CN103384731A - Sulfuric acid electrolysis method and sulfuric acid electrolysis device - Google Patents
Sulfuric acid electrolysis method and sulfuric acid electrolysis device Download PDFInfo
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- CN103384731A CN103384731A CN2012800105271A CN201280010527A CN103384731A CN 103384731 A CN103384731 A CN 103384731A CN 2012800105271 A CN2012800105271 A CN 2012800105271A CN 201280010527 A CN201280010527 A CN 201280010527A CN 103384731 A CN103384731 A CN 103384731A
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- sulfuric acid
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- sulphuric acid
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 241
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 93
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 16
- 239000010432 diamond Substances 0.000 claims abstract description 16
- 235000011149 sulphuric acid Nutrition 0.000 claims description 101
- 239000001117 sulphuric acid Substances 0.000 claims description 101
- 239000005864 Sulphur Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 125000006850 spacer group Chemical group 0.000 claims description 32
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 29
- 239000012530 fluid Substances 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract 2
- 239000008151 electrolyte solution Substances 0.000 description 25
- 230000014759 maintenance of location Effects 0.000 description 23
- 238000004140 cleaning Methods 0.000 description 22
- 238000005406 washing Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 13
- 239000012776 electronic material Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 239000013626 chemical specie Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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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
- C25B1/30—Peroxides
-
- 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
- C25B1/29—Persulfates
-
- 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
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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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- Organic Chemistry (AREA)
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- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
In order to eliminate negative effects due to the accumulation of sulfur in an electrolysis cell for the electrolysis of sulfuric acid, an electrolysis device (1) is provided with: an electrolysis cell (2) which allows sulfuric acid solution to be brought in and released; an electrode constituted by a conductive diamond electrode; a pumping means for pumping sulfuric acid solution into the electrolysis cell; a power supply unit (3) for applying a voltage between the anode and cathode of the electrode; and a power control unit (4) for controlling the power supply unit such that voltage is applied in the forward direction between the anode and cathode during normal electrolysis, and polarity inversion, wherein the voltage applied between the anode and cathode is reversed under a predetermined condition, is executed. The electrolysis device is capable of continuing to perform electrolysis in a stable manner by carrying out normal operations, wherein electrolysis is conducted by applying a voltage in the forward direction between the anode and the cathode, and carrying out polarity inversion operations in between normal operations, wherein the voltage applied to the anode and cathode is reversed, so as to dissolve sulfur deposits, which are produced in the electrolysis cell during a normal operation, in the sulfuric acid solution during an inversion operation.
Description
Technical field
The present invention relates to the sulfuric acid electrolysis is generated electrolysis process and the electrolyzer of persulfuric acid.
Background technology
Known peroxy-disulfuric acid and permonosulphuric acid (below be referred to as persulfuric acid) that the sulphuric acid soln electrolysis is generated is used for the method for the cleaning etc. of semiconductor material.
Generate at electrolysis sulfuric acid in one of the method for persulfuric acid, the sulphuric acid soln that circulates between electrode on one side in tank room, to anode in electrode and negative electrode between apply volts DS implement electrolysis on one side.As the structure of this tank room, one pole chamber (anode and negative electrode are a pair of) is arranged, use the multipole chamber of bipolar electrode etc., but the relation of an antianode and negative electrode is identical.For pole distance is kept certain, usually use spacer, use the containment members such as O type circle for hermetic electrolyte liquid.As the tank room of this structure, the tank room (with reference to patent documentation 1) that for example has the present application people to propose.
The summary of tank room is shown in Fig. 7 (a).Configuration space thing 22 is to guarantee runner 23 between anode 20 and negative electrode 21.Be formed with inlet opening 22a, be formed with fluid hole 22b at outlet side at inlet side on spacer 22, these inlet openings 22a, fluid hole 22b consist of by comparing quite narrow runner with runner 23.In addition, configure O type circle 24 as containment member, to guarantee the stopping property of runner 23 between spacer 22 and electrode.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2007-262531 communique
Summary of the invention
Invent technical problem to be solved
, just know for a long time if electrolysis sulfuric acid produces H at negative electrode usually
2(gas), and in a single day sulfuric acid be exposed in reducing atmosphere, will become S (sulphur of solid) or H
2S (gas).
Therefore, if continued running, the dark place part at all ends of electrode surface, particularly electrode and O type circle generates sulphur or generates relevant chemical species with sulphur.If fine S particle is attached to electrode surface and growth, soon will be from stripping electrode, move along the trickling of electrolytic solution, adhere to, accumulate at crevices such as tank room fluid hole and tank room inlet openings, the problem that may stop up soon etc.It is believed that this problem in the situation that sulfuric acid concentration is high, current density is high, reach the high easily generation of voltage across poles.
Near the situation that sulphur is accumulated in O type circle section and fluid hole is shown in Fig. 7 (b).Can infer as A in figure, sulphur is separated out, and final precipitate is peeled off and moved, soon the outlet of the chamber of obstruction or chamber inlet as B in figure.
So, the purpose of this invention is to provide electrolysis process and the electrolyzer of the obstruction in a kind of system of accumulating and preventing from being caused by the sulphur precipitate of the sulphur that prevents from following the electrolysis of sulphuric acid soln and separate out.
The technical scheme that the technical solution problem adopts
namely, in sulfuric acid electrolysis process of the present invention first invention is characterised in that, in tank room, at least connecing liquid level is made of conductive diamond and comprises at least in a plurality of electrodes of anode and negative electrode, sulphuric acid soln more than circulation 70 quality % between above-mentioned anode and above-mentioned negative electrode is implemented electrolysis on one side on one side, thereby generate the electrolysis process of persulfuric acid, wherein, apply forward voltage and implement the routine operation of above-mentioned electrolysis between the anode of above-mentioned electrode and negative electrode, implement simultaneously to make the change poles operation of the voltage reversal that puts on above-mentioned anode and negative electrode during above-mentioned routine operation, the sulphur precipitate that generates in tank room when making above-mentioned routine operation is dissolved in above-mentioned sulphuric acid soln when above-mentioned change poles operation in.
