515.0A
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Inventor
土门宏纪
藤井宏治
小坂纯子
加藤昌明
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De Nora Permelec Ltd
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Chlorine Engineers Corp Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Abstract

The present invention relates to an apparatus for producing sulfuric acid that contains a large amount of an oxidizing substance by electrolyzing sulfuric acid, and specifically relates to an apparatus for safely and highly efficiently producing electrolyzed sulfuric acid that contains a large amount of an oxidizing substance by producing diluted sulfuric acid that is controlled in temperature and concentration within an electrolysis apparatus and then electrolyzing the diluted sulfuric acid under temperature-controlled conditions. The present invention provides an apparatus for electrolyzing sulfuric acid, which comprises a positive electrode-side electrolysis unit and a negative electrode-side electrolysis unit, and which is provided with, at least within the positive electrode-side electrolysis unit: a positive electrode-side diluted sulfuric acid generation loop A for diluting concentrated sulfuric acid, which is a supplied starting material, and then adjusting the temperature and the concentration of the thus-diluted sulfuric acid to desired values; and a positive electrode-side electrolyzed sulfuric acid generation loop B for producing electrolyzed sulfuric acid by electrolyzing the diluted sulfuric acid, the temperature and the concentration of which are adjusted to desired values in the loop A, and then adjusting the temperature and the concentration of the thus-produced electrolyzed sulfuric acid to desired values. The present invention also provides a method for electrolyzing sulfuric acid.

Description

Sulfuric acid electrolyzer and sulfuric acid electrolysis process
Technical field
The present invention relates to sulfuric acid electrolyzer and the sulfuric acid electrolysis process of the manufacture of the electrolysis sulfuric acid by sulfuric acid electrolysis is contained to a large amount of oxidizing substances.Particularly, relate to by generating the controlled dilute sulphuric acid of temperature and concentration and then this temperature and the controlled dilute sulphuric acid of concentration are carried out to electrolysis in sulfuric acid electrolyzer, carry out efficiently and generate safely sulfuric acid electrolyzer and the sulfuric acid electrolysis process of the electrolysis sulfuric acid that contains oxidizing substance.
Background technology
In the past, the medicament that in oxygenant in processing as the cmp in the pretreating reagent of Metal plating or etching reagent, semiconductor devices manufacture, wet analysis, the washing composition of organic oxygenant, silicon wafer etc. is used in various manufacturing process, in checking technique, has been used persulfuric acid.This persulfuric acid is known as " oxidizing substance ", knownly by sulfuric acid electrolysis, is generated, and has realized plant-scale electrolysis manufacture.
In the present invention, described " oxidizing substance " refers to persulfuric acid, the hydrogen peroxide such as peroxy-disulfuric acid, permonosulphuric acid, and described " electrolysis sulfuric acid " refers to by sulfuric acid being carried out to the product that electrolysis is manufactured, and it comprises above-mentioned oxidizing substance and unreacted sulfuric acid.
The electrolysis sulfuric acid that comprises oxidizing substance and unreacted sulfuric acid generating in sulfuric acid electrolyzer (being designated hereinafter simply as " electrolysis sulfuric acid ") in semi-conductor manufacturing process for removing resist, Organic Pollutants, pollution metal etc.For these purposes, therefore the higher effect of removing of known oxygen voltinism material concentration is better, sulfuric acid electrolyzer is had to following requirement: can generate the electrolysis sulfuric acid that contains greater concn oxidizing substance, by electrolysis, to generate the efficiency of oxidizing substance the decomposability higher and oxidizing substance that generates low.In sulfuric acid electrolysis, for generate the electrolysis sulfuric acid that contains high density oxidizing substance, further improve because of electrolysis generate oxidizing substance efficiency, reduce the decomposability of this oxidizing substance, require to supply with to sulfuric acid electrolyzer the sulfuric acid of the lower concentration that is adjusted to desired concn.
Yet, generally speaking, sulfuric acid is sold with the form of 98% or 96% the vitriol oil, thereby, in order to supply with concentration through the low-concentration sulfuric acid (also referred to as dilute sulphuric acid) of the dilution of adjustment to sulfuric acid electrolyzer, what be necessary in the liquid supply arrangement of factory newly-built special use stores tank, supply line, and this situation needs the equipment cost of great number.In addition, compare with the vitriol oil, the volume of low-concentration sulfuric acid is larger, and therefore there are the following problems: compare with transporting the vitriol oil, the shipment and delivery cost of medicine also increases.
If can adjust efficiently sulfuric acid concentration in sulfuric acid electrolyzer, equipment cost, shipment and delivery cost etc. can be prepared to the required cost of dilute sulphuric acid and be suppressed at inferior limit, thereby can realize the sulfuric acid electrolysis that electrolysis low-concentration sulfuric acid generates oxidizing substance efficiently simultaneously.In addition, if can make as far as possible to form by the vitriol oil, generate the mechanism of dilute sulphuric acid and the machine and the circuit that by dilute sulphuric acid, are generated containing the mechanism of the electrolysis sulfuric acid of oxidizing substance reach universalization, can realize miniaturization and the summary of sulfuric acid electrolyzer.
Patent documentation 1 has been recorded electrolysis sulfuric acid in electrolyzer and has been generated the technology of persulfuric acid, in its 0011 section, recorded following content: " sulfuric acid that generates persulfuric acid by being used in is the low-concentration sulfuric acid of concentration range in 2～11mol/L, can improve the formation efficiency of persulfuric acid ".
Persulfuric acid plenum system has been proposed in patent documentation 2, recorded following content for its 0026 section: " being just supplied to the sulfuric acid concentration ranges of the electrolytic solution in electrolysis reaction device; by making it, be the low-concentration sulfuric acid of 10～18M (mol/L), can improve the formation efficiency of persulfuric acid ".
In 0012 section and 0018 section of patent documentation 3, recorded a kind of method, it is " by using the sulfuric acid of different concns as electrolytic solution; thereby improving for when generating the current efficiency of electrolysis sulfuric acid, efficiently and stably generate the method for oxidizing substance ".
Then, although disclose in the method that patent documentation 1～3 is recorded, can realize high efficiency generation by the sulfuric acid of electrolysis lower concentration, and the unexposed density adjusting method about sulfuric acid.
In order to manufacture the dilute sulphuric acid of lower concentration, generally be necessary the vitriol oil to mix with pure water next suitable adjustment sulfuric acid concentration, but when sulfuric acid is mixed with pure water, can produce a large amount of heats of dilution, and then occur bumping or produce in large quantities steam, the mist owing to the heat of dilution.Therefore, the problem existing is: if for from carrying out the tank of sulfuric acid concentration adjustment, the exhaust of equipment do not add any processing just with exhaust equipment, the equipment connection of removing the evil, in exhaust equipment, the equipment of removing the evil, sulfuric acid can be sneaked into, burn into performance degradation can be directly caused thus.
As the method for removing sulfuric acid contained in the water electrolytic gas being produced by electrolysis reaction device, a kind of gas-liquid separation mechanism is disclosed in patent documentation 4.But, although the steam, the sulfuric acid in mist that produce while carrying out sulfuric acid concentration adjustment in its device are more than sulfuric acid contained in water electrolytic gas, but for steam and the removing of mist of carrying out producing when sulfuric acid concentration is adjusted, do not disclose, also unexposed for sulfuric acid concentration inflation method.
In patent documentation 5 relevant for by washing after used sulfuric acid reconcentration, dilute and cooling and carry out the record that electrolysis again generates the method for persulfuric acid, but need to used sulfuric acid in the washing of supplying with lower concentration is temporarily concentrated, thereby, spatter property is different, and has the problem of security aspect.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-66464 communique
Patent documentation 2: TOHKEMY 2008-111184 communique
Patent documentation 3: TOHKEMY 2010-34521 communique
Patent documentation 4: TOHKEMY 2007-262532 communique
Patent documentation 5: TOHKEMY 2008-244310 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of sulfuric acid electrolyzer and sulfuric acid electrolysis process, the heat that it produces in the time of can removing the heat of dilution that produces when diluting concentrated sulfuric acid is become to the sulfuric acid of lower concentration and electrolysis, adjustment can generate the electrolytic condition of oxidizing substance efficiently, inhibition is owing to the mist of the heat of dilution, the generation of steam, and the drop that condenses of sneaking into the mist of exhaust system, the sulfuric acid that steam brings etc. is also removed from exhaust system, electrolysis more efficiently generates oxidizing substance, long-term safety and stably working.
The method of dealing with problems
In order to address the above problem, the invention provides a kind of sulfuric acid electrolyzer, in thering is the sulfuric acid electrolyzer 1 of anode side electrolysis portion 20 and cathode side electrolysis portion 23, at least in anode side electrolysis portion 20, be provided with dilution and be adjusted to the anode side dilute sulphuric acid generation loop A of required temperature and concentration and the anode side electrolysis sulfuric acid generation loop B that the dilute sulphuric acid electrolysis generating in this dilute sulphuric acid generation loop A is generated to electrolysis sulfuric acid and the electrolysis sulfuric acid of generation is adjusted to required temperature and concentration as the vitriol oil of base feed and by the dilute sulphuric acid after dilution; Above-mentioned anode side dilute sulphuric acid generates in the A of loop, anode side tank 31, anode side vitriol oil supply unit 32 and anode side water cooler 34 configure successively, they are linked and are formed loop by anode side by-pass line 36, and, any part in the A of Gai loop is connected with can be to the anode side pure water supply line 10 of supplying with pure water in the A of loop, in addition, be also connected with the anode side vitriol oil supply line 27 of supplying with the vitriol oil to above-mentioned anode side vitriol oil supply unit 32 for realizing; Above-mentioned anode side electrolysis sulfuric acid generates in the B of loop, the anolyte compartment 4 that inside in above-mentioned anode side tank 31 and electrolyzer 2 is provided with anode 3 is linked and is formed loop by anode side circulation line 37, and described electrolyzer 2 comprises anolyte compartment's 4 cathode compartments 7 that form by barrier film 5; The vitriol oil that is supplied to anode side vitriol oil supply unit 32 from above-mentioned anode side vitriol oil supply line 27 is diluted by the pure water of supplying with from above-mentioned anode side pure water supply line 10, and the low-concentration sulfuric acid after dilution is adjusted to required temperature and concentration during the A internal recycle of above-mentioned loop, generates and be adjusted into temperature required and dilute sulphuric acid concentration; The dilute sulphuric acid generating is supplied to the anolyte compartment 4 of above-mentioned electrolyzer 2 via the anode side circulation line 37 that forms above-mentioned loop B, in Gai anolyte compartment 4, generate electrolysis sulfuric acid, and the electrolysis sulfuric acid generating is adjusted to required temperature and concentration during the B internal recycle of above-mentioned loop, generates and be adjusted into temperature required and electrolysis sulfuric acid concentration.
