TW201231730A - Electrically conductive diamond electrode, and sulfuric acid electrolysis method and sulfuric acid electrolysis apparatus each utilizing same - Google Patents

Abstract

The present invention is an electrically conductive diamond electrode which comprises an electrically conductive base and an electrically conductive diamond layer coated on the surface of the electrically conductive base, and which is characterized in that (1) the electrically conductive diamond layer has a thickness of 1-25 μm, (2) a potential window fulfills formula (1), and (3) the ratio (A/B) of a diamond component (A) to a non-diamond component (B) as determined by Raman spectroscopy fulfills formula (2): (1) 2.1 V = potential window = 3.5 V; (2) 1.5 -1 in Raman spectroscopy; B = the intensity at a wave number of 1500 cm-1 in Raman spectroscopy). The present invention provides: an electrically conductive diamond electrode in which the thickness of an electrically conductive diamond layer and the crystallinity of electrically conductive diamond are regulated so as to achieve high electrode durability and high oxidizable substance production efficiency at a low cell voltage; and a sulfuric acid electrolysis method and a sulfuric acid electrolysis apparatus, each of which utilizes the electrode.

Description

201231730 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a conductive diamond electrode and a sulfuric acid electrolysis method and a sulfuric acid electrolysis apparatus which directly electrolyze a sulfur-stable stable raw material using a conductive diamond electrode. [Prior Art] As a pretreatment agent or a shut-off agent for metal electrolysis, an oxidizing agent in chemical mechanical polishing treatment in the manufacture of semiconductor elements, an oxidizing agent for organic substances in wet analysis, and a cleaning material for crushing crystals, or Check the process used in the process _ 'can use too much or touch salt. Squamous persulfate or persulfate is called an "oxidizing substance". It is known that this "oxidizing substance" is produced by electrolysis of sulfuric acid and has been produced by electrolysis on an industrial scale. In the case of Yu Shuming, the term "oxidizing substance" refers to persulfuric acid or hydrogen peroxide, which is a general term for peroxydisulfuric peroxymonosulfuric acid. When an "oxidizing substance" which is produced by electrolysis is used for cleaning or surface treatment of a member, it is a method in which the higher the total concentration is, the better the effect is, and the second concentration is the liquid medicine. In addition, in the manufacturing of the material, the electrolysis method is used, and the electric power unit calculated from the electrolysis waste, the electrolysis current, and the current efficiency, and the crane efficiency which is stable over time and high, are required for less production. Therefore, for the improvement of the productivity, it is sought to achieve (4) the high conductivity of the electrode made by the manufacture of the upper rib electrode. Since the electrode life is prolonged, a clean electrolyte without 100145902 201231730 self-consumption can be produced. Waiting for it. The second plant has a method of electrolyzing sulfuric acid which is made by electrolyzing the nucleus of the electric diamond to produce a sulfuric acid electrolysis method and a cleaning method for the round processed material. Force sulfur u矽曰曰^ package 11 diamond electrode and more commonly used as the button to generate the 'j under salt electrode · large, so the Jiang Yi Shi ratio, due to the generation of oxygen overvoltage, the stone claw酉夂 Electrolytic oxidation - and the stability of the _ _ _ _ _ _ _ _ _ _ _ _ In addition, it has the advantages of strong parent and long electrode life. In other words, the lead-electrode_stone electrode has higher efficiency and higher durability than other electrode catalysts (pt, pb〇2, etc.), and can produce a clean renewed rod without contamination from the electrode,戌 胄 胄 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 。 。 Patent Document 1 discloses a method in which a sulfuric acid electrolysis method for producing sulfuric acid is used, and a concentrated sulfuric acid is electrolyzed to produce an inventory containing persulfuric acid. The cleaning liquid is supplied to the object to be cleaned with an anti-cut wafer to be cleaned, and the used cleaning liquid having a reduced concentration of persulfuric acid is recovered, and the electrolysis is further performed. The same - cleaning solution is used for cleaning, but it has the relationship between the crystallinity of the conductive f-stone electrode, the Raman spectral characteristic/potential range, and the oxidizing substance in persulfuric acid or cleaning solution such as peroxodisulfate. The productivity of current efficiency and cell voltage is not disclosed. According to Patent Document 2, for a multi-crystal diamond for a tool, the strength of the diamond is increased by the intensity of the ruled thickness of the Raman (4) by the higher intensity of the diamond. Method The diamond system described in Document 2 has a film thickness of two = "The carbon-type drill obtained by the patented Raman spectroscopy" is set to 2.0 by carbon/drilling carbon. Peak ratio (for non-drilling electrodes, for conductive drills and 'the phase of the potential range where the diamond is not electricity one: as the electrolysis characteristics of disulfuric acid and other tears, the solution is not pure. For the purpose of the Raman spectroscopy, the electroconductive electrode for the ozone water-making device is used as the electroconductive electrode for the ozone-based conductive film, and the conductive diamond electrode of the conductive film of the carbon is described in Patent Document 3. The integral intensity of the peak at 1340 Cm ± 20 cm. InInt<m〇> and the integral intensity of the peak existing at 1580-2 〇W Int<measurement> satisfy the following formula' Durable electrode, ozone water with high current efficiency Making device.