The sulfuric acid electrolysis process of the second invention is characterised in that, in the first invention, Yi Bian sulphuric acid soln is flowed in above-mentioned tank room outside above-mentioned tank room, Yi Bian implement above-mentioned electrolysis, the above-mentioned sulphuric acid soln through electrolysis is flowed out to outside above-mentioned tank room.
The sulfuric acid electrolysis process of the 3rd invention is characterised in that, in the first or second invention, has the delay section that the above-mentioned sulphuric acid soln that supplies to circulate is detained in above-mentioned tank room.
The sulfuric acid electrolysis process of the 4th invention is characterised in that in first～the 3rd any of inventing, to have the narrowed flow path section of flowing for above-mentioned sulphuric acid soln in above-mentioned tank room.
The sulfuric acid electrolysis process of the 5th invention is characterised in that, in the 3rd invention, disposes the spacer of the runner of guaranteeing sulphuric acid soln between above-mentioned electrode, forms above-mentioned delay section by this spacer or by this spacer and other members.
The sulfuric acid electrolysis process of the 6th invention is characterised in that, in the 5th invention, is provided with containment member between above-mentioned electrode and above-mentioned spacer, forms above-mentioned delay section by the sealing member at least.
The sulfuric acid electrolysis process of the 7th invention is characterised in that, in the 5th or the 6th invention, is formed with the fluid hole that the above-mentioned sulphuric acid soln of confession as narrowed flow path section passes through in above-mentioned spacer.
The sulfuric acid electrolysis process of the 8th invention is characterised in that, in any of the 5th～the 7th invention, is formed with the inlet opening that the above-mentioned sulphuric acid soln of confession as narrowed flow path section passes through in above-mentioned spacer.
The sulfuric acid electrolysis process of the 9th invention is characterised in that, in first～the 8th any of inventing, be provided with the circulation line that is connected to the entrance of above-mentioned tank room from the outlet of above-mentioned tank room, have narrowed flow path section at the upstream side of the delay section of this circulation line and/or tank room.
The sulfuric acid electrolysis process of the tenth invention is characterised in that, in any of the first～the 9th invention, the operation of above-mentioned change poles is implemented by continuing to carry out the routine operation of specified time.
The sulfuric acid electrolysis process of the 11 invention is characterised in that, in any of the first～the tenth invention, the operation of above-mentioned change poles is based on the judgement of the precipitation state of above-mentioned sulphur and implements.
The sulfuric acid electrolysis process of the 12 invention is characterised in that, in first～the 11 any of inventing, satisfies at least one in following condition (a)～(c):
(a) concentration of the above-mentioned sulfuric acid in above-mentioned tank room is more than 85 quality %;
(b) the sulfuric acid temperature of above-mentioned tank room entrance is more than 70 ℃;
(c) current density in above-mentioned electrolysis is 50A/dm
2Above.
The sulfuric acid electrolyzer of the 13 invention is characterised in that to possess:
Sulphuric acid soln can feed liquor and the tank room of fluid;
Mode with the above-mentioned sulphuric acid soln of circulation in gap each other is configured in above-mentioned tank room and connects at least a plurality of electrodes that comprise at least anode and negative electrode that liquid level is made of conductive diamond;
Guarantee the spacer in above-mentioned interelectrode gap;
The narrowed flow path section of the above-mentioned sulphuric acid soln circulation of the confession that this spacer has;
Above-mentioned tank room is carried the liquor charging section of sulphuric acid soln;
To executing alive power supply unit between the above-mentioned anode of above-mentioned electrode and above-mentioned negative electrode; With
Power control part, this power control part carries out following control to above-mentioned power supply unit: to applying forward voltage between above-mentioned anode and above-mentioned negative electrode, implement to make simultaneously the change poles that puts on the voltage reversal between above-mentioned anode and above-mentioned negative electrode under predetermined condition when the electrolysis of routine.
The sulfuric acid electrolyzer of the 14 invention is characterised in that to possess:
Sulphuric acid soln can feed liquor and the tank room of fluid;
Mode with the above-mentioned sulphuric acid soln of circulation in gap each other is configured in above-mentioned tank room and connects at least a plurality of electrodes that comprise at least anode and negative electrode that liquid level is made of conductive diamond;
Guarantee the spacer in above-mentioned interelectrode gap;
The delay section of the above-mentioned sulphuric acid soln delay of confession that forms by this spacer or by this spacer and other members;
To executing alive power supply unit between the above-mentioned anode of above-mentioned electrode and above-mentioned negative electrode; With
Power control part, this power control part carries out following control to above-mentioned power supply unit: implement to make the change poles that puts on the voltage reversal between above-mentioned anode and above-mentioned negative electrode when the electrolysis of routine.
According to the present invention, switch on one side by the sulphuric acid soln that circulates between electrode on one side, be accumulated in the dark place etc. of electrode surface and O type circle at solid sulfur or its precursor before, carrying out change poles and making its electrode surface is oxidisability, carry out the above electrolysis of certain hour, thereby can effectively solid sulfur or its precursor be returned as sulfuric acid or sulfate ion.Sustainable about 10～100 hours of change poles operation.
By repeating at a certain time interval this operation, can prevent the obstruction with the chamber of accumulating of sulphur.Definite method as the timed interval, can be based on experience according to certain runtime or the processing sheet number that has carried out cleaning etc. determine, but sulphur is in case accumulate gradually, the required voltage of rated current (voltage across poles) that circulates rises gradually, so can be when switching on by current control, often monitor voltage, thereby begin the change poles operation when voltage rises to prescribed value.In addition, also monitor voltage in the time of can stating change poles on the implementation, this voltage drop is to prescribed value, and the change poles that stops this moment operating.
Below, the reaction form when electrolysis is shown.
In electrolytic solution, sulfuric acid and water molecules are following to be dissociated, and has SO
4 2-, HSO
4 -, H
+Plasma.
Wherein, H
+(with H
3O
+Synonym) and HSO
4 -Concentration reaches peak value when sulfuric acid concentration is 70 quality %～80 quality %, reduces in the greater concn side, on the other hand, the sulfuric acid molecule H that does not dissociate
2SO
4(aq) concentration sharply rises.In addition, the sulphuric acid soln of high density is strongly-acid, so OH
-Concentration low.