In addition, the 2nd settling mode of the present invention is to provide a kind of above-mentioned sulfuric acid electrolyzer, and it is further provided with dilution and as the vitriol oil of base feed, obtains the sulfuric acid of lower concentration the cathode side electrolysis loop B ' that the cathode side dilute sulphuric acid that the sulfuric acid of this lower concentration is adjusted to required temperature and concentration is generated to loop A ' and this dilute sulphuric acid is generated to the logical liquid of the dilute sulphuric acid generating in the A ' of loop to cathode compartment 7 and makes it to circulate in the device of described cathode side electrolysis portion 23; Cathode side dilute sulphuric acid generates in the A ' of loop, cathode side tank 38, cathode side vitriol oil supply unit 39 and cathode side water cooler 41 configure successively, they are linked and are formed loop by cathode side by-pass line 43, and, any part in the A ' of Gai loop is connected with can be to the cathode side pure water supply line 12 of supply pure water in the A ' of loop, in addition, be also connected with the vitriol oil supply line 29 of supplying with the vitriol oil to above-mentioned cathode side vitriol oil supply unit 39 for realizing; In cathode side electrolysis loop B ', the cathode compartment 7 that the inside in above-mentioned cathode side tank 38 and electrolyzer 2 is provided with negative electrode 6 is linked and is formed loop by cathode side circulation line 44, and described electrolyzer 2 comprises anolyte compartment's 4 cathode compartments 7 that form by barrier film 5; The vitriol oil that is supplied to cathode side vitriol oil supply unit 39 from cathode side vitriol oil supply line 29 is diluted by the pure water of supplying with from above-mentioned cathode side pure water supply line 12, the sulfuric acid of the lower concentration after dilution is adjusted to required temperature and concentration during the A ' internal recycle of above-mentioned loop, generates and is adjusted into temperature required and dilute sulphuric acid concentration; The dilute sulphuric acid generating is supplied to the cathode compartment 4 of electrolyzer 2 via the cathode side circulation line 44 that forms above-mentioned loop B ', be to carry out during the B ' internal recycle of loop temperature and concentration through the electrolysis of the dilute sulphuric acid adjusted.
In addition, the 3rd settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, wherein, on described anode side Guan31 top, via anodic gas vent line 102, be connected with anode side gas-liquid separation mechanism 91 and anode side mist separator 92, and make the connection of connecting successively of anode side gas-liquid separation mechanism 91 and anode side mist separator 92, the bottom separately of this anode side gas-liquid separation mechanism 91 and this anode side mist separator 92 possesses for discharging the pumping equipment of the inner liquid of accumulating separately, this pumping equipment possesses and has the structure that has been communicated with anode side gas-liquid separation mechanism 91 and anode side mist separator 92.
In addition, the 4th settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, wherein, on described anode side Guan31 top, via anodic gas vent line 102, be connected with anode side gas-liquid separation mechanism 91 and anode side mist separator 92, and make the connection of connecting successively of this anode side gas-liquid separation mechanism 91 and anode side mist separator 92, the bottom separately of this anode side gas-liquid separation mechanism 91 and this anode side mist separator 92 possesses for discharging the pumping equipment of the inner liquid of accumulating separately, described pumping equipment has the structure that has been communicated with anode side gas-liquid separation mechanism 91 and anode side mist separator 92, and, on described cathode side Guan38 top, via cathode gas vent line 103, be connected with cathode side gas-liquid separation mechanism 96 and cathode side mist separator 97, and make the connection of connecting successively of described cathode side gas-liquid separation mechanism 96 and cathode side mist separator 97, the bottom separately of this cathode side gas-liquid separation mechanism 96 and this cathode side mist separator 97 possesses for discharging the pumping equipment of the inner liquid of accumulating separately, and described pumping equipment has the structure that has been communicated with cathode side gas-liquid separation mechanism 96 and cathode side mist separator 97.
In addition, the 5th settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, and wherein, described anode side mist separator 92 is connected with ozone decomposed mechanism 93.
In addition, the 6th settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, and wherein, described cathode side mist separator 97 is connected with hydrogen processing mechanism.
In addition, the 7th settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, wherein, described dilute sulphuric acid generates in the A of loop and is set side by side with a plurality of described anode side tanks, after the electrolysis sulfuric acid containing oxidizing substance that makes to generate stores in of this anode side tank, switch valve, thus the electrolysis sulfuric acid containing the oxidizing substance of prescribed concentration in other anode side tanks, generated.
In addition, the 8th settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, its formation make can by store the electrolysis sulfuric acid liquor charging containing the oxidizing substance of prescribed concentration in the anode side tank use point (use point) to sulfuric acid electrolyzer during in, with other anode side tanks, generate the electrolysis sulfuric acid containing the oxidizing substance of prescribed concentration.
In addition, the 9th settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, and wherein, described anode 3 is conductive diamond electrodes.
In addition, the 10th settling mode of the present invention is to provide a kind of sulfuric acid electrolyzer, and wherein, described barrier film 5 is porousness fluorine-type resin films of fluorine type resin cationic exchange membrane or process hydrophilicity-imparting treatment.
In addition, the 11st settling mode of the present invention is to provide a kind of sulfuric acid electrolysis process, and the method comprises: with the sulfuric acid electrolyzer described in above-mentioned any one, generate and be adjusted into temperature required and electrolysis sulfuric acid concentration.
In addition, the 12nd settling mode of the present invention is to provide a kind of sulfuric acid electrolysis process, the method comprises: use the sulfuric acid electrolyzer described in above-mentioned any one, and use porousness fluorine-type resin film as described barrier film 5, when the water entrainment of carrying secretly during by this porousness fluorine-type resin film because of positively charged ion causes the liquid measure of the dilute sulphuric acid solution of circulation in the cathode side electrolysis loop B ' of described catholyte portion 23 to increase, termly or when the liquid level of described cathode side tank 38 reaches specified altitude assignment, discharge the liquid of specified amount, prevent thus the overflow of this cathode side tank 38.
In addition, the 13rd settling mode of the present invention is to provide a kind of sulfuric acid electrolysis process, the method comprises: use the sulfuric acid electrolyzer described in above-mentioned any one, and use porousness fluorine-type resin film as described barrier film 5, at the water entrainment of carrying secretly during by this porousness fluorine-type resin film because of positively charged ion, cause the sulfuric acid concentration of the dilute sulphuric acid solution generating in described catholyte Bu23 loop A ' to be reduced to prescribed concentration when following, to described cathode side vitriol oil supply unit 39, supplement the vitriol oil, keep thus the dilute sulphuric acid concentration of certain limit.
In addition, the 14th settling mode of the present invention is to provide the sulfuric acid electrolysis process described in above-mentioned any one, wherein, the dilute sulphuric acid that dilute sulphuric acid in described anode side electrolysis portion 20 generates in loop A or described cathode side electrolysis portion 23 generates in the A ' of loop, carry out temperature adjustment, the temperature that makes the dilute sulphuric acid before electrolysis is below 30 ℃.
In addition, the 15th settling mode of the present invention is to provide the sulfuric acid electrolysis process described in above-mentioned any one, wherein, electrolysis sulfuric acid in described anode side electrolysis portion 20 generates in the cathode side electrolysis loop B ' in loop B or described cathode side electrolysis portion 23, carry out temperature adjustment, the temperature that has made to occur the electrolytic solution of electrolysis is below 30 ℃.
In addition, the 16th settling mode of the present invention is to provide the sulfuric acid electrolysis process described in above-mentioned any one, wherein, the dilute sulphuric acid that dilute sulphuric acid in described anode side electrolysis portion 20 generates in loop A or described cathode side electrolysis portion 23 generates in the A ' of loop, carry out concentration adjustment, the sulfuric acid concentration that makes the dilute sulphuric acid before electrolysis is 2～10mol/L.
The effect of invention
According to sulfuric acid electrolyzer of the present invention and sulfuric acid electrolysis process, can in sulfuric acid electrolyzer, generate and be controlled as required assigned temperature and the dilute sulphuric acid of concentration, and can under the controlled condition of temperature, realize the electrolysis to this dilute sulphuric acid, thus, can be efficiently and generate safely the electrolysis sulfuric acid that contains a large amount of oxidizing substances, and, can manufacture the electrolytic solution that contains oxidizing substance with high density that prior art cannot realize with high current efficiency.
Accompanying drawing explanation
[Fig. 1] illustrates the overall diagram of an example of sulfuric acid electrolyzer of the present invention.
The process picture sheet that [Fig. 2] describes each operations such as the temperature of the sulfuric acid that utilizes the sulfuric acid electrolyzer of Fig. 1 and carry out and concentration adjustment, electrolysis, supply, discharge opeing processing.
[Fig. 3] illustrates the figure of the anode side electrolysis portion 20 in another example of sulfuric acid electrolyzer of the present invention.
The process picture sheet that [Fig. 4] describes each operations such as the temperature of the sulfuric acid that utilizes the sulfuric acid electrolyzer of Fig. 3 and carry out and concentration adjustment, electrolysis, supply, discharge opeing processing.
Nomenclature
A: anode side dilute sulphuric acid generates loop
B: anode side electrolysis sulfuric acid generates loop
A ': cathode side dilute sulphuric acid generates loop
B ': cathode side electrolysis loop
1: sulfuric acid electrolyzer
2: electrolyzer
3: anode
4: anolyte compartment
5: barrier film
6: negative electrode
7: cathode compartment
10: anode side pure water supply line
11: anode side pure water supply valve
12: cathode side pure water supply line
13: cathode side pure water supply valve
20: anode side electrolysis portion
21: anolyte compartment's inlet valve
22: anolyte compartment's outlet valve
23: cathode side electrolysis portion
24: cathode compartment inlet valve
25: cathode compartment outlet valve
27: anode side vitriol oil supply line
28: anode side vitriol oil supply valve
29: cathode side vitriol oil supply line
30: cathode side vitriol oil supply valve
31: anode side tank
32: anode side vitriol oil supply unit
33: anode side recycle pump
34: anode side water cooler
35: anode side by-pass valve
36: anode side by-pass line
37: anode side circulation line
38: cathode side tank
39: cathode side vitriol oil supply unit
40: cathode side recycle pump
41: cathode side water cooler
42: cathode side by-pass valve
43: cathode side by-pass line
44: cathode side circulation line
49: the 1 anode side tanks
50: the 2 anode side tanks
51～58: switch valve
91: anode side gas-liquid separation mechanism
92: anode side mist separator
93: ozone decomposed mechanism
94: anode side gas pipeline tapping valve
95: anode side drain line
96: cathode side gas-liquid separation mechanism
97: cathode side mist separator
98: the cathode gas equipment of removing the evil
99: cathode side gas piping tapping valve
100: cathode side drain line
102: anodic gas vent line
103: cathode gas vent line
110: anode can escape route
111: anode can outlet valve
112: cathode can escape route
113: cathode can outlet valve
the embodiment of invention
Below, the example for enforcement of the present invention, illustrates by reference to the accompanying drawings.