Int<1340>/lnt<1580>5 However, Patent Document 3 discloses that the diamond-like carbon system represents amorphous hard carbon and has a structure different from that of a conductive diamond having a crystal structure. However, 'Patent Document 3' uses the diamond-like carbon as an electrode, the relationship between the crystallinity of the conductive diamond electrode and the Raman spectral characteristic/potential range, and the crystallinity of the conductive diamond electrode and the peroxydisulfide. The current efficiency of the oxidizing substance in the persulfuric acid or the cleaning liquid and the productivity of the electrolytic cell voltage are not disclosed in the relationship of 100145902 6 201231730. However, the correlation between the crystallinity of the conductive diamond electrode and the Raman green characteristic/potential range is not clear, and the durability of the electrode cannot be made by the method such as Lee (4). Conductive diamond electrode with high oxidizing agent f generation efficiency at high and low • t solution voltage. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a conductive material which is excellent in durability and has an efficient production efficiency of an oxidizing substance under a low electrolytic cell voltage. A diamond electrode, a sulfuric acid electrolysis method using the same, and a sulfuric acid electrolysis device. The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, the crystallinity of the conductive diamond and the electrolysis property (the durability of the electrode, the voltage of the electrolytic sample, and the current efficiency of the oxidizing substance) are closely related. In addition, in the evaluation of twinning, the above electrolysis performance was successfully achieved by specifying the film thickness of the conductive diamond film, the breadth of the potential range, and the peak intensity ratio of the Raman spectrum. (Means for Solving the Problem) b 100145902 201231730 In order to solve the above problems, the present invention provides a conductive diamond electrode comprising a conductive substrate and a conductive diamond layer coated on the surface of the conductive substrate, and 1) The thickness of the conductive diamond layer is 1 to 25 /zm, 2) the potential range satisfies the formula (1), 3) the ratio of the diamond component A to the non-diamond component B obtained by Raman spectroscopy (A/B) Satisfy the formula (2). Knife 2.1 VS potential range S3.5 V ... (1) 1.5 < A / B ^ 6.5 . " (2) A = Raman spectrum analysis wave number 1300 cm, 1 intensity B = Raman In the spectral analysis, the intensity of the wave number is 1500 cm·1. The second solution of the present invention is to provide an electrode using a conductive diamond layer containing 1000 to 6000 ppm of boron as the conductive diamond layer. Further, a third means of solving the present invention is to provide an electrode in which the above-mentioned conductive base system uses a tantalum substrate. Further, a fourth solution of the present invention is to provide a sulfuric acid electrolysis method which is divided into an anode chamber and a cathode chamber by a separator, and a conductive drill is disposed in the anode chamber; and an anode is provided in the cathode chamber. A sulfuric acid electrolysis method in which an electrolytic solution containing sulfuric acid ions is supplied to the anode chamber and the cathode chamber to perform electrolysis to generate an oxidizing substance in the anolyte in the anode chamber, and a specific conductive diamond electrode is used as the upper side. 100145902 201231730 A conductive diamond electrode is described, and the above electrolyte containing a sulfate ion is made into a solution containing a sulfate ion having a concentration of 2 to 14 mol/l. Further, the fifth means for solving the present invention is to provide a method for electrolyzing sulfuric acid which is applied to the above-mentioned electric secretory towel, and the acid concentration of the solution containing the sulfur sulphide is 4 to 28 mol/l. According to a sixth aspect of the present invention, there is provided a sulfuric acid electrolysis apparatus which is divided into an anode chamber and a cathode chamber by a diaphragm, and a conductive diamond anode is disposed in the anode chamber, and a cathode is disposed in the cathode chamber. A sulfuric acid electrolysis device that externally supplies an electrolyte containing sulfuric acid ions to the anode chamber and the cathode chamber to perform electrolysis to generate an oxidizing substance in the anolyte in the anode chamber, and uses the above (four) diamond electrode, and uses A separator