At negative electrode, H
+Be attracted, accept electronics and become hydrogen H as shown in following reaction formula
2
2Ｈ
++2ｅ
－→Ｈ
2
HSO
4 -And SO
4 2-Be attracted to anode, as shown in following reaction formula, discharge electronics and become persulfuric acid H
2S
2O
8
2ＨＳＯ
4 －→Ｓ
2Ｏ
8 2－+2Ｈ
++2ｅ
－
2ＳＯ
4 2－→Ｓ
2Ｏ
8 2－+2ｅ
－
In addition, the electrolysis of the water as shown in following reaction formula occurs also at anode, O produces oxygen
2
2ＯＨ
－→Ｏ
2+2Ｈ
++4ｅ
－
For the redox-potential that occurs about the electrode reaction of sulfuric acid and water, known Fig. 4, Pourbaix diagram (Japanese: Pourbaix Line figure) shown in Figure 5.
If describe sulfuric acid under sulfuric acid concentration=92 quality %, temperature=60 ℃ and the electromotive force of water based on Pourbaix diagram, expression, be shown in Figure 6 side by side.Formula numbering in figure is based on the numbering of the formula on the figure shown in Fig. 4,5.
The sulfuric acid that uses in tank room is high density, so pH is about-2.In anode side, demonstrate according to O
2＞O
3＞H
2O
2＞H
2S
2O
8Order generate with low potential, but in fact generate a large amount of O
2, be then H
2S
2O
8The electromotive force of negative electrode is S＞H
2＞H
2The order of S.In fact, at indoor H
2Be primary product, but as electromotive force, also be enough to generate S.If the S that generates is not trapped in the surface of electrode etc., can again be returned as sulfuric acid with the oxidizing substance reaction in solution, if but have delay section, S can accumulate herein gradually.
If consider from the angle of the formation efficiency of persulfuric acid, in fact be equivalent to participate in O by 80～90% in the electronics of anode
2Generation, remaining 10～20% generation that contribute to persulfuric acid.O
2Be discharged from outside system, persulfuric acid becomes sulfuric acid after being used to oxidizing reaction, be back to indoor and recycle solution, thereby water is consumed and sulfuric acid concentration thickens gradually in the tank room of electrolysis sulfuric acid.
As mentioned above, although prevent fully that at negative electrode being created on principle of sulphur from being difficult, utilize the oxidizing substance (persulfuric acid etc.) that generates at anode, the sulphur oxidation can be returned as sulfuric acid.Cause oxidation smoothly in the situation that solution is detained, suitable is carries out change poles and generate persulfuric acid near delay section, thereby removes the sulphur of delay section.
In the present invention, be better to have the delay section that is detained for sulphuric acid soln in tank room.Delay section does not mean the specific position of tank room, may produce in different positions delay section according to the structure of each tank room.Delay section easily is formed at the position that the circulation of sulphuric acid soln is hindered.
Delay section easily is formed at the angle recess jumpy on the surfaces such as the corner of member, is formed at cross part, containment member and the electrode of electrode and spacer or the cross part of spacer etc.
In addition, have in tank room in the long-pending narrowed flow path section situation than other part less of cross section of fluid channel, precipitate fills up and easily stops up runner, so in the tank room with narrowed flow path section, the present invention is useful especially.Narrowed flow path section is at the position in the downstream side that is positioned at tank room, locate more easily to become problem such as fluid hole etc., the precipitate of peeling off after accumulating in delay section flows with sulphuric acid soln, above-mentioned precipitate adheres to and is accumulated in the inlet opening place of tank room, soon occur to stop up etc., also might cause the problem that sulphuric acid soln flows that hinders.
According to contriver's research so far as can be known, be more than 85 quality % and current density is 50A/dm at sulfuric acid concentration
2In above situation, Sulfur capacity is easily separated out and is accumulated.When sulfuric acid concentration is higher than this, need to set current density lower.In addition, reaching the condition of 40～70 ℃ with the chamber inlet temperature turns round.But, can think that resistance rises if sulphur is separated out, switched on, indoor resistance increase, chambers temp rise, and accelerate separating out of sulphur.Qualitatively, can think because moisture distribute quickening, the cause that the concentration of particularly locating in shown in Figure 7 delay section etc. significantly rises.Special not preferred chamber inlet temperature surpasses the running of 70 ℃.
According to above content as can be known, the problem of sulphur precipitate in satisfying following 3 conditions any 1 easily occur when above, particularly desirably implement the present invention under this condition.
(a) sulfuric acid concentration in tank room is more than 85 quality %;
(b) the sulfuric acid temperature of tank room entrance is more than 70 ℃;
(c) current density is 50A/dm
2Above.
In the electronic material that uses sulfuric acid electrolyte cleaned, the TOC concentration after cleaning was 0～10mg/l, has hardly organism.
The effect of invention
According to the present invention described above, in tank room during the electrolysis sulphuric acid soln, can obtain to avoid sulphur precipitate or precursor to accumulate and situation about having problems, the effect that can continue to carry out stable electrolysis.
Description of drawings
Fig. 1 means the figure of the one chip cleaning system of the tank room that possesses one embodiment of the present invention.
Fig. 2 means the figure of the batch-type cleaning system of the tank room that possesses one embodiment of the present invention.
Fig. 3 means that use does not possess the figure of batch-type cleaning system of the tank room of change poles function.
Fig. 4 means the figure of Pourbaix diagram.
Fig. 5 means the figure of Pourbaix diagram.
Fig. 6 means that the sulfuric acid concentration based on Pourbaix diagram is that 92 quality %, temperature are the figure of the electromotive force of the sulfuric acid of 60 ℃ and water.
Fig. 7 means the figure of the accumulated state of the structure of tank room and sulphur.
Embodiment
(embodiment 1)
Below, possess the cleaning system of the electrolyzer of one embodiment of the present invention based on description of drawings.
In addition, in the explanation of this embodiment, for tank room, describing with the tank room that has anode and negative electrode as electrode, still, as electrode, can be also to possess the electrode of bipolar electrode except anode, negative electrode.In addition, as tank room, can be also so that the gapped mode configuring multi-layer of the mutual tool of electrode electrode, the tank room that the circulation sulphuric acid soln carries out electrolysis between each electrode.