Fig. 1 is the figure that an example of sulfuric acid electrolyzer 1 of the present invention is shown.Sulfuric acid electrolyzer 1 has anode side electrolysis portion 20 and cathode side electrolysis portion 23,2 is electrolyzer.This electrolyzer 2 is divided into anolyte compartment 4 and cathode compartment 7 by barrier film 5, is provided with anode 3 in anolyte compartment 4, is provided with negative electrode 6 in cathode compartment 7.Anolyte compartment 4 is arranged at the anode side electrolysis portion 20 of sulfuric acid electrolyzer 1, the invention is characterized in and forms as described below this anode side electrolysis portion 20.
Anode side electrolysis portion 20 is formed with anode side dilute sulphuric acid and generates loop A and anode side electrolysis sulfuric acid generation loop B.First, in the device of Fig. 1 example, anode side dilute sulphuric acid generates in the A of loop and configures successively anode side tank 31, anode side vitriol oil supply unit 32, anode side recycle pump 33, anode side water cooler 34, and they are linked and formed loop by anode side by-pass line 36.And its formation makes it possible to by being configured in the liquid circulation of the anode side by-pass valve 35 interrupt circuitry A between anode side water cooler 34 and anode side tank 31.
In addition, in the device of Fig. 1 example, anode side tank 31 is connected with anode side pure water supply line 10, and anode side vitriol oil supply unit 32 is connected with anode side vitriol oil supply line 27.The vitriol oil that is supplied to anode side vitriol oil supply unit 32 via anode side vitriol oil supply valve 28 from anode side vitriol oil supply line 27 is in anode side tank 31, by the pure water of supplying with via anode side pure water supply valve 11 from anode side pure water supply line 10, diluted, become the sulfuric acid of lower concentration.Sulfuric acid after dilution is adjusted to required temperature and concentration during the A internal recycle of loop.Anode side dilute sulphuric acid generates temperature required and dilute sulphuric acid concentration that is adjusted to generating in the A of loop, is supplied to and forms the anolyte compartment 4 that anode side electrolysis sulfuric acid generates the electrolyzer 2 of loop B, carries out electrolysis.Anode side electrolysis sulfuric acid generates loop B as described later.
In above-mentioned loop A, for the pure water being supplied in anode side tank 31, use the liquidometer being equipped with in not shown integrating flowmeter or tank to carry out quantitatively, and be supplied to anode side tank 31.Integrating flowmeter can use the integrating flowmeter of ultrasonic type, electromagnetic type, section's formula (Corioli) etc., and operating device is according to the supply of controlling pure water from measured value or the signal of integrating flowmeter or liquid level sensor and stop supply.It should be noted that, anode side pure water supply line 10 connection portion is not limited to, in the example ，Shi loop A of Fig. 1, for it, position is set and be not particularly limited.Inlet valve ，22Shi anolyte compartment, 21Shi anolyte compartment outlet valve, by opening and closing aptly these valves and anode side by-pass valve 35, dilute sulphuric acid generates in loop A or electrolysis sulfuric acid generation loop B and circulates at dilute sulphuric acid respectively.In addition, the 24th, cathode compartment inlet valve, the 25th, cathode compartment outlet valve.
Anode side electrolysis sulfuric acid generates in the B of loop, anode side tank 31 is linked and is formed loop by anode side circulation line 37 with the anolyte compartment 4 of electrolyzer 2, and its formation makes it possible to utilize and is disposed at the dilute sulphuric acid that each pipeline valve midway generates anode side dilute sulphuric acid to generate in the A of loop and circulates in anode side electrolysis sulfuric acid generation loop B.
In above-mentioned loop B, carry out passed through the electrolysis of the dilute sulphuric acid of temperature and concentration adjustment in above-mentioned loop A, generate electrolysis sulfuric acid, the electrolysis sulfuric acid that cycle period in above-mentioned loop B is generated mixes with the dilute sulphuric acid through adjustment in above-mentioned loop A, and electrolysis sulfuric acid is adjusted to required temperature and concentration.In addition,, for the portion in contact with the electrolyte of these pipelines, machine, must use sulfuric acid or containing the sulfuric acid of oxidizing substance, there is the material of erosion resistance.For example, can use fluoro-resin, the quartz etc. such as tetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA).
In Fig. 1 23 shows the cathode side electrolysis portion of sulfuric acid electrolyzer 1.Portion 20 is same with anode side electrolysis, in cathode side electrolysis portion 23, be formed with the cathode side dilute sulphuric acid generation loop A ' and the middle cathode side electrolysis loop B ' circulating through logical liquid to the cathode compartment 7 of dilute sulphuric acid of adjusting of Jiang Gai loop A ' that the vitriol oil are adjusted into the dilute sulphuric acid of required temperature and concentration.
In the exemplified device of Fig. 1, above-mentioned loop A ' is by cathode side tank 38, cathode side vitriol oil supply unit 39, cathode side recycle pump 40, cathode side water cooler 41, cathode side by-pass valve 42, cathode side by-pass line 43 and be disposed at each pipeline valve midway and form.And in the device of this example, cathode side tank 38 is connected with cathode side pure water supply line 12, cathode side vitriol oil supply unit 39 is connected with cathode side vitriol oil supply line 29.The vitriol oil that is supplied to cathode side vitriol oil supply unit 39 from cathode side vitriol oil supply line 29 via cathode side vitriol oil supply valve 30 dilutes at the interior pure water by being supplied to cathode side tank 38 from cathode side pure water supply line 12 via cathode side pure water supply valve 13 of cathode side tank 38, becomes the dilute sulphuric acid of lower concentration.And then this dilute sulphuric acid, during the A ' internal recycle of above-mentioned loop, is adjusted to required temperature and concentration.Be adjusted to the cathode compartment 7 that temperature required and dilute sulphuric acid concentration is supplied to the electrolyzer 2 that is arranged at above-mentioned loop B ', carry out electrolysis.
Can it be configured to: can use the liquidometer being equipped with in not shown integrating flowmeter or each tank to carry out quantitatively the pure water being supplied in cathode side tank 38, and be supplied to cathode side tank 38.Integrating flowmeter can use the integrating flowmeter of ultrasonic type, electromagnetic type, section's formula etc., and operating device basis is from the measured value of integrating flowmeter or liquid level sensor or the supply of signal control pure water and stop supply.It should be noted that, cathode side pure water supply line 12 connection portion, in the A ' of loop, arranges position for it and is not particularly limited.
In addition, for the portion in contact with the electrolyte of these pipelines, machine, must use sulfuric acid or containing the sulfuric acid of oxidizing substance, there is the material of erosion resistance, for example, can use the fluoro-resin such as PTFE, PFA, quartzy etc.
Above-mentioned cathode side electrolysis loop B ' is by cathode compartment 7, cathode side circulation line 44, the cathode side tank 38 of electrolyzer 2 and be disposed at each pipeline valve configurations midway and form circlewise.In above-mentioned loop B ' in cathode side electrolysis portion 23, carry out the electrolysis of dilute sulphuric acid, but electrode reaction only produces hydrogen, can not generate electrolysis sulfuric acid, therefore, above-mentioned loop B ' internal recycle has and is adjusted to temperature required and dilute sulphuric acid concentration.
Anode side vitriol oil supply unit 32 and cathode side vitriol oil supply unit 39 can be configured in anode side recycle pump 33 and the inlet side of cathode side recycle pump 40 or the optional position of outlet side.But, in the situation that supply with the vitriol oil to the pure water boosting, at the position of boosting, can generate heat significantly and produce bubble because of the dilution of the vitriol oil, thereby there is a possibility of further boosting, from security aspect, consider, preferred disposition is at the inlet side of anode side recycle pump 33 and cathode side recycle pump 40.Sulfuric acid concentration can generate by generate loop A and cathode side dilute sulphuric acid to above-mentioned anode side dilute sulphuric acid the volumetric ratio of the amount of the pure water that loop A ' supplies with and the known vitriol oil of concentration and adjust.The volume of each liquid can quantitatively be controlled with integrating flowmeter etc.
In the present invention, as described anode 3, preferably use conductive diamond electrode.In this case, with use Pt, PbO 2situation Deng electrode catalyst is compared, oxygen overvoltage is high, so persulfuric acid formation efficiency is high, and chemistry and mechanical endurance all high, the pollution from anode does not occur, thereby can generate the sulphuric acid soln as electrolytic solution of abrasive and as the electrolysis sulfuric acid of electrolysate.For above-mentioned reason, the anode 3 using in electrolyzer 2 is preferably used conductive diamond electrode.
On the other hand, for negative electrode 6, from the aspect of spatter property, consider, preferably use the conductive diamond electrode of excellent corrosion resistance, but also can use the electrode of being made by the such brass alloys for valve (valve metal) of the precious metals such as platinum, titanium, zirconium, tantalum, the niobium sulfuric acid to erosion resistance and graphite, the such carbon material of glass carbon.
According to the inventor's research, when adjusting sulfuric acid concentration, if possessed in the recycle system in the loop B of electrolyzer 2, carry out, due to the heat of dilution, the inside of electrolyzer 2 will reach a high temperature, and damaging appears in barrier film 5.Therefore, in the present invention, avoid this situation, when carrying out sulfuric acid concentration adjustment, in anode side electrolysis portion 20, avoided the logical liquid to electrolyzer 2, utilized antianode side by-pass line 36Tong Ye loop A to carry out circulating cooling.In addition, for the same reason, in cathode side electrolysis portion 23, avoided the logical liquid to electrolyzer 2, utilized and carry out circulating cooling to cathode side by-pass line 43Tong Ye loop A ', thereby carry out concentration adjustment and the temperature adjustment of sulfuric acid.