comprising a fluororesin-based cation exchange membrane or a hydrophilized porous dielectric resin crucible is used as the separator. A seventh solution of the present invention is to provide a sulfuric acid electrolysis method, which is divided into an anode chamber and a cathode chamber by a separator, a conductive diamond anode is disposed in the anode chamber, and a cathode is disposed in the cathode chamber, and the cathode is externally A sulfuric acid electrolysis method for generating an oxidizing substance in an anolyte in the anode chamber by supplying an electrolyte containing sulfuric acid ions to the anode chamber and the cathode chamber, and using the above-described conductive diamond electrode as the conductive diamond electrode Further, the above electrolyte containing sulfate ions is electrolyzed under the conditions satisfying the formulas (3) and (4). ΙΟΟ^Χ^ 10000 ...(3) 100145902 9 201231730 25<Υ<250 (4) X = current value / anolyte amount (A/l) Υ = current density (A/dm2) Further, the present invention The eighth solution is to provide a sulfuric acid electrolysis method for electrolyzing a solution containing sulfate ions under the above-mentioned electrolysis conditions under the condition of satisfying (10). & 18000^Z^ 1080000 (5) Ζ = amount of electricity per unit volume (c / 电流 current value X electrolysis time / anolyte amount (Α · s / 1) (effect of the invention) Conductive diamond according to the present invention The electrode, the sulfuric acid electrolysis method using the same, and the sulfuric acid electrolysis device can be manufactured with high current efficiency - an electrode that cannot be achieved by conventional techniques (4) s, a chemical substance solution. The stomach depends on the degree of oxygen of the agricultural system [implementation] The present invention has found that there is a loose relationship between the crystallinity of the conductive diamond electrode and the current efficiency, that is, the crystallinity of the conductive diamond electrode and the electrolysis of sulfuric acid when the upper diamond electrode is assembled in the electrolytic cell. There is a close relationship between the concentration of the electrode and the current efficiency of the oxidizing substance solution produced by the electrode. The carbon atoms formed by the diamond system are combined according to the cubic crystal of the fat blending, and the band gap system is wide and 100145902 201231730 /;; Aspect 'The wealth of the guide diamond fine H is imparted with conductivity by containing impurities of the opposite bloodstone. Eight-> ^'t ^^ - High electrical conductivity Point of view The higher the impurity concentration, the better, the other side is 4, and the concentration of the right side is too high. The crystallinity in the present invention indicates that the second is a lack of durability. In the case of regularity or carbon removal, in the case of non-diamond components, graphite components, and non-zero diamonds, the film thickness of the conductive diamond layer is thinner. In the case of carbon material ^, the crystallinity is lower ^ mu II is more than the actual view of the shirt of the material field (4), the following is not clear, the film thickness of the conductive diamond layer can be clearly understood, by pulling Mann Spectrum is divided into diamond components A, non-diamonds account for eight pounds, and the ratio of non-diamond components B (A/B) is a factor of the table's ambiguity'. By specifying these, the durability of the electrode can be obtained. Electrolysis, oxidizing substance electricity at a lower electrolytic cell voltage: South, can produce high concentration of oxidizing (4) dissolved (four) conductive _ stone electrode, sulphuric acid electrolysis method and sulphuric acid electrolysis device In order to make the present invention constitute a conductive diamond electrode, the conductivity is: the above guide The film thickness of the electric diamond layer is satisfied by the formula (1)', and the ratio of the lock stone obtained by Raman spectroscopy to the non-stone component B (A/B) satisfies the formula (2). /, drill 2.1 VS Potential range 5 v ... (1) 1.5 < A / B ^ 6.5 ... (2) 100145902 201231730 A = the intensity of the wave number in Raman spectroscopy B = the number of waves in Raman spectroscopy 15 〇〇 (^_1 First, the reason for limiting the film thickness of the conductive diamond electrode is described. The thickness of the conductive diamond layer is preferably from 1 to 25 Å, more preferably the thickness of the conductive diamond layer (four) When it is thin, the production time of the above-mentioned conductive diamond layer can be shortened, and