Be formed with inlet opening 22a, be formed with fluid hole 22b at outlet side at inlet side on spacer 22, these inlet openings 22a, fluid hole 22b consist of by comparing quite narrow runner with runner 23, and inlet opening 22a, fluid hole 22b are equivalent to narrowed flow path of the present invention section.In addition, configure O type circle 24 as containment member, to guarantee the stopping property of runner 23 between spacer 22 and anode 20 and negative electrode 21.Material as consisting of spacer 22 it is desirable to have insulativity, the starting material of erosion resistance (for example tetrafluoroethylene system).
In above-mentioned tank room 2, the corner angle section of electrode 20,21 internal surface and spacer 22 or the inner surface side of O type circle 24 form the delay section 25 that hinders the sulphuric acid soln circulation.Tank room 2 is configured in the below according to the mode that forms to the upper reaches with inlet side, and outlet side is configured in the top.
Above-mentioned tank room 2 is connected with electrolytic solution retention basin 10 by the first circulation line 5, can carry out the logical liquid of circulation of sulphuric acid soln between tank room 2 and electrolytic solution retention basin 10.Namely, the first circulation line 5 send into side being connected with tank room 2 with mode that the inlet side of tank room 2 is communicated with, the first circulation line 5 return to side to be connected with tank room 2 with the mode of the outlet side connection of tank room 2.
The side of returning at the first circulation line 5 is provided with gas-liquid separation groove 6.This gas-liquid separation groove 6 is used for taking in the sulphuric acid soln of air inclusion, after the gas delivery in sulphuric acid soln, then is expelled to outside system, this gas-liquid separation groove 6 can use known gas-liquid separation groove, as the present invention, as long as can realize gas-liquid separation, just its structure is not particularly limited.
In addition, the side of sending at the first circulation line 5 is provided with the recycle pump 7 that makes sulphuric acid soln circulation and the water cooler 8 that sulphuric acid soln is cooling.The first circulation line 5 and recycle pump 7 are equivalent to liquor charging of the present invention section.Water cooler 8 is used for cooling sulphuric acid soln, makes it reach the liquid temperature of suitable electrolysis such as 40～70 ℃ of grades.As the present invention, its structure is not particularly limited.Consist of electrolyzer of the present invention by above-mentioned tank room 2, direct supply 3, power control part 4, the first circulation line 5, gas-liquid separation groove 6, recycle pump 7, water cooler 8.
In addition, above-mentioned electrolytic solution retention basin 10 is connected by the side of sending into of liquid-feeding pump 12 with the second circulation line 11.
Be provided with well heater 13 on the liquor charging direction of the second circulation line 11.In the downstream side of well heater 13, the liquor charging direction front of the second circulation line 11 is connected with one chip washing unit 15.
Above-mentioned well heater 13 has the pipeline of quartzy system, for example utilizes that the near infrared ray well heater carries out the transience heating to sulphuric acid soln, can obtain sulphuric acid soln as the condition instant heating sulphuric acid soln of the liquid temperature of 150～220 ℃ in one chip washing unit 15.
In above-mentioned one chip washing unit 15, for example electronic material substrate 100 is loaded in universal stage is first-class and be fixed, make the sulphuric acid soln that contains persulfuric acid flow to from nozzle that semiconductor material is first-class to be processed.
In addition, in present embodiment, the washing unit take washing unit as one chip is illustrated, but as the present invention, the classification of washing unit is not limited by this, can be the washing unit of batch-type yet.
One chip washing unit 15 is connected with the side of returning of the second circulation line 11.In the side of returning of the second circulation line 11, the Return-ing direction front that is disposed with pump 16, reactive tank 17, liquid-feeding pump 18, water cooler 19, the second circulation lines 11 along Return-ing direction is connected with above-mentioned electrolytic solution retention basin 10.
Then, the action of the cleaning system that formed by said structure described.
Storing sulfuric acid concentration in electrolytic solution retention basin 10 is that 85～96 quality %, liquid temperature are the sulphuric acid soln of 50～80 ℃.Above-mentioned sulphuric acid soln is recycled pump 7 and carries by the first circulation line 5, after being adjusted at water cooler 8 temperature (40～70 ℃) that is fit to electrolysis, is imported into the liquid feeding side of tank room 2, flows in runner 23 from inlet opening 22a.
In tank room 2, utilize that between direct supply 3 antianodes, negative electrode, forward applies voltage, will be imported into the sulphuric acid soln electrolysis in tank room 2.In addition, by this electrolysis, in tank room 2, generate the oxidizing substance that contains persulfuric acid in anode side, produce oxygen simultaneously, produce hydrogen at cathode side.These oxidizing substances and gas are interior mobile at runner 23 with the state that mixes with above-mentioned sulphuric acid soln.Be sent to the first circulation line 5 at the interior mobile sulphuric acid soln of runner 23 by fluid hole 22b.The sulphuric acid soln that is sent from fluid hole 22b is sent to gas-liquid separation groove 6 by the first circulation line 5, and above-mentioned gas is separated.In addition, above-mentioned gas is discharged to outside the native system system, carries out safe handling with catalyst-assembly (not shown) etc.
At gas-liquid separation groove 6, the sulphuric acid soln after gas delivery is contained persulfuric acid, further by after the returning to side and be back to electrolytic solution retention basin 10 of the first circulation line 5, carry out electrolysis by repeatedly delivering to tank room 2, improve the concentration of persulfuric acid.When persulfuric acid concentration reached suitable degree, the part of the sulphuric acid soln in electrolytic solution retention basin 10 was delivered to well heater 13 by the side of sending into of the second circulation line 11 by liquid-feeding pump 12.