While carrying out sulfuric acid concentration adjustment in anode side electrolysis Bu20 loop A and cathode side electrolysis Bu23 loop A ', can produce in some cases steam, the mist of a large amount of heats of dilution owing to sulfuric acid.In the present invention, these steam, the mist of carrying secretly in the gas that electrolysis produces is sent to the discharge point of destination of removing the evil outside unit of water electrolytic gas, in order to prevent their corrosion, preferably at the anodic gas vent line 102 rear that is connected in anode side tank 31, gas-liquid separation mechanism 91 and anode side mist separator 92 are set.Similarly, preferably at the cathode gas vent line 103 rear that is connected in cathode side tank 38, cathode side gas-liquid separation means 96 and cathode side mist separator 97 are set.
Then the water electrolytic gas, electrolysis being produced describes.The anodic gas producing in the anolyte compartment of electrolyzer 2 can comprise poisonous ozone in some cases.Therefore, preferably at anode side mist separator 92 rears, be provided as the remove the evil ozone decomposition catalyst of mechanism 93 of ozone, become oxygen to carry out ozone reduction innoxious, or be expelled to outside device after utilizing air, non-active gas to dilute fully.As ozone decomposition catalyst, use the situation of manganese peroxide more, when the acid solutions such as sulfuric acid low with pH contacts, can there is dissolving and lose ozone decomposed ability in manganese peroxide in some cases.In addition,, even if the liquid of contact is water, the in the situation that of being coated by water on ozone decomposition catalyst surface, catalyzer cannot contact with ozone gas, also can lose ozone decomposed ability in this case.Therefore, in order to process ozone in device, make equipment safety and turn round, preferably utilize gas-liquid separation mechanism 91 and mist separator 92 from water electrolytic gas, to remove mist elimination and steam.In addition, remove the situation of considering in advance the steam of supplying with the possibility that has mist formation, dewfall, for the pipeline of supplying gas, generally use the metal-made pipelines such as stainless steel, can, because contacting and corrode with sulfuric acid mist, dewfall, therefore substantially be necessary outside device, not discharge the water electrolytic gas containing these in this case.
The hydrogen of the cathode gas producing in the cathode compartment due to electrolyzer 2 has combustibility, explosivity, therefore, preferably at cathode side mist separator 97 rear, hydrogen burning catalyst is set, make the hydrogen and air mixed the burning that produce, after changing into harmless water vapor, discharge, or be expelled to outside device after utilizing air, non-active gas to dilute fully.Thereby hydrogen burning catalyst has the function that air and hydrogen burning are removed the evil to hydrogen, but as the effective constituent that is conducive to burning, the catalyzer that use containing precious metal more.Usually, in the situation that catalyst surface is coated by liquid such as water, hydrogen cannot contact with catalyzer, thereby causes hydrogen burning Disability.In addition, remove the situation of considering in advance the steam of supplying with the possibility that has mist formation, dewfall, for the pipeline of supplying gas, generally use the metal-made pipelines such as stainless steel, can, because contacting and corrode with sulfuric acid mist, dewfall, therefore substantially be necessary outside device, not discharge the water electrolytic gas containing these in this case.
Anode side gas-liquid separation mechanism 91 and cathode side gas-liquid separation mechanism 96 can be used following mechanism: use the containers such as pipeline, tank, utilize water electrolytic gas to come separated electrolysis to produce the mechanism of gas and sulfuric acid with the difference in specific gravity of liquid in water electrolytic gas; Extend the residence time of water electrolytic gas in container, so that mist drops on container Nei mechanism; Etc.. Mist separator 92 and 97 can use: in the container of tubular, used the mesh of the material with resistance to chemical reagents, the mechanism of porous material; Thereby the mechanism that the residence time that can extend water electrolytic gas falls mist; Etc..In addition, by carrying out cooling to gas-liquid separation mechanism, mist separator and the pipeline that connects them, make saturated vapor drops, make thus the hydrogenesis in water electrolytic gas, thereby the moisture that increases gas-liquid separation mechanism, mist separator is removed efficiency, the drag-out of minimizing to follow-up circuit, this is also effective means.
While sneaking into a large amount of steam, mist in anode side gas-liquid separation mechanism 91, cathode side gas-liquid separation mechanism 96, anode side mist separator 92 and cathode side mist separator 97, can, because fluid retention stops up gas flow path in inner, cause the exhaust of anode side tank 31 and cathode side tank 38 to carry out in some cases.Therefore, preferably make anode side gas-liquid separation mechanism 91, cathode side gas-liquid separation mechanism 96, anode side mist separator 92 and cathode side mist separator 97 can discharge termly the liquid that inside stores.
The discharge opeing of anode side gas-liquid separation mechanism 91 and anode side mist separator 92 can be by opening anode side gas pipeline tapping valve 94, utilizing anode side drain line 95 to carry out.The discharge opeing of cathode side gas-liquid separation mechanism 96 and cathode side mist separator 97 can be by opening cathode side gas piping tapping valve 99, utilizing cathode side drain line 100 to carry out.
Here, for gas-liquid separation, the state during for the object of each equipment and the work of electrolysis sulfuric acid apparatus describes.
(1) when sulfuric acid dilutes
In the A of loop, be provided with anode side water cooler 34, when dilute sulphuric acid, liquid temperature rises to higher than room temperature.Now, in the gas space of the anode side tank 31 than pipeline broadness, may exist comprise with anode side tank 31 in dilute sulphuric acid concentration/temperature of storing reach the gas (air) of the water vapor pressure of balance.This moisture vapor gas, by the tank skin face under the room temperature contacting with moisture vapor gas, pipeline wall cooling, condenses into water droplet.
Sulfuric acid dilution action stores the pure water of specified amount in anode side tank 31, pipeline while being included in beginning, in circulation way, inject the sulfuric acid of specified amount, and mix, therefore, liquid level in anode side tank 31 is followed the injection of sulfuric acid and is risen, gas in anode side tank 31 is discharged to anode side tank 31 outer (anodic gas vent line 102 tops) at leisure, produces flowing of air.Follow flowing of this air, the above-mentioned water droplet that is attached to wall is moved in anodic gas vent line 102.
(2) during electrolysis
During electrolysis, different from above-mentioned (1), not because of dilution, to cause heating but because electrolysis causes heating, produce thus the phenomenon identical with above-mentioned (1).In addition, in the formation shown in Fig. 1, if the action of above-mentioned (1), the heat of being mixed with sulfuric acid by pure water and causing is promptly removed by anode side water cooler 34, but the heat that the electrolysis occurring in electrolyzer 2 causes can cause the temperature of electrolytic solution to raise, and be supplied in anode side tank 31, thereby can infer than above-mentioned (1) and produce more water vapor (water droplet).In addition during electrolysis, because electrolysis is from the electrode gas that produces electrolysis, and be included in electrolytic solution with the form of trickle bubble.This trickle bubble moves in gas phase in anode side tank 31 from electrolytic solution, and trickle bubble produces the trickle spittle during explosion on liquid level, and its form with mist is included in the gas in anode side tank 31.
(3) about each mechanism
Be connected in the anode side mist separator 92 on anode side gas-liquid separation mechanism 91 tops, the separatory membrane with minute aperture does not allow mist to pass through, thus can gas molecule and mist (because fine and in gas floating drop) is separated.Along with utilizing the fractional dose of the isolated mist of this separatory membrane to increase, become at leisure drop, become and can flow with the form of liquid.
By the isolated liquid a of anode side gas-liquid separation mechanism 91 because gravity (deadweight) flows to gas-liquid separation mechanism 91 downsides.In addition, in anode side mist separator 92, isolated mist flocks together becomes drop, and due to deadweight, 92 times side flow of anode side mist separator, travel to anode side gas-liquid separation mechanism 91.A is same with aforesaid liquid, by the isolated liquid b of anode side mist separator 92, flows to anode side gas-liquid separation mechanism 91 downsides in anode side gas-liquid separation mechanism 91.The liquid a and the b that flow to anode side gas-liquid separation mechanism 91 downsides are focused to before anode side gas pipeline tapping valve 94, when anode side gas pipeline tapping valve 94 is opened, under Gravitative Loads, are discharged to outside device.Therefore, for the discharge by gas-liquid separation mechanism, the isolated liquid of mist separator, the relation of the height location of each equipment is important, must from top, be at least anode side mist separator 92, anode side gas-liquid separation mechanism 91, anode side gas pipeline tapping valve 94 successively.Can select arbitrarily the opportunity of the switching of gas piping tapping valve 94.
It should be noted that, for being connected in the cathode side mist separator 97 on the cathode side gas-liquid separation 96 of mechanism top, also preferred same formation.
In order effectively to carry out the discharge opeing in gas-liquid separation mechanism and mist separator, can utilize pressure difference.For example, in anode side drain line 95 and cathode side drain line 100, not shown pressure reducer is set, by to reducing pressure in gas-liquid separation mechanism and mist separator, form and anodic gas and the reciprocal air-flow of cathode gas, can effectively carry out the discharge opeing of the sulfuric acid in gas-liquid separation mechanism and mist separator thus.
As other method, outlet side at anode side mist separator 92 and cathode side mist separator 97 arranges not shown non-active gas supply unit, by advertising non-active gas in reverse direction in gas-liquid separation mechanism and mist separator with anodic gas and cathode gas, can effectively carry out the discharge opeing of the sulfuric acid in gas-liquid separation mechanism and mist separator thus.As non-active gas, can use for example nitrogen.
The barrier film 5 using in electrolyzer 2 is preferably used porousness fluorine-type resin film or the fluorine type resin cationic exchange membrane that has passed through hydrophilicity-imparting treatment.In the situation that using fluorine type resin cationic exchange membrane, when positively charged ion sees through ion-exchange membrane from anode side cathode side, under the impact of carried secretly water entrainment, the sulfuric acid concentration of anode rises with the process of electrolysis time, the liquid measure of anode side reduces simultaneously, the sulfuric acid concentration of negative electrode is because being diluted and reduce by water entrainment, and liquid measure increases simultaneously.