the crystallinity of the conductive stony stone is lowered. If the crystallinity is low, the (4) oxidizing substance is low in the power plant. Therefore, if the film thickness becomes too thin, the substrate is exposed due to the corrosion of the substrate. Or the film peels off during electrolysis, etc., and becomes a lack of electrode. Moreover, if the film thickness becomes too thick and is larger than 25 _, the crystal riding property becomes high, and no substrate is exposed, the electrolyte does not permeate to Since the base material is improved in the conductivity of the electrode, the current efficiency of the oxidizing substance is low and the voltage of the electrolytic cell is high. Therefore, the thickness of the conductive diamond electrode of the present invention is preferably 丨 25 25 m. In the present invention, the potential range is a potential region in which no hydrogen or oxygen is generated in the electrolytic reaction of water. When the breadth of the potential range is large, the conductive region is conductive. The crystallinity of the diamond film is the same, and the durability of the electrode is improved. However, if the breadth of the potential range becomes larger than 3.5 V, the current efficiency of the oxidizing substance becomes lower, and the cell voltage becomes higher. The breadth of the scope becomes small At 21 V, the durability of the electrode becomes low. 100145902

S 12 201231730 Further, when the peak intensity ratio A/B of the Raman spectrum is large, the junction of the conductive diamond film becomes high, and the polarity of the electrode is improved. However, if the peak intensity ratio A/B of the Raman spectrum becomes larger than 6.5, the current efficiency of the oxidizing substance becomes low, and the electrolytic cell voltage becomes high. On the other hand, when the Raman spectral intensity ratio is smaller than Α/Β杈, the crystallinity of the conductive diamond film is lowered, and the efficiency of the oxidizing substance is increased, and the electrolytic cell voltage is lowered. However, if the peak intensity ratio Α/Β of the Raman spectrum is 1.5 or less, the durability of the electrode becomes low. The conductive diamond layer preferably contains 1 to 6 ppm of boron, more preferably 3,000 to 5,000 ppm of stone. The higher the concentration of the stone is, the lower the crystallinity is. The electrode having a lower voltage of the electrolytic cell and higher current efficiency of the oxidizing property (4) is preferable. However, if the bribe is too high and is larger than _〇ppm, it becomes an electrode to which tin is attached, and the electrode lacks durability. Therefore, the conductive diamond electrode of the present invention preferably contains 1 〇〇〇~〇〇鹏 boron . The conductive substrate is not particularly limited, and a group, a crane, a chin, a sharp, or the like can be used. When a hard substrate is used, an electrode having better adhesion can be produced. Therefore, the shape of the conductive substrate is preferably further It is not particularly limited, and a plate shape, a miscellaneous shape, a tubular shape, a spherical shape, or the like can be used. The conductive substrate may contain impurities such as boron or carbon. Hereinafter, an example of the implementation of the sulfuric acid electrolysis method and the sulfuric acid electrolysis apparatus of the present invention will be described in detail with reference to the drawings. Fig. 1 is a view showing an example of an electrolytic cell used in the sulfuric acid electrolysis method of the present invention and the sulfuric acid electrolysis apparatus used in 100145902 13 201231730. The electrolytic cell is divided into an anode chamber 3 and a cathode chamber 4, and the anode chamber 3 is a porous PTFE (Poly Tetra Fluoro Ethylene') separator 9 to accommodate the conductive diamond anode 10, and is housed with the above-mentioned sulfuric acid containing The electrolyte of ions; the cathode chamber 4 houses the conductive diamond cathode 12 and is filled with sulfuric acid having the same degree of radiance as the anode chamber 3. An anolyte supply port 7 is connected to the anode chamber 3, and sulfuric acid as an anolyte is supplied to the anode chamber 3 through the anolyte supply port 7. Further, the catholyte supply port 8 is connected to the cathode chamber 4, and the catholyte is supplied to the cathode chamber 4 through the shai catholyte supply port 8. The oxidizing substance solution generated in the anode chamber 3 is discharged from the anolyte discharge port ^. Further, hydrogen and sulfuric acid generated in the cathode chamber 4 are discharged from the cathode liquid discharge port 