In well heater 13, pass through runner by the near infrared ray heater heats while comprise the sulphuric acid soln of persulfuric acid.During liquor charging, it is desirable to adjust the flow of sulphuric acid soln, make from the entrance of well heater 13 that the logical liquid time till use is less than 1 minute one chip washing unit 15, is better to be less than 20 seconds, is more preferably to be less than 10 seconds.In addition, in one chip washing unit 15, flow in the time of 500～2000mL/ minute is appropriate, under this flow, according to the above-mentioned logical liquid time be less than that the condition of 1 minute is set the length of the runner of well heater 13, cross section of fluid channel is long-pending and long at the pipeline of second circulation line 11 in its downstream side, cross section of fluid channel is long-pending etc.In one chip washing unit 15, when supplying with sulphuric acid soln to electronic material substrate 100, has the liquid temperature of the scope of 150 ℃～220 ℃.
In one chip washing unit 15, for example be provided with 1 * 10
12～1 * 10
16Atom/cm
2The semiconductor materials such as silicon wafer of the resist layer of ion are cleaning object.
By one side, this electronic material substrate 100 is rotated on not shown universal stage, on one side never illustrated nozzle little by little drip the high temperature that contains persulfuric acid sulphuric acid soln etc. so that it contacts with electronic material substrate 100, remove thereby effectively the pollutents such as resist layer on electronic material substrate 100 are peeled off.
Clean the sulphuric acid soln that uses and discharge from one chip washing unit 15, delivered to reactive tank 17 and store in reactive tank 17 by pump 16 by the side of returning of the second circulation line 11.Store and contain the residual organic matters such as resist layer that washed by one chip washing unit 15 in the sulphuric acid soln of reactive tank 17, storing during reactive tank 17, residual organic matter is by the contained oxidizing substance oxygenolysis of sulphuric acid soln.In addition, the time that stores of the above-mentioned sulphuric acid soln in reactive tank 17 can be adjusted arbitrarily according to content of residual organic matter etc. etc.At this moment, from one chip washing unit 15 sustainable supply high temperature and contain the sulphuric acid soln of persulfuric acid, reactive tank 17 is maintained suitable temperature.
In reactive tank 17, the sulphuric acid soln that the residual organic matter that contains is oxidized have been decomposed utilizes liquid-feeding pump 18 to be back to electrolytic solution retention basin 10 by the water cooler 19 that is arranged on the second circulation line 11.
In addition, if the sulphuric acid soln of high temperature is back to electrolytic solution retention basin 10, can cause promoting to store the decomposition of the persulfuric acid in the sulphuric acid soln of electrolytic solution retention basin 10, so above-mentioned sulphuric acid soln is imported in electrolytic solution retention basin 10 after being cooled to the suitable temperature of 50～80 ℃ of left and right at the device 19 that is cooled.The send into side of sulphuric acid soln by the first circulation line 5 that is imported in electrolytic solution retention basin 10 is sent to tank room 2, generates persulfuric acid by electrolysis, and the side of returning by the first circulation line 5 is sent to electrolytic solution retention basin 10 again.By repeating this circulation, sustainable generation persulfuric acid.
By aforesaid operations, carry the sulphuric acid soln contain persulfuric acid, it is refluxed, thus can be to the scavenging solution of the high temperature of the persulfuric acid that contains high density as sustainable supply in the one chip washing unit 15 that uses side.
In addition, though not explanation in above-mentioned also can be configured at the upstream side of reactive tank 17, drain line branch is connected in the second circulation line 11, in the suitable moment, sulphuric acid soln can not delivered to reactive tank 17 and be expelled to outside system.
Often little by little discharge sulphuric acid soln by drain line, the material that can prevent by this resist layer doped element accumulated in the solution in system and other not oxygenolysis is accumulated and is reached high density.This operation can be by being arranged on the switch-valve on return line and drain line on-off control etc. carry out.
In above-mentioned cleaning system, by continuously running duty, in tank room 2, as mentioned above electrode surface, particularly electrode week the end and the delay section 25 that becomes the dark place part of O type circle generate sulphur or generate relevant chemical species with sulphur.If with its placement, can grow gradually as mentioned above, cause and peel off and the obstruction of narrowed flow path.
So, in the present invention, when the time length of electrolysis reaches the specified time or the processing sheet number of electronic material substrate 100 when reaching the regulation sheet and counting, can judge when separating out of sulphur composition reaches to a certain degree etc., control by power control part 4, make the change poles operation that puts on the voltage reversal between anode 20 and negative electrode 21 from direct supply 3, carry out electrolysis.Thus, waiting sulphur precipitate of separating out to be played near the oxidizing substance dissolving that generates the negative electrode 21 of anodize at change poles near negative electrode 21, move together with sulphuric acid soln.By the change poles operation is continued to a certain degree, the sulphur precipitate can be eliminated or reduced, then can continue to carry out stable electrolysis.After the elimination of sulphur precipitate or reducing, continuous service under this state, again carry out change poles before the negative electrode place's sulphur precipitate after change poles or its precursor are accumulated, make reversely to be applied to the voltage reversal between anode 20 and negative electrode 21 and forward applies voltage, carry out electrolysis.
If the repetition aforesaid operations can continue to carry out stable electrolysis for a long time.
Usually, in the change poles that adheres to for organism, negative electrode is different with anode, thus the change poles time be restricted, but in this embodiment, because being all diamond electrode, so (10～100 hours) conventional operation carries out for a long time under the state of change poles.
In addition, the time that continues to carry out the operation after change poles can adopt common electrolysis time to reach the situation of predetermined specified time.Specified time can be determined the concentration of the energising amount of considering accumulation, sulphuric acid soln, temperature, logical liquid speed etc. are rear, or obtains according to experiment.In addition, the sheet number of electronic material substrate 100 that also can be after cleaning reaches the regulation sheet when counting, and implements the change poles operation.
Although the time length that also can make the operation after change poles is fixing, diamond electrode, it is desirable to the time length is fixed in order to make the adamantine wearing and tearing equalization of following operation in the situation that the two sides is laminated with diamond layer with the thickness of equalization.
In addition, as other opportunitys of implementing the change poles operation, can utilize the result of the degree of separating out of the sulphur of inferring in tank room.Namely, when the degree of separating out of the sulphur of inferring reaches predetermined degree, implement the change poles operation.The degree of separating out of sulphur can be judged according to the electrolysis voltage that rises when carrying out electrolysis with constant current as above.If namely this voltage reaches predetermined electrolysis voltage, be considered as separating out of sulphur and carry out, thereby implement the change poles operation.