The liquid measure of cathode side is controlled by opening and closing cathode can outlet valve 113 and is undertaken, no matter be the situation of regularly discharging or situation about controlling according to the liquid level of tank, be all by opening cathode can outlet valve 113, liquid is expelled to outside device under Gravitative Loads.The management of output can adopt the whole bag of tricks, for example, can be by the liquid level sensor of measuring Low position is set at cathode side tank 38, at liquid, discharge to proceed to and when liquid level reaches this sensor location, close cathode can outlet valve 113 and control.On the opportunity of opening as cathode can outlet valve 113, can adopt any situation in following situation: monitor electrolysis time and electrical current value, and calculate and carry the water yield secretly, the situation of opening by these values when reaching prescribed value; The liquid level sensor of measuring High position is set at cathode side tank 38, at water entrainment, accumulates the situation of opening when liquid level is increased to this sensor location that proceeds to.
In addition, for the gas in balance cathode side Guan38 space, can via cathode gas vent line 103, flow into from the cathode gas equipment 98 of removing the evil.
While causing catholyte to increase because of water entrainment, the liquid level that can cause cathode side tank 38 rises and then surpasses the capacity of cathode side tank 38, thereby in cathode side tank 38, when arriving specified altitude assignment, opens jar liquid surface cathode can outlet valve 113, the liquid of being discharged specified amount by cathode can vent pipe 112, prevents the amount of storing surplus thus.The control of the liquid level of cathode side tank 38 can be used not shown liquid level sensor etc.Like this, when the water entrainment of carrying secretly during by porousness fluorine-type resin film because of positively charged ion causes the liquid measure of the dilute sulphuric acid solution of catholyte portion 23 to increase, by termly or discharge the liquid of specified amount when the liquid level of cathode side tank 38 reaches the height of appointment, can prevent the overflow of cathode side tank 38.
On the other hand, continue to use if do not discharge catholyte, the existence of water entrainment can cause the sulfuric acid of negative electrode further to be diluted, and concentration reduces, and electric conductivity significantly reduces.While using for a long time not changing catholyte, utilize not shown concentration meter for sulfuric acid to monitor the sulfuric acid concentration of catholyte, from cathode side sulfuric acid supply unit 39, supplement the vitriol oil, also can control and make it reach finite concentration.
For example, measure electrolysis time and current value, obtain the water yield of carrying secretly being calculated by measured value, then, calculate before electrolysis electrolyte content in the cathode side tank 38 through adjusting and sulfuric acid concentration thereof and add above-mentioned sulfuric acid concentration while carrying the water yield secretly, in the situation that the sulfuric acid concentration calculating is lower than calculating the sulfuric acid amount that should add for returning to specialized range in specialized range, with under meter, the sulfuric acid amount calculating is carried out quantitatively, the vitriol oil is injected at position from from cathode side sulfuric acid supply unit 39 to cathode side electrolysis loop B ' working order simultaneously, sulfuric acid concentration in thus can control cathode liquid.In order to reduce the change of electrolytic condition, slow down the injection speed of the vitriol oil and control, make supplying temperature control and pond in sulfuric acid concentration not exceed in specialized range be important.
In anode side electrolysis Bu20 loop B, carry out after fixed time electrolysis, the electrolysis sulfuric acid reaching in the anode side tank 31 of oxidizing substance concentration of appointment is supplied to the use point outside device by anode can escape route 110, anode can outlet valve 111.It should be noted that, in the cathode side electrolysis loop B ' of cathode side electrolysis portion 23, carry out after fixed time electrolysis, the electrolytic solution in cathode side tank 38 is expelled to outside device by cathode can escape route 112, cathode can outlet valve 113.
If the electrolysis sulfuric acid in anode side tank 31 is cleared, again start the adjustment of sulfuric acid concentration.Now, in order to reduce the usage quantity of medicine, anticathode liquid carries out concentration control, monitors the characteristic values such as concentration, electric conductivity, can Reusability during characteristic value remains prescribed value.Although the temperature of cathode side, the control of concentration are not directly connected to persulfuric acid formation efficiency, for following reason, preferably control.That is, for following reason, it is necessary that the temperature, concentration of carrying out cathode side controlled: catholyte can be by the barrier film 5 anode liquid conduction temperature as cationic exchange membrane, and this can hinder anode temperature is controlled in specialized range; In the situation that anolyte is different from the concentration of catholyte, as the barrier film 5 of cationic exchange membrane, become the interface of the two poles of the earth liquid concentration difference, thereby become the position that produces the heat of dilution, the temperature of electrolytic solution is controlled to become and is difficult to carry out, and affects persulfuric acid formation efficiency; As the barrier film 5 of cationic exchange membrane, because of overheated, there is deteriorated, dimensional change; Because of the overheated water vapor bubble that produces, occurred pool resistance increases; Etc..
Fig. 2 illustrates the sulfuric acid concentration adjustment of sulfuric acid electrolyzer 1 of Fig. 1 and the figure of the operation of electrolysis.The operation of anode side electrolysis portion 20 as shown in Figure 2, comprises following operation.
1) pure water is supplied with operation
By anode side pure water supply line 10 anode side tanks 31, supply with pure water.
2) pure water circulating process
Drive anode side pump 33, so that pure water circulation.Now, anode chamber 4 does not lead to liquid, but by anode side by-pass line 36, pure water is circulated in the A of loop.
3) vitriol oil is supplied with operation
In the pure water of anode side vitriol oil supply unit 32Xiang loop A internal recycle, supply with the vitriol oil, and circulate constantly, thus the vitriol oil and pure water are mixed.In the method, after just the vitriol oil being mixed with pure water, solution enters anode side water cooler 34, thereby the heat of dilution that the vitriol oil produces while mixing with pure water is removed immediately, has suppressed the generation of steam, mist.And, owing to the temperature of the anode side vitriol oil supply unit 32 of the heat of dilution, rise and be inhibited, the breakage that can protect pipeline around, pump, valve etc. to avoid Yin Gaore to cause, distortion etc.
4) gas vent line discharge opeing operation
By opening anode side gas pipeline tapping valve 94, by anode side drain line 95, carried out the discharge opeing of anode side gas-liquid separation mechanism 91 and anode side mist separator 92.This operation can be above-mentioned 3) vitriol oil supplies with operation, following 5) dilute sulphuric acid concentration adjusts operation and 6) carry out at any time in electrowinning process.
5) sulfuric acid temperature and concentration are adjusted operation
Make on one side that dilute sulphuric acid solution is cooled to below the temperature that reaches required at loop A internal recycle, preferred temperature below 30 ℃, Yi Bian mix.In sulfuric acid temperature, be in the solution below 30 ℃, the current efficiency that generates oxidizing substance is high, therefore preferably before electrolysis, is cooled to below 30 ℃.In addition, sulfuric acid concentration can be 2～10mol/L.This be because, when sulfuric acid concentration surpasses 10mol/L, the current efficiency that generates oxidizing substance sharply reduces, current efficiency is below 60%; On the other hand, sulfuric acid concentration during lower than 2mol/L, tails off as the sulfate ion in the solution of oxidizing substance raw material, and current efficiency is reduced to below 60%, therefore, preferably makes sulfuric acid concentration in above-mentioned scope.
As described above anode side electrolysis portion 20 carry out operation during, in cathode side electrolysis portion 23, also carry out equally as illustrated in fig. 2 following operation.
1) pure water is supplied with operation
By cathode side pure water supply line 12, to cathode side tank 38, supply with pure water.
2) pure water circulating process
Drive cathode side pump 40, so that pure water is at loop A ' internal recycle.Now, not to the logical liquid of cathode compartment 7, but make pure water be circulated to cathode side tank 38 by cathode side by-pass line 43.
3) vitriol oil is supplied with operation
In the pure water of cathode side vitriol oil supply unit 39Xiang loop A ' internal recycle, supply with the vitriol oil, and circulate constantly, thus the vitriol oil and pure water are mixed.In the method, after just the vitriol oil being mixed with pure water, solution enters cathode side water cooler 41, thereby the heat of dilution that the vitriol oil produces while mixing with pure water is removed immediately, has suppressed the generation of steam, mist.Now; if the supply flow rate of the vitriol oil reaches the flow below 20% with respect to circular flow; owing to the temperature of the cathode side vitriol oil supply unit 39 of the heat of dilution, rise and be inhibited, the breakage that can protect pipeline around, pump, valve etc. to avoid Yin Gaore to cause, distortion etc.
4) gas vent line discharge opeing operation
By opening cathode side gas piping tapping valve 99, by cathode side drain line 100, carried out the discharge opeing of cathode side gas-liquid separation mechanism 96 and cathode side mist separator 97.This operation can be above-mentioned 3) vitriol oil supplies with operation, following 5) dilute sulphuric acid concentration adjusts operation and 6) carry out at any time in electrowinning process.
5) sulfuric acid temperature and concentration are adjusted operation
Make on one side that dilute sulphuric acid solution is cooled to the temperature that reaches required below at loop A ' internal recycle, preferred temperature below 30 ℃, Yi Bian be mixed to even.In sulfuric acid temperature, be in the solution below 30 ℃, the current efficiency that generates oxidizing substance is high, therefore preferably before electrolysis, is cooled to below 30 ℃.
In addition, sulfuric acid concentration can be 2～10mol/L.This be because, when sulfuric acid concentration surpasses 10mol/L, the current efficiency that generates oxidizing substance sharply reduces, current efficiency is below 60%; On the other hand, sulfuric acid concentration during lower than 2mol/L, tails off as the sulfate ion in the solution of oxidizing substance raw material, and current efficiency is reduced to below 60%, therefore, preferably makes sulfuric acid concentration in above-mentioned scope.
Because anode side is completely separated with cathode side, so anode side and the cathode side operation 1 of carrying out)～5) be identical, can carry out completely independently separately.
As mentioned above, anode side dilute sulphuric acid at anode side and cathode side generates in loop A and cathode side dilute sulphuric acid generation loop A ', and the dilute sulphuric acid that is adjusted to temperature required and desired concn carries out electrolysis in the electrowinning process of anode side electrolysis sulfuric acid generation loop B and cathode side electrolysis loop B '.
6) electrowinning process
Electrowinning process is above-mentioned 1)～5) operation of carrying out after anode side, cathode side all finish, dilute sulphuric acid solution being carried out to electrolysis.The dilute sulphuric acid solution that all circulates in anode side electrolysis portion 20 and cathode side electrolysis portion 23, carries out electrolysis.If solution temperature is that below 30 ℃, current efficiency is high, thereby the solution temperature in electrolysis can be controlled at below 30 ℃.