2. Furthermore, 5 is an anode power supply terminal, 6 is a cathode power supply terminal, n is a conductive substrate of a conductive diamond anode, 13 is a conductive substrate of the conductive diamond cathode 12, 14 is a sealing material for the electrolytic cell, 15 is The cooling jacket '16 is a cooling water discharge port' 17 is a cooling water supply port. The conductive f-crystal diamond anode 1 and the conductive diamond cathode U in the present month are composed of a conductive diamond layer coated on the surfaces of the conductive substrates u and 13. The coating method of the conductive I·green diamond layer is not particularly limited, and any of them may be used. As a representative of I·sheng's side, you can choose hot silk cvD (chemieal Vap〇r

Dep〇S1-, chemical vapor deposition), microwave plasma (four) method, DC-Current, DC) arc nozzle plasma cvd method. 100145902

14 S 201231730 Further, as the cathode, another cathode such as platinum may be used instead of the conductive diamond cathode 12. The electrolyte containing sulfate ion (HS〇4-4S〇42-) in the present invention preferably contains 2 to 14 mol/l of sulfuric acid ion, preferably 3 to 9 m〇i/i of sulfuric acid ion. If the sulfate ion concentration (HSCV or SO/-) is less than 2 mol/b, the current efficiency of the oxidizing substance is lower due to less reactants. Further, when the concentration of the sulfuric acid ion is larger than Umom, the viscosity of the electrolytic solution becomes high, and the gas detachment is deteriorated, and (4) the rate is increased. The decrease in the conductivity of the electrolytic solution is such that the electrolytic cell voltage is higher. Therefore, in the present invention, the sulfuric acid ion concentration of the above-mentioned electrolyte containing sulfate ions is set to 2 to 14 mol/l. The acid (H+) concentration of the electrolyte containing sulfate ions in the present invention is in the range of * to 28 m·, preferably in the range of 6 to 18 m〇i/i. If the acid (H+) is less than 4 m〇1/1, the conductivity of the electrolyte is low and the cell voltage is high. On the other hand, when the acid concentration (H+) is higher than 28 m〇i/i., the current efficiency of the oxidizing substance is lower. In the present invention, the acid concentration of the above-mentioned electrophoresis containing sulfur is set to 4 to 28 m〇m. Further, in the sulfuric acid electrolysis method of the present invention, it is preferred to use the above-mentioned conductive diamond electrode 'and satisfy the 100SXS 1_0, preferably 3G()sXs6_, γ at x = current value / anolyte amount (A / 1). = current density (A/dm2) 100145902 201231730 The electrolyte containing the sulfate ion is electrolyzed under the condition that 25 < Y < 25G is satisfied. The current efficiency of the oxidizing substance is low. If X is less than 100, the X is more than 10 _, and the inside of the tank is filled with the generated gas, and the electrolytic cell voltage becomes high. Further, in the sulfuric acid electrolysis method of the present invention, when the current density Y (A/dm2) is 25 Torr, the current efficiency of the oxidizing substance is lower. On the other hand, if the right γ is 25 Å or more, the heat generation is changed. Obviously, it becomes difficult to control the temperature of the electrolyte. Further, the outgassing property is inferior, the bubble ratio is increased, and the conductivity of the electrolytic solution is lowered to become a higher electric cell. Therefore, in the present invention, it is set to the range of 100SXS10000, 25<Y<250. Further, in the sulfuric acid electrolysis method of the present invention, it is preferred to use a description of the conductive vermiculite electrode 'and at Z = the amount of electricity per unit volume (c / 1) = current value parent electrolysis time / anolyte amount (A · s /1) The electrolyte containing the sulfate ion is electrolyzed under the condition of satisfying 18000$ζ$1〇8〇〇〇〇, preferably 100G〇〇SZS_()〇〇. When z is less than 18,000, the concentration of the oxidizing substance becomes low. On the other hand, if Z is more than 1,080,000, the current efficiency of the oxidizing substance becomes low, so the range is set to 18000 SZS 1080000. The porous PTFE separator 9 of the present invention divides the anode chamber 3 and the cathode chamber 4, and exhibits conductivity by ion exchange or electrolyte flowing through the pores in the separator between the anode chamber 3 and the cathode chamber 4. By. The constituent material is not limited to 100145902 16 201231730. In particular, it is preferable to use a separator containing a fluororesin-based cation exchange membrane or a hydrophilized