(embodiment 2)
Then, above-mentioned electrolyzer 1 is applied to the embodiment 2 of batch-type rinse bath 30 based on Fig. 2 explanation.In addition, in this embodiment 2 with the structure tag prosign of above-mentioned embodiment 1 synonym, omit or simply its explanation.
Above-mentioned tank room 2 is connected with electrolytic solution retention basin 10 by the first circulation line 5.The side of returning at the first circulation line 5 is provided with gas-liquid separation groove 6, is provided with successively recycle pump 7, water cooler 8 in the side of sending into of the first circulation line 5.
The discharge opeing side of batch-type rinse bath 30 is connected the second circulation line 31 and is connected with liquid feeding side, be provided with liquid-feeding pump 32 and well heater 33 in the side of returning of the second circulation line 31.Electronic material substrate 100 is immersed in sulphuric acid soln in batch-type rinse bath 30, the resist layer etc. that is attached to electronic material substrate 100 is peeled off cleaning.At this moment, Yi Bian utilize the not shown heating parts such as well heater or heat exchanger to control so that the temperature of batch-type rinse bath 30 reaches 120～190 ℃, Yi Bian make the sulphuric acid soln circulation.
The second circulation line 31 is connected with in the downstream side of liquid-feeding pump 32 and in the upstream side branch of well heater 33 and returns to the 3rd circulation line 35, returns to that the liquor charging of the 3rd circulation line 35 is distolateral to be connected with electrolytic solution retention basin 10 by water cooler 37.
Electrolytic solution retention basin 10 by liquid-feeding pump 36 with send into the 3rd circulation line 34 and be connected.Sending into the 3rd circulation line 34 is connected with the second circulation line 31 interflow in the downstream side of well heater 33.
Above-mentioned well heater 33 adopts the structure same with above-mentioned well heater 13.
Then, the action of the cleaning system that formed by said structure described.
Storing sulfuric acid concentration in electrolytic solution retention basin 10 is that 85～96 quality %, liquid temperature are the sulphuric acid soln of 50～90 ℃, this sulphuric acid soln is recycled pump 7 and carries by the first circulation line 5, after being adjusted at water cooler 8 temperature (40～80 ℃) that is fit to electrolysis, be imported into runner 23 from the inlet opening 22a of tank room 2.
In tank room 2, utilize that between direct supply 3 antianodes, negative electrode, forward applies voltage, will be imported into the sulphuric acid soln electrolysis in tank room 2.Be sent to the first circulation line 5 by the sulphuric acid soln after electrolysis by fluid hole 22b, at gas-liquid separation groove 6 with gas delivery.
At gas-liquid separation groove 6 with the above-mentioned sulphuric acid soln after gas delivery by after the returning to side and be back to electrolytic solution retention basin 10 of the first circulation line 5, carry out electrolysis by repeatedly delivering to tank room 2, improve the concentration of persulfuric acid.If persulfuric acid concentration reaches suitable degree, the part of the sulphuric acid soln in electrolytic solution retention basin 10 is delivered to second circulation line 31 in the downstream side of well heater 33 by liquid-feeding pump 36 by sending into the 3rd circulation line 34, with the sulphuric acid soln interflow of the second circulation line 31.Sulphuric acid soln behind the interflow is imported in batch-type rinse bath 30.
In addition, the sulphuric acid soln in batch-type rinse bath 30 utilizes liquid-feeding pump 32 to circulate by the second circulation line 31.At this moment, sulphuric acid soln is heated by well heater 33 and is imported in batch-type rinse bath 30.
In well heater 33, Yi Bian make the sulphuric acid soln that contains persulfuric acid by runner, Yi Bian use heater heats.At this moment, and send into the sulphuric acid soln that the 3rd circulation line 34 carries and mix by above-mentioned, heat when interior being supplied to batch-type rinse bath 30, make it have the liquid temperature of the scope of 120 ℃～190 ℃.
At the interior cleaning electronic material of batch-type rinse bath 30 substrate 100.A part of cleaning the sulphuric acid soln that uses circulates in the second circulation line 31 on one side and is heated by well heater 33 and be returned to batch-type rinse bath 30 on one side, simultaneously rest part is back to electrolytic solution retention basin 10 by returning to the 3rd circulation line 35.At this moment, the sulphuric acid soln device 37 that is cooled is cooled to 40～70 ℃ that are fit to electrolysis.
In electrolytic solution retention basin 10, sulphuric acid soln is recycled pump 7 by the first circulation line 5 and delivers to tank room 2 to carry out the generation of persulfuric acid, is back to electrolytic solution retention basin 10.
By repeating the circulation of above-mentioned sulphuric acid soln, can carry out the cleaning of electronic material substrate 100 under the state of persulfuric acid concentration stabilize.
By keep running status in above-mentioned cleaning system, in tank room 2, as mentioned above at delay section's 25 generation sulphur or the chemical species relevant with the sulphur generation.In this embodiment, by carrying out the control of power control part 4 with the moment of regulation, also can implement to make the change poles operation that puts on the voltage reversal of 21, anode 20 and negative electrode from direct supply 3, continue to carry out electrolysis.By this, make near the sulphur precipitate dissolving that grade is separated out negative electrode.By the change poles operation is continued to a certain degree, the sulphur section of separating out can be eliminated or reduces, then can continue to carry out stable electrolysis.
(comparative example)
In this example, except do not have power control part 4 in embodiment 2, have the structure same with embodiment 2, describe based on Fig. 3.In tank room 2, with direct supply 3 often antianode side and cathode side apply forward voltage, can carry out the electrolysis of sulphuric acid soln.
In this example, also can the electrolysis sulphuric acid soln and effective cleaning semiconductor substrate etc. are cleaned material.But, As time goes on, generating the precipitate of sulphur in tank room, the sulphur precipitate of peeling off stops up the narrowed flow path section of tank room 2 etc., makes cleansing power descend or the cleaning difficulty that becomes itself.In addition, if the sulphur precipitate of peeling off arrives the narrowed flow path such as inlet opening of tank room, can produce the problem of stopping up runner or mobile variation.