7) anolyte (electrolysis sulfuric acid) is supplied with operation
The electrolysis sulfuric acid generating in electrowinning process is adjusted to after required temperature and required concentration in anode side electrolysis Bu20 loop B, is supplied to use point.This is called to electrolysis sulfuric acid liquid and supplies with operation.At this electrolysis sulfuric acid liquid, supply with in operation, be that described electrowinning process carries out after fixed time electrolysis, or utilize not shown concentration monitor device to monitor oxidizing substance concentration, the anolyte that concentration is arrived to prescribed concentration is supplied to outside system.Can be supplied to corrosion-proof agent stripper, etching system etc., to the not restriction of connected device, equipment.
In sulfuric acid electrolyzer of the present invention, for measuring the concentration monitor device of oxidizing substance concentration, sulfuric acid concentration, can be arranged in device or the exterior line of logical liquid electrolysis sulfuric acid.The measured value that concentration monitor device obtains can be for: control the current value that is supplied to electrolyzer; Determine the output opportunity of the signals such as the device output CRANK PULSES of carrying electrolysis sulfuric acid to washing device etc. from sulfuric acid electrolyzer, liquor charging signal, alarm; Etc..It should be noted that, for the mensuration mode of concentration monitor device, be not particularly limited.
8) catholyte discharge opeing operation
In electrowinning process because the existence of water entrainment causes that catholyte increases, the liquid level of cathode side tank 38 is while arriving specified location, cathode can outlet valve 113 can temporarily be opened, and discharges on a small quantity catholyte.
The catholyte generating in electrowinning process is discharged by the cathode side electrolysis loop B ' of cathode side electrolysis portion 23.This is called to catholyte discharge opeing operation.This catholyte discharge opeing operation is the operation of all being discharged from cathode side tank 38 carrying secretly water-reducible catholyte.It can carry out discharge opeing by presetting the access times of catholyte when reaching this number of times, also can utilize not shown concentration meter for sulfuric acid to measure the sulfuric acid concentration of catholyte, carries out discharge opeing when concentration is reduced to designated value.It should be noted that, negative electrode discharge opeing operation can be supplied with operation with anolyte and carries out simultaneously, but can not carry out with electrowinning process simultaneously.
In other examples of the present invention, anode side electrolysis portion 20 is interior can carry 2 above anode side tanks, for example, can make each tank share liquor charging special use, dilute sulphuric acid outside device and adjust special-purpose, the special-purpose such function of electrolysis, or by sharing the special-purpose such function of liquor charging special use, dilute sulphuric acid adjustment and electrowinning process, can generate at short notice efficiently thus a large amount of sulfuric acid containing oxidizing substance.In cathode side electrolysis portion 23, also can similarly possess and there is a plurality of Guan mechanism.Sulfuric acid electrolyzer 1 can carry 2 above electrolyzers 2, also can 2 pairs of above positive cathode sets be set for 1 electrolyzer, forms dipolar configuration.
Fig. 3 is illustrated in the figure that is provided with the example of a plurality of anode side tanks in anode side electrolysis portion 20.Cathode side electrolysis portion 23 is not shown, and it is identical with the cathode side electrolysis portion 23 in Fig. 1.Shown sulfuric acid electrolyzer is as follows: in the A of loop, be set up in parallel the 1st anode side tank 49 and the 2nd anode side tank 50, in the 1st anode side tank 49, store after the electrolysis sulfuric acid of the oxidizing substance that contains generation, switch switch valve 51～58, thereby can in the 2nd anode side tank 50, generate the electrolysis sulfuric acid containing the oxidizing substance of prescribed concentration.
(1) be to store the sulfuric acid after electrolysis in the 1st anode side tank 49, thereby and switch all valves in the 2nd anode side tank 50, similarly manufacture electrolysis sulfuric acid during, electrolysis sulfuric acid can be supplied to use point from the 1st anode side tank 49.By repeating this process, nothing is interruptedly supplied with electrolysis sulfuric acid continuously, meanwhile,
(2) can in the 1st anode side tank 49 and the 2nd anode side tank 50, manufacture and store the electrolysis sulfuric acid of sulfuric acid concentration/oxidizing substance concentration separately, thereby the use of Dui Liangge position point carries out liquor charging, or to the different use operation of the oxidizing power requiring, carry out liquor charging from 1 table apparatus.
In addition, as mentioned above, the cathode side tank in cathode side electrolysis portion 23 also can arrange a plurality of as anode side tank.
Fig. 4 illustrates the sulfuric acid concentration adjustment of sulfuric acid electrolyzer 1 of Fig. 3 and the figure of the operation of electrolysis.What illustrate is that water cooler, sulfuric acid mixing tank only have the situation of (sharing).First, as follows to the specification shown in Fig. 4 left side.
1) pure water is supplied with operation
Open switch valve 55, by anode side pure water supply line 10 anode side tanks 49, supply with pure water.The water yield of supplying with can by according to from be arranged at the liquid level sensor of tank 49 signal, from the signal that is arranged at the integrating flowmeter of anode side pure water supply line 10, switch valve 55 is closed to carry out quantitatively.It should be noted that, be attached to the switch valve the 52, the 54th of anode side tank 50, close.
2) pure water circulating process
Drive anode side pump 33, so that pure water circulation.Now, outlet valve 22, anolyte compartment, anode side by-pass valve 35Wei Kai， anolyte compartment inlet valve 21 is for closing.The logical liquid in anode chamber 4, does not make pure water at loop A internal recycle by anode side by-pass line 36.
3) vitriol oil is supplied with operation
In the pure water of anode side vitriol oil supply unit 32Xiang loop A internal recycle, supply with the vitriol oil, and circulate constantly, thus the vitriol oil and pure water are mixed.In the method, after just the vitriol oil being mixed with pure water, solution enters anode side water cooler 34, thereby the heat of dilution that the vitriol oil produces while mixing with pure water is removed immediately, has suppressed the generation of steam, mist.And, owing to the temperature of the anode side vitriol oil supply unit 32 of the heat of dilution, rise and be inhibited, the breakage that can protect pipeline around, pump, valve etc. to avoid Yin Gaore to cause, distortion etc.
4) gas vent line discharge opeing operation
By opening anode side gas pipeline tapping valve 94, by anode side drain line 95, carried out the discharge opeing of anode side gas-liquid separation mechanism 91 and anode side mist separator 92.This operation can be above-mentioned 3) vitriol oil supplies with operation, following 5) dilute sulphuric acid concentration adjusts operation and 6) carry out at any time in electrowinning process.
5) sulfuric acid temperature and concentration are adjusted operation
Make on one side that dilute sulphuric acid solution is cooled to below the temperature that reaches required at loop A internal recycle, preferred temperature below 30 ℃, Yi Bian mix.In sulfuric acid temperature, be in the solution below 30 ℃, the current efficiency that generates oxidizing substance is high, therefore preferably before electrolysis, is cooled to below 30 ℃.
In addition, sulfuric acid concentration can be 2～10mol/L.This be because, when sulfuric acid concentration surpasses 10mol/L, the current efficiency that generates oxidizing substance sharply reduces, current efficiency is below 60%; On the other hand, sulfuric acid concentration during lower than 2mol/L, tails off as the sulfate ion in the solution of oxidizing substance raw material, and current efficiency is reduced to below 60%, therefore, preferably makes sulfuric acid concentration in above-mentioned scope.
As mentioned above, in the anode side dilute sulphuric acid generation loop A of anode side, the dilute sulphuric acid that is adjusted to temperature required and desired concn carries out electrolysis in the electrowinning process of anode side electrolysis sulfuric acid generation loop B.
6) electrowinning process
Electrowinning process is above-mentioned 1)～5) operation of carrying out, dilute sulphuric acid solution being carried out to electrolysis after finishing.In Fig. 4, anticathode side does not illustrate, but identical with the situation of above-mentioned Fig. 2, and cathode side also carries out above-mentioned 1 as anode side)～5) each operation.
In anode side electrolysis portion 20, make dilute sulphuric acid solution circulated and carry out electrolysis.Because solution temperature is that 30 ℃ of current efficiency when following are high, so the solution temperature in electrolysis can be controlled at below 30 ℃.
Close anode side by-pass valve 35, open outlet valve 22, anolyte compartment, anolyte compartment inlet valve 21, between anode side Guan49Yu anolyte compartment 4, circulate.
To electrolyzer 2, supply with galvanic current, with given supply electric current, carry out the electrolysis of specified time, obtain the electrolysis sulfuric acid containing the oxidizing substance of normality.Close switch valve 51,53, the electrolysis sulfuric acid of the oxidizing substance containing normality of generation stores in anode can 49.
7) anolyte (electrolysis sulfuric acid) is supplied with operation
The electrolysis sulfuric acid generating in electrowinning process is adjusted to required temperature and required oxidizing substance concentration in the anode side electrolysis sulfuric acid of anode side electrolysis portion 20 generates loop B, is supplied to use point.This is called to electrolysis sulfuric acid liquid and supplies with operation.At this electrolysis sulfuric acid liquid, supply with in operation, be that described electrowinning process carries out after fixed time electrolysis, or utilize not shown concentration monitor device to monitor oxidizing substance concentration, the anolyte that concentration is arrived to prescribed concentration is supplied to outside system.Can be supplied to corrosion-proof agent stripper, etching system etc., to the not restriction of connected device, equipment.
With this 7) anolyte supplies with operation concurrently shown in ，Ru Tu4 right side, for anode side tank 50, as above-mentioned 1) and supply with pure water, after this as carry out 1 followingly) → 6).
1) pure water is supplied with operation
Open switch valve 56, by anode side pure water supply line 10 anode side tanks 50, supply with pure water.The water yield of supplying with can by according to from be arranged at the liquid level sensor of tank 50 signal, from the signal that is arranged at the integrating flowmeter of anode side pure water supply line 10, switch valve 56 is closed to carry out quantitatively.It should be noted that, be attached to the switch valve the 52, the 54th of anode side tank 50, open.
2) pure water circulating process
Drive anode side pump 33, so that pure water circulation.Now, outlet valve 22, anolyte compartment, anode side by-pass valve 35Wei Kai， anolyte compartment inlet valve 21 is for closing.The logical liquid in anode chamber 4, does not make pure water at loop A internal recycle by anode side by-pass line 36.
3) vitriol oil is supplied with operation
In the pure water of anode side vitriol oil supply unit 32Xiang loop A internal recycle, supply with the vitriol oil, and circulate constantly, thus the vitriol oil and pure water are mixed.In the method, after just the vitriol oil being mixed with pure water, solution enters anode side water cooler 34, thereby the heat of dilution that the vitriol oil produces while mixing with pure water is removed immediately, has suppressed the generation of steam, mist.And, owing to the temperature of the anode side vitriol oil supply unit 32 of the heat of dilution, rise and be inhibited, the breakage that can protect pipeline around, pump, valve etc. to avoid Yin Gaore to cause, distortion etc.