porous fluororesin. In the present invention, if the separator is not provided, the oxidizing substance is electrolytically reduced at the cathode, and the concentration of the oxidizing substance is lowered. Therefore, the porous PTFE separator 9 is preferably provided. The constituent material of the liquid contact portion of the sulfuric acid electrolytic solution, the piping, the pump, the gas-liquid separation tank, and the like in the present invention is not particularly limited to sulphuric acid PTFE, PFA (polyfluoroalkoxy-H, etc., fluororesin, glass, Quartz. The electrolyte containing sulfuric acid ions in the present invention may contain impurities in addition to sulfate ions, but the current efficiency of persulfuric acid formed by sulfuric acid or sulfuric acid and water is high, so that it can be compared with the product. The reaction is carried out by the oxidizing substance generated by electrolysis = the reason why the concentration of the oxidizing substance in the machine solution is lowered, so: the second electric substance. Moreover, the field of the woman, the former A Jia does not contain the organic whole product In the case of the towel, since it is adversely affected by the element as an impurity, it is preferable not to contain the metal τ Λ. In the invention, it is preferable to set the electrolysis temperature of the electrolysis to 0 to 5 〇 / the lower the dish. When the current efficiency of the emulsifying substance becomes too high, the electric seam is reduced to a high H, and the conductivity of the electrolytic solution is lowered, and the electrolysis cell rate is increased to a temperature of 〇~ machine. ^^' Therefore, it is better to 100145902 Further, in the present invention, the presence or absence of the circulation of the electrolytic solution is not limited, and if the rhododendron/Ι Ι ΛΑ ^ ^ 17 201231730: ring, the electrolyte can be efficiently cooled, and the electrolyte is circulated. The amount of anolyte refers to the amount of all the electrolyte on the anode side in the 糸 以 以 , , , , , , , , , , , 糸 糸 糸 糸 本 本 本 本 : : : : : : : : : : : : : : : : : : : : 2: 吏: lyolysis only the amount of liquid refers to the anode side of the electrolytic cell; the positive aspect of the liquid is shown in the figure 2] is the sulphuric acid electrolysis of the present invention which oxidizes the anolyte and the catholyte The method and the electric (4) 2 are both b. The electrolyte containing the sulfate ion is supplied from the anolyte supply line 18' and is supplied to the anode chamber 3 of the electrolytic cell using the anolyte U 19 and the flow meter 2, in the anode chamber 3. Electrolysis is carried out, using the flow meter 22, the anolyte circulation/discharge pump 23, and circulating in the anode chamber 3 by the anolyte circulation pipe (four). At this time, the line body is separated from the anode liquid fraction _%, and the gas is self-generated. The discharge port 27 is discharged at the end of the electrolysis. The mass solution is discharged from the oxidizing substance cold liquid discharge line 24 using the flow meter 22, the anolyte circulation/discharge port 23, and the cathode is supplied from the catholyte supply line 28 and the catholyte supply pump 29, the flow meter%, (4) The electrolyte containing sulfuric acid ions is supplied to the cathode chamber 4 of the desolvation tank 21, and electrolysis is performed in the cathode chamber 4, using the flow meter 3, the catholyte circulation/discharge fruit 32, and the cathode chamber 4 through the catholyte circulation line 34. At this time, the generated gas is separated from the cathode side gas-liquid separator 35, and is discharged from the generated gas discharge port.: At the end of the electrolysis, the catholyte is flowmeter Μ, the catholyte circulation field is used to produce the pump 100145902 18 201231730 32 And discharged from the catholyte discharge line 33. Further, the electrolytic cell 21 is cooled by the cooling jacket 15 and the cooling water circulation line 37. Further, the temperature of the electrolytic solution was measured by measuring the temperature of the electrolytic solution of the anolyte discharge port 1 shown in Fig. 1 . Fig. 2-2 shows another example of the sulfuric acid electrolysis method and the sulfuric acid electrolysis apparatus of the present invention which circulate the catholyte only without circulating the anolyte to produce the oxidizing substance solution in a single pass. Except that the oxidizing substance solution is produced in a single pass without circulating the anolyte, FIG. 2-2 is the same step as FIG. 2-1, and the same symbols are used for the symbols, so the steps of FIG. 2-2 