Above, describe the present invention based on above-mentioned embodiment, but the present invention is not limited to the content of above-mentioned embodiment, can carry out suitable change in not departing from the scope of the present invention.
Embodiment
One: the embodiment that uses one chip cleaning system shown in Figure 1 is described.
At sulfuric acid concentration=92 quality %, tank room entrance liquid temperature=60 ℃, current density=35A/dm
2Condition under continuous service.Change poles is namely implemented in the electrolysis that often continues to carry out 50 hours, and after repeating to continue for 10 times 50 hours, change poles, internal examination is carried out in the chamber of opening, and result does not confirm adhering to of sulphur fully.
Its two: the embodiment that uses batch-type cleaning system shown in Figure 2 is described.
At sulfuric acid concentration=85 quality %, tank room entrance liquid temperature=50 ℃, current density=50A/dm
2Condition under continuous service.Each 50 wafer of processing, change poles is carried out in 40 batches of every processing.After it was repeated 8 times, internal examination was carried out in the chamber of opening, and result does not confirm adhering to of sulphur fully.
(comparative example)
As shown in Figure 3, use the batch-type cleaning system that does not possess the change poles function, at sulfuric acid concentration=85 quality %, tank room entrance liquid temperature=50 ℃, current density=50A/dm
2Condition under continuous service, result voltage when surpassing 100 batches begins to rise, flow quantity also descends gradually at leisure.When the flow quantity in average Room 1 reduces by half, the chamber of opening checks, found that at chamber export department runner to have the obstruction that is caused by sulphur.
The explanation of symbol
1 electrolyzer
2 tank rooms
20 anodes
21 negative electrodes
22 spacers
The 22a inlet opening
The 22b fluid hole
23 runners
3 direct supplys
4 power control parts
5 first circulation lines
7 recycle pumps
8 water coolers
10 electrolytic solution retention basins
15 one chip washing units
30 batch-type rinse baths
Claims (14)
1. sulfuric acid electrolysis process, it is in tank room, at least connecing liquid level is made of conductive diamond and comprises at least in a plurality of electrodes of anode and negative electrode, sulphuric acid soln more than circulation 70 quality % between described anode and described negative electrode is implemented electrolysis on one side on one side, thereby generate the electrolysis process of persulfuric acid, it is characterized in that, apply forward voltage and implement the routine operation of described electrolysis between the anode of described electrode and negative electrode, implement simultaneously to make the change poles operation of the voltage reversal that puts on described anode and negative electrode during described routine operation, the sulphur precipitate that generates in tank room when making described routine operation is dissolved in described sulphuric acid soln when described change poles operation in.
2. sulfuric acid electrolysis process as claimed in claim 1, is characterized in that, Yi Bian sulphuric acid soln is flowed in described tank room outside described tank room, Yi Bian implement described electrolysis, the described sulphuric acid soln through electrolysis flowed out to outside described tank room.
3. sulfuric acid electrolysis process as claimed in claim 1 or 2, is characterized in that, has the delay section that the described sulphuric acid soln that supplies to circulate is detained in described tank room.
4. sulfuric acid electrolysis process as described in any one in claim 1～3, is characterized in that, has the narrowed flow path section of flowing for described sulphuric acid soln in described tank room.
5. sulfuric acid electrolysis process as claimed in claim 3, is characterized in that, disposes the spacer of the runner of guaranteeing sulphuric acid soln between described electrode, forms described delay section by this spacer or by this spacer and other members.
6. sulfuric acid electrolysis process as claimed in claim 5, is characterized in that, is provided with containment member between described electrode and described spacer, forms described delay section by the sealing member at least.
7. sulfuric acid electrolysis process as described in claim 5 or 6, is characterized in that, is formed with the fluid hole that the described sulphuric acid soln of confession as narrowed flow path section passes through in described spacer.
8. sulfuric acid electrolysis process as described in any one in claim 5～7, is characterized in that, is formed with the inlet opening that the described sulphuric acid soln of confession as narrowed flow path section passes through in described spacer.
9. sulfuric acid electrolysis process as described in any one in claim 1～8, it is characterized in that, be provided with the circulation line that is connected to the entrance of described tank room from the outlet of described tank room, have narrowed flow path section at the upstream side of the delay section of this circulation line and/or tank room.
10. sulfuric acid electrolysis process as described in any one in claim 1～9, is characterized in that, described change poles operation is implemented by continuing to carry out the routine operation of specified time.
11. sulfuric acid electrolysis process as described in any one in claim 1～10 is characterized in that, the judgement that described change poles operation is based on the precipitation state of described sulphur is implemented.
12. sulfuric acid electrolysis process as described in any one in claim 1～11 is characterized in that, satisfies at least one in following condition (a)～(c):
(a) concentration of the described sulfuric acid in described tank room is more than 85 quality %;
(b) the sulfuric acid temperature of described tank room entrance is more than 70 ℃;
(c) current density in described electrolysis is 50A/dm
2Above.
13. the sulfuric acid electrolyzer is characterized in that, possesses:
Sulphuric acid soln can feed liquor and the tank room of fluid;
Mode with the described sulphuric acid soln of circulation in gap each other is configured in described tank room and connects at least a plurality of electrodes that comprise at least anode and negative electrode that liquid level is made of conductive diamond;
Guarantee the spacer in described interelectrode gap;
The narrowed flow path section of the described sulphuric acid soln circulation of the confession that this spacer has;
Described tank room is carried the liquor charging section of sulphuric acid soln;
To executing alive power supply unit between the described anode of described electrode and described negative electrode; With
Power control part, this power control part carries out following control to described power supply unit: to applying forward voltage between described anode and described negative electrode, implement to make simultaneously the change poles that puts on the voltage reversal between described anode and described negative electrode under predetermined condition when the electrolysis of routine.