4) gas vent line discharge opeing operation
By opening anode side gas pipeline tapping valve 94, by anode side drain line 95, carried out the discharge opeing of anode side gas-liquid separation mechanism 91 and anode side mist separator 92.This operation can be above-mentioned 3) vitriol oil supplies with operation, following 5) dilute sulphuric acid concentration adjusts operation and 6) carry out at any time in electrowinning process.
5) sulfuric acid temperature and concentration are adjusted operation
Make on one side that dilute sulphuric acid solution is cooled to below the temperature that reaches required at loop A internal recycle, preferred temperature below 30 ℃, Yi Bian mix.In sulfuric acid temperature, be in the solution below 30 ℃, the current efficiency that generates oxidizing substance is high, therefore preferably before electrolysis, is cooled to below 30 ℃.
In addition, sulfuric acid concentration can be 2～10mol/L.This be because: the sulfuric acid that sulfuric acid concentration is 2～10mol/L, its current efficiency that generates oxidizing substance is higher than sulfuric acid more than 10mol/L; On the other hand, while being less than 2mol/L, as the sulfate ion in the solution of oxidizing substance raw material, tail off, current efficiency reduces.
As mentioned above, the dilute sulphuric acid that is adjusted to temperature required and desired concn in the A of the loop of anode side carries out electrolysis in the electrowinning process of loop B.
6) electrowinning process
Electrowinning process is above-mentioned 1)～5) operation of carrying out, dilute sulphuric acid solution being carried out to electrolysis after finishing.In Fig. 4, anticathode side does not illustrate, but identical with the situation of described Fig. 2, and cathode side also carries out above-mentioned 1 as anode side)～5) each operation.
In anode side electrolysis portion 20, make dilute sulphuric acid solution circulated and carry out electrolysis.Because solution temperature is that 30 ℃ of current efficiency when following are high, so the solution temperature in electrolysis can be controlled at below 30 ℃.
Close anode side by-pass valve 35, open outlet valve 22, anolyte compartment, anolyte compartment inlet valve 21, between anode side Guan50Yu anolyte compartment 4, circulate.
To electrolyzer 2, supply with galvanic current, with given supply electric current, carry out the electrolysis of specified time, obtain the electrolysis sulfuric acid containing the oxidizing substance of normality.Then, close switch valve 52,54, the electrolysis sulfuric acid of the oxidizing substance containing normality of generation stores in anode can 50.
Then, from anode side tank 50 to using point to supply with electrolysis sulfuric acid, in anode side tank 49, start again pure water and supply with operation, so repeatedly.
Embodiment
Below in conjunction with embodiment and comparative example, the present invention is carried out to more specific description, but the present invention is not subject to the restriction of following examples.
<embodiment 1>
Adopt sulfuric acid electrolyzer and the sulfuric acid electrolysis process shown in Fig. 1 and Fig. 2 to carry out.
Being equipped on the anode 3 of electrolyzer 2 and negative electrode 6 has used respectively and coatedly on the silicon plate of bore 200mm φ has given the conductive diamond electrode that the diamond of electroconductibility forms because of doped with boron.Current density is 100A/dm 2.
For anode side, cathode side, it is all as follows that sulfuric acid temperature and concentration are adjusted operation, and the vitriol oil is diluted with pure water, prepared the dilute sulphuric acid of temperature through the prescribed concentration of adjustment.
The working procedure of anode side is as follows.
1) by anode side pure water supply line 10 anode side tanks 31, supply with pure water, and stored.The feed rate of pure water is used the integrating flowmeter of not shown ultrasonic wave mode to weigh rear supply.
2) drive anode side recycle pump 33, make pure water at loop A internal recycle.
3) pure water of Dui Zheng loop A internal recycle, by supplying with the vitriol oil in anode side vitriol oil supply unit 32Xiang loop A, carries out the generation of dilute sulphuric acid.The feed rate of the vitriol oil is used the integrating flowmeter of not shown ultrasonic wave mode to carry out supplying with after weighing.
4) because of the vitriol oil, mix the heat of dilution producing with pure water cooling by anode side water cooler 34 in circulation, and temperature is adjusted to below 30 ℃, and meanwhile, the dilute sulphuric acid solution obtaining with pure water diluting concentrated sulfuric acid is uniformly mixed fully by circulating.
The working procedure of cathode side is as follows.
1) by cathode side pure water supply line 12, to cathode side tank 38, supply with pure water, and stored.The feed rate of pure water is used the integrating flowmeter of not shown ultrasonic wave mode to carry out supplying with after weighing.
2) drive cathode side recycle pump 40, make pure water at loop A ' internal recycle.
3) pure water of Dui Zheng loop A ' internal recycle, by supplying with the vitriol oil in cathode side vitriol oil supply unit 39Xiang loop A ', carries out the generation of dilute sulphuric acid.The feed rate of the vitriol oil is used the integrating flowmeter of not shown ultrasonic wave mode to carry out supplying with after weighing.
4) because of the vitriol oil, mix the heat of dilution producing with pure water cooling by cathode side water cooler 41 in circulation, and temperature is adjusted to below 30 ℃, and meanwhile, the dilute sulphuric acid solution obtaining with pure water diluting concentrated sulfuric acid is uniformly mixed fully by circulating.
In anode side and cathode side, complete after sulfuric acid concentration adjustment and temperature adjustment, by at anode side Open valve 21 and valve 22, valve-off 35, form loop B, by opening cathode compartment inlet valve 24 and cathode compartment outlet valve 25 at cathode side, closing cathode side by-pass valve 42, form cathode side electrolysis loop B ', difference is supplied with dilute sulphuric acid solution to electrolyzer circulation on one side, to electrolyzer supply galvanic current carry out electrolysis on one side, thereby generate the electrolysis sulfuric acid containing oxidizing substance.
Then, by aforesaid method, the sulfuric acid concentration before electrolysis is adjusted to the scope that is adjusted to 1.8～16.7mol/L after operation by sulfuric acid concentration.For catholyte, also by being applied to cathode side, same method carried out concentration adjustment.After dilute sulphuric acid solution is cooling, carried out electrolysis.Condition is as follows.
Figure BDA0000410972530000251
For the dilute sulphuric acid that adopts above-mentioned working procedure and above-mentioned condition electrolysis to obtain, from the not shown sampling line of being paid by electrolysis section, take solution, and the total amount of the oxidizing substance that generates in dilute sulphuric acid that adopted the quantitative assay of KI volumetry.
Table 1 shows the mensuration example of the total oxidizing substance concentration at the different dilute sulphuric acid temperature for electrolysis, under same volume capacity density.Sulfuric acid concentration is 3.7mol/L.When temperature surpasses 30 ℃, gained concentration reduces.
Table 1
Figure BDA0000410972530000261
Known, the current efficiency of being obtained by total oxidizing substance concentration significantly reduces near 30 ℃, and hence one can see that, in order to generate efficiently oxidizing substance, uses to be adjusted to 30 ℃ of following dilute sulphuric acids to carry out electrolysis be effective.
Total oxidizing substance concentration when table 2 shows sulfuric acid concentration and is 1.8～16.7mol/L and the result of current efficiency.Current density is 100A/dm 2, volume capacity density is 25Ah/L.Known, the current efficiency of being obtained by total oxidizing substance concentration is shown as more than 60% scope when sulfuric acid concentration is 2.0～10.0mol/L, in Bi Gaixi region and Bi Cinong region all sharply reduce.
Table 2
Figure BDA0000410972530000262
Thereby table 3 shows the cooling example that keeps 30 ℃ that continues to carry out electrolytic solution in electrolysis, and in electrolysis, stop cooling, cause electrolyte temperature to rise to the example of 51 ℃ because of the heating of electrolysis.
Table 3
Figure BDA0000410972530000271
As shown in Table 3, in continuing to be cooled to the example of 30 ℃, obtained the oxidizing substance concentration of 1.51mol/L; On the other hand, in electrolysis, stop cooling, because the heating of electrolysis causes electrolyte temperature, rise in the example of 51 ℃, oxidizing substance concentration terminates in 0.72mol/L, fails to carry out the good electrolysis of efficiency.
<comparative example 1>
Then, as a comparative example 1, the hybrid position that shows the vitriol oil and pure water is in anode side tank and the situation of gas-liquid separation mechanism and mist separator is not set.Dilute sulphuric acid at this comparative example 1 generates in operation, cooling improper, and plant failure has occurred.
In comparative example 1, in order to adjust the dilute sulphuric acid solution ，Cong Guan top of 6mol/L, in tank, drop into after ultrapure water 2.6L, the 98 quality % sulfuric acid Cong Guan bottoms of 5.9L are dropped into.Arbitrary solution is room temperature.Ultrapure water supply flow rate is 3L/min, and 98 quality % sulfuric acid supply flow rates are 0.2～1L/min.
Inner at tank, because ultrapure water mixes and produces the heat of dilution with sulfuric acid, cause solution temperature to rise, thereby produced a large amount of steam.And cause that by this steam the inwall of gas vent line is attached with mist.
After the supply of 98 quality % sulfuric acid finishes, ejector priming circulates solution in tank and heat exchanger, and dilute sulphuric acid solution is cooled to 25 ℃.After cooling end, make solution in tank and electrolyzer circulation, start electrolysis.Solution temperature in electrolysis is 27 ℃, and the air pressure of the gas vent line of anode and negative electrode is 3～5kPa, but electrolysis starts the air pressure of cathode can after 10 minutes, sharply rises and reaches 200kPa, occurs extremely, therefore stops at circulate soln in tank and electrolyzer.
Now, the existence of the steam producing due to the heat of dilution because of sulfuric acid, the liquid that the mist that produced when sulfuric acid dilution has been detained in the inside of the filter that arranges between the hydrogen burning tower of equipment setting and the vapor condenses of removing the evil in cathode can and as cathode side forms, this liquid causes air filter to stop up, therefore cathode gas is trapped between cathode can and filter, produces high pressure.When take apart in release residual voltage Hou，Jiang pond, on cationic exchange membrane, confirmed communicating pores.