14. the sulfuric acid electrolyzer is characterized in that, possesses:
Sulphuric acid soln can feed liquor and the tank room of fluid;
Mode with the described sulphuric acid soln of circulation in gap each other is configured in described tank room and connects at least a plurality of electrodes that comprise at least anode and negative electrode that liquid level is made of conductive diamond;
Guarantee the spacer in described interelectrode gap;
The delay section of the described sulphuric acid soln delay of confession that forms by this spacer or by this spacer and other members;
To executing alive power supply unit between the described anode of described electrode and described negative electrode; With
Power control part, this power control part carries out following control to described power supply unit: implement to make the change poles that puts on the voltage reversal between described anode and described negative electrode when the electrolysis of routine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011042427A JP2012180538A (en) | 2011-02-28 | 2011-02-28 | Method and apparatus for electrolyzing sulfuric acid |
| JP2011-042427 | 2011-02-28 | ||
| PCT/JP2012/054371 WO2012117927A1 (en) | 2011-02-28 | 2012-02-23 | Sulfuric acid electrolysis method and sulfuric acid electrolysis device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103384731A true CN103384731A (en) | 2013-11-06 |
Family
ID=46757864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800105271A Pending CN103384731A (en) | 2011-02-28 | 2012-02-23 | Sulfuric acid electrolysis method and sulfuric acid electrolysis device |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20130319875A1 (en) |
| JP (1) | JP2012180538A (en) |
| KR (1) | KR20130135895A (en) |
| CN (1) | CN103384731A (en) |
| TW (1) | TWI437127B (en) |
| WO (1) | WO2012117927A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971463A (en) * | 2014-04-14 | 2015-10-14 | 永久电极株式会社 | Method and apparatus of decomposing fluorinated organic compound |
| CN106917104A (en) * | 2017-03-17 | 2017-07-04 | 南开大学 | A kind of method of use BDD electrodes electro synthesis persulfate |
| CN108043205A (en) * | 2017-12-21 | 2018-05-18 | 双盾环境科技有限公司 | A kind of self-loopa hydrogen peroxide new desulfurization process |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6191720B1 (en) * | 2016-03-25 | 2017-09-06 | 栗田工業株式会社 | Persulfuric acid solution production and supply apparatus and method |
| JP6866751B2 (en) * | 2017-04-25 | 2021-04-28 | 栗田工業株式会社 | Cleaning system |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233231A (en) * | 1996-10-15 | 1999-10-27 | 安德列亚斯·魏斯贝克 | Method to reduce or prevent scaling |
| JP2007262531A (en) * | 2006-03-29 | 2007-10-11 | Kurita Water Ind Ltd | Electrolytic cell and sulfuric acid recycling type cleaning system using the electrolytic cell |
| CN101061261A (en) * | 2004-09-17 | 2007-10-24 | 栗田工业株式会社 | Cleaning system of sulfuric acid recycling type and persulfuric acid feeder of sulfuric acid recycling type |
| JP2008132468A (en) * | 2006-10-31 | 2008-06-12 | Institute Of National Colleges Of Technology Japan | Electrolysis type water treatment method |
| JP2010156034A (en) * | 2009-01-05 | 2010-07-15 | Japan Organo Co Ltd | Apparatus and method for producing persulfuric acid |
| TW201043734A (en) * | 2009-03-24 | 2010-12-16 | Kurita Water Ind Ltd | Functionality solution supply system and functionality solution supply method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3766037A (en) * | 1972-02-11 | 1973-10-16 | Andco Inc | Electrochemical processes for the removal of contaminants from aqueous media |
| JP3465367B2 (en) * | 1994-08-23 | 2003-11-10 | 東陶機器株式会社 | Ion-rich water generator |
| JP2006278838A (en) * | 2005-03-30 | 2006-10-12 | Kurita Water Ind Ltd | Sulfuric acid recycling type cleaning system |
-
2011
- 2011-02-28 JP JP2011042427A patent/JP2012180538A/en active Pending
-
2012
- 2012-02-23 CN CN2012800105271A patent/CN103384731A/en active Pending
- 2012-02-23 US US14/000,239 patent/US20130319875A1/en not_active Abandoned
- 2012-02-23 WO PCT/JP2012/054371 patent/WO2012117927A1/en active Application Filing
- 2012-02-23 KR KR1020137020767A patent/KR20130135895A/en active Search and Examination
- 2012-02-24 TW TW101106122A patent/TWI437127B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233231A (en) * | 1996-10-15 | 1999-10-27 | 安德列亚斯·魏斯贝克 | Method to reduce or prevent scaling |
| CN101061261A (en) * | 2004-09-17 | 2007-10-24 | 栗田工业株式会社 | Cleaning system of sulfuric acid recycling type and persulfuric acid feeder of sulfuric acid recycling type |
| JP2007262531A (en) * | 2006-03-29 | 2007-10-11 | Kurita Water Ind Ltd | Electrolytic cell and sulfuric acid recycling type cleaning system using the electrolytic cell |
| JP2008132468A (en) * | 2006-10-31 | 2008-06-12 | Institute Of National Colleges Of Technology Japan | Electrolysis type water treatment method |
| JP2010156034A (en) * | 2009-01-05 | 2010-07-15 | Japan Organo Co Ltd | Apparatus and method for producing persulfuric acid |
| TW201043734A (en) * | 2009-03-24 | 2010-12-16 | Kurita Water Ind Ltd | Functionality solution supply system and functionality solution supply method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971463A (en) * | 2014-04-14 | 2015-10-14 | 永久电极株式会社 | Method and apparatus of decomposing fluorinated organic compound |
| CN106917104A (en) * | 2017-03-17 | 2017-07-04 | 南开大学 | A kind of method of use BDD electrodes electro synthesis persulfate |
| CN108043205A (en) * | 2017-12-21 | 2018-05-18 | 双盾环境科技有限公司 | A kind of self-loopa hydrogen peroxide new desulfurization process |
| CN108043205B (en) * | 2017-12-21 | 2019-05-24 | 双盾环境科技有限公司 | A kind of self-loopa hydrogen peroxide sulfur removal technology |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI437127B (en) | 2014-05-11 |
| WO2012117927A1 (en) | 2012-09-07 |
| KR20130135895A (en) | 2013-12-11 |
| US20130319875A1 (en) | 2013-12-05 |
| TW201241237A (en) | 2012-10-16 |
| JP2012180538A (en) | 2012-09-20 |
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