Industrial applicibility
According to sulfuric acid electrolyzer of the present invention and sulfuric acid electrolysis process, can in device, generate temperature and the controlled dilute sulphuric acid of concentration, and can under the controlled condition of temperature, to this dilute sulphuric acid, carry out electrolysis, thus, can be efficiently and generate safely the sulfuric acid that contains a large amount of oxidizing substances.In addition, can provide following sulfuric acid electrolyzer and sulfuric acid electrolysis process, it can manufacture the high oxygen concentration voltinism substance solution that prior art cannot realize with high current efficiency, can stably generate oxidisability active material.

Claims (16)

1. a sulfuric acid electrolyzer, this sulfuric acid electrolyzer (1) has anode side electrolysis portion (20) and cathode side electrolysis portion (23), wherein,
At least in anode side electrolysis portion (20), be provided with anode side dilute sulphuric acid and generate loop (A) and anode side electrolysis sulfuric acid generation loop (B), described anode side dilute sulphuric acid generates loop (A) dilution as the vitriol oil of base feed, and the sulfuric acid after dilution is adjusted to required temperature and concentration, described anode side electrolysis sulfuric acid generates loop (B) this dilute sulphuric acid is generated to the dilute sulphuric acid electrolysis generating in loop (A) and generates electrolysis sulfuric acid, and the electrolysis sulfuric acid of generation is adjusted to required temperature and concentration
Described anode side dilute sulphuric acid generates in loop (A), dispose successively anode side tank (31), anode side vitriol oil supply unit (32) and anode side water cooler (34), they are linked and are formed loop by anode side by-pass line (36), and, any part in Gai loop (A) is connected with can supply with the anode side pure water supply line (10) of pure water in (A) to loop, in addition, also be connected with the anode side vitriol oil supply line (27) of supplying with the vitriol oil to described anode side vitriol oil supply unit (32) for realizing
Described anode side electrolysis sulfuric acid generates in loop (B), the anolyte compartment (4) that inside in described anode side tank (31) and electrolyzer (2) is provided with anode (3) is linked and is formed loop by anode side circulation line (37), described electrolyzer (2) comprises anolyte compartment (4) cathode compartment (7), this anolyte compartment (4) cathode compartment (7) forms by barrier film (5)
The vitriol oil that is supplied to anode side vitriol oil supply unit (32) from described anode side vitriol oil supply line (27) is diluted by the pure water of supplying with from described anode side pure water supply line (10), and, the sulfuric acid of the lower concentration after dilution is adjusted to required temperature and concentration during the internal recycle of described loop (A), generation is adjusted into temperature required and dilute sulphuric acid concentration
The dilute sulphuric acid generating is supplied to the anolyte compartment (4) of described electrolyzer (2) via the anode side circulation line (37) that forms described loop (B), in Gai anolyte compartment (4), generate electrolysis sulfuric acid, and, the electrolysis sulfuric acid generating is adjusted to required temperature and concentration during the internal recycle of described loop (B), generates and is adjusted into temperature required and electrolysis sulfuric acid concentration.
2. sulfuric acid electrolyzer according to claim 1, it is further provided with cathode side dilute sulphuric acid and generates loop (A ') and cathode side electrolysis loop (B ') in the device of described cathode side electrolysis portion (23), described cathode side dilute sulphuric acid generates loop (A ') dilution and as the vitriol oil of base feed, obtains the sulfuric acid of lower concentration, and the sulfuric acid of this lower concentration is adjusted to required temperature and concentration, described cathode side electrolysis loop (B ') makes this dilute sulphuric acid generate the dilute sulphuric acid generating in loop (A ') to be circulated in cathode compartment (7)
Cathode side dilute sulphuric acid generation loop (A ') in, dispose successively cathode side tank (38), cathode side vitriol oil supply unit (39) and cathode side water cooler (41), they are linked and are formed loop by cathode side by-pass line (43), and, in any part in Gai loop (A ') is connected with can be to loop (A '), supply with the cathode side pure water supply line (12) of pure water, in addition, also be connected with the vitriol oil supply line (29) of supplying with the vitriol oil to described cathode side vitriol oil supply unit (39) for realizing
Cathode side electrolysis loop (B ') in, the cathode compartment (7) that inside in described cathode side tank (38) and electrolyzer (2) is provided with negative electrode (6) is linked and is formed loop by cathode side circulation line (44), described electrolyzer (2) comprises anolyte compartment (4) cathode compartment (7), this anolyte compartment (4) cathode compartment (7) forms by barrier film (5)
The vitriol oil that is supplied to cathode side vitriol oil supply unit (39) from cathode side vitriol oil supply line (29) is diluted by the pure water of supplying with from described cathode side pure water supply line (12), and the sulfuric acid of the lower concentration after dilution is adjusted to required temperature and concentration during the internal recycle of described loop (A '), generation is adjusted into temperature required and dilute sulphuric acid concentration
The dilute sulphuric acid generating is supplied to the cathode compartment (7) of electrolyzer (2) via the cathode side circulation line (44) that forms described loop (B '), be to carry out during the internal recycle of loop (B ') temperature and concentration through the electrolysis of the dilute sulphuric acid adjusted.
3. sulfuric acid electrolyzer according to claim 1, wherein, on described anode side tank (31) top, via anodic gas vent line (102), in the mode being communicated with of connecting successively, be connected with anode side gas-liquid separation mechanism (91) and anode side mist separator (92), the bottom of this anode side gas-liquid separation mechanism (91) and this anode side mist separator (92) possesses for discharging the pumping equipment of the inner liquid of accumulating separately, and described pumping equipment has the structure that has been communicated with anode side gas-liquid separation mechanism (91) and anode side mist separator (92).
4. sulfuric acid electrolyzer according to claim 2, wherein, on described anode side tank (31) top, via anodic gas vent line (102), in the mode being communicated with of connecting successively, be connected with anode side gas-liquid separation mechanism (91) and anode side mist separator (92), the bottom of this anode side gas-liquid separation mechanism (91) and this anode side mist separator (92) possesses for discharging the pumping equipment of the inner liquid of accumulating separately, described pumping equipment has the structure that has been communicated with anode side gas-liquid separation mechanism (91) and anode side mist separator (92)
And, on described cathode side tank (38) top, via cathode gas vent line (103), in the mode being communicated with of connecting successively, be connected with cathode side gas-liquid separation mechanism (96) and cathode side mist separator (97), the bottom of this cathode side gas-liquid separation mechanism (96) and this cathode side mist separator (97) possesses for discharging the pumping equipment of the inner liquid of accumulating separately, and described pumping equipment has the structure that has been communicated with cathode side gas-liquid separation mechanism (96) and cathode side mist separator (97).
5. according to the sulfuric acid electrolyzer described in claim 3 or 4, wherein, described anode side mist separator (92) is connected with ozone decomposed mechanism (93).
6. sulfuric acid electrolyzer according to claim 4, wherein, described cathode side mist separator (97) is connected with hydrogen processing mechanism.
7. sulfuric acid electrolyzer according to claim 1 and 2, wherein, described dilute sulphuric acid generates in loop (A) and is set side by side with a plurality of described anode side tanks, and after the electrolysis sulfuric acid containing oxidizing substance that makes to generate stores in of this anode side tank, switch valve, thus the electrolysis sulfuric acid containing the oxidizing substance of prescribed concentration in other anode side tanks, generated.
8. sulfuric acid electrolyzer according to claim 7, its formation make by store the electrolysis sulfuric acid liquor charging containing the oxidizing substance of prescribed concentration in the anode side tank use point to sulfuric acid electrolyzer during in, with other anode side tanks, generate the electrolysis sulfuric acid containing the oxidizing substance of prescribed concentration.
9. sulfuric acid electrolyzer according to claim 1 and 2, wherein, described anode (3) is conductive diamond electrode.
10. sulfuric acid electrolyzer according to claim 1 and 2, wherein, described barrier film (5) is for fluorine type resin cationic exchange membrane or passed through the porousness fluorine-type resin film of hydrophilicity-imparting treatment.
11. 1 kinds of sulfuric acid electrolysis processs, it comprises: the sulfuric acid electrolyzer in right to use requirement 1～10 described in any one generates and is adjusted to temperature required and electrolysis sulfuric acid concentration.
12. 1 kinds of sulfuric acid electrolysis processs, it comprises: right to use requires the sulfuric acid electrolyzer described in any one in 1～10, and use porousness fluorine-type resin film as described barrier film (5), when the water entrainment of carrying secretly during by this porousness fluorine-type resin film because of positively charged ion causes the liquid measure of the dilute sulphuric acid solution of circulation in cathode side electrolysis loop in described catholyte portion (23) (B ') to increase, termly or when the liquid level of described cathode side tank (38) reaches specified altitude assignment, discharge the liquid of specified amount, prevent thus the overflow of this cathode side tank (38).
13. 1 kinds of sulfuric acid electrolysis processs, it comprises: right to use requires the sulfuric acid electrolyzer described in any one in 1～10, and use porousness fluorine-type resin film as described barrier film (5), at the water entrainment of carrying secretly during by this porousness fluorine-type resin film because of positively charged ion, cause the sulfuric acid concentration of the dilute sulphuric acid solution generating in loop in described catholyte portion (23) (A ') to be reduced to prescribed concentration when following, to described cathode side vitriol oil supply unit (39), supplement the vitriol oil, keep thus the dilute sulphuric acid concentration of certain limit.
Sulfuric acid electrolysis process in 14. claims 11～13 described in any one, wherein, dilute sulphuric acid generation loop (A) in described anode side electrolysis portion (20) or the dilute sulphuric acid generation loop in described cathode side electrolysis portion (23) (A ') in, carry out temperature adjustment, the temperature that makes the dilute sulphuric acid before electrolysis is below 30 ℃.
Sulfuric acid electrolysis process in 15. claims 11～13 described in any one, wherein, electrolysis sulfuric acid generation loop (B) in described anode side electrolysis portion (20) or the cathode side electrolysis loop in described cathode side electrolysis portion (23) (B ') in, carry out temperature adjustment, the temperature that has made to occur the electrolytic solution of electrolysis is below 30 ℃.
Sulfuric acid electrolysis process in 16. claims 11～13 described in any one, wherein, dilute sulphuric acid generation loop (A) in described anode side electrolysis portion (20) or the dilute sulphuric acid generation loop in described cathode side electrolysis portion (23) (A ') in, carry out concentration adjustment, the sulfuric acid concentration that makes the dilute sulphuric acid before electrolysis is 2～10mol/L.
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TWI518209B (en) 2016-01-21
JPWO2012121270A1 (en) 2014-07-17

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