are omitted. Description. [Examples] Next, the present invention will be specifically described by way of examples and comparative examples. However, the invention is not limited to the embodiments. Further, the Raman spectral characteristics of the electrode produced in the present invention, the film thickness measurement of the conductive diamond electrode, the boron concentration measurement, the durability test of the electrode, the measurement of the potential range, and the electrolysis containing the sulfate ion used for electrolysis The production of the liquid and the measurement of the concentration of the oxidizing substance in the produced oxidizing substance solution were carried out by the following methods. <Raman spectrum characteristic measurement> In order to measure whether or not a conductive diamond can be produced and to measure the A/b intensity ratio, surface Raman measurement of the electrode was performed. • Measuring device. Raman spectrophotometer manufactured by Thermo Fisher Scientific / 100145902 19 201231730 • Type: AIMEGA XR • Laser light: 532 nm • Exposure time: 2.00 seconds • Exposure times: 20 • Base exposure: 20 • Grating :672 lines/mm • Measurement width: 700~2000 cm·1 • Splitter aperture: 25 /zm slit • Low-decomposition energy measurement in low-power laboratory • Measurement position: equal from the two edges of the longest distance of the electrode The ground was divided into three equal portions, and the center position was measured to confirm the average value. • Spectral correction: The intensity at 2000 cm·1 is subtracted from the intensity of the entire range. • Diamond composition: peak intensity in the range of wave number nOOiSOcm·1, intensity of wave number 1300 cm-1 when no peak is confirmed • Non-diamond component: peak of wave range 15〇〇±50 cm-1 Intensity, when the peak value is not confirmed, the intensity of the wave number 15〇〇cm·1 will show Raman activity in the range of wave number UOOiSOcm-1, that is, within the range of wave number 1300±50 cnT A case where a peak or a wide waveform is displayed is judged to be a conductive diamond electrode. <Measurement of Conductive Diamond Film Thickness> From the two edges of the longest distance of the electrode, the conductive diamond electrode 100245902 201231730 or the like was divided into five equal parts. Use scanning electronic display manufacturer: Saki, trade name: drive 49_10kV acceleration power plant firm =

Observe the obtained profile and shoot at least one of all the cut samples. D <fume concentration measurement> Using secondary ion mass spectrometry (manufacturer: ULVAC · PHI, trade name: PHI ADEPT H)! 〇), and - sub-ion ο,, - sub-ion energy 3 k^, detection The surface of the electrode was measured under the condition that the polarity of the region (10) was twice positive. The concentration conversion is performed by combining the standard concentration sample of B in the sinking composition, and the relative sensitivity coefficient is obtained, and the coefficient is substituted into the test. <Durability Test of Conductive Diamond Electrode> _ The electrode prepared by using the anode and the cathode is formed by the electrolytic cell 21 with the separator shown in Fig. 2 as the sulfuric acid shown in Fig. 2 The apparatus was electrolyzed, and the production of the oxidizing substance solution was carried out under the following conditions. Current density: 100 A/dm Electrolysis time: 12 h Anode volume: 200 ml Electrolyte temperature: 35 〇C Cooling water temperature: 15 °C Anolyte flow rate: 1 1/min Catholyte flow rate: 1 1/min 100145902 21 201231730 Anolyte: 4.2 mol/l sulphuric acid (prepared by sulphuric acid manufactured by Kanto Chemical Co., Ltd. for use in the electronics industry). Catholyte: 4.2 mol/l sulphuric acid (diluted with pure water from the electronics industry) (Prepared by sulfuric acid manufactured by Kanto Chemical Co., Ltd. for the electronics industry) Separator: (POREFLON (registered trademark) manufactured by Sumitomo Electric FinePolymer Co., Ltd.) The electrode after the completion of the electrolysis was visually observed, and the peeling of the unrecognized conductive diamond film was set. In the case of the durability, it was confirmed that the peeling was extremely low, and the one that was tolerated by the medium 5 was cut into one or more half of the area. <Measurement of potential range> The measurement of the potential range was carried out by cyclic voltammetry to measure the redox decomposition voltage. That is, 4.2 mol/l of sulfuric acid was used as the electrolytic solution, the electrode on which the conductive diamond layer was formed on the substrate was used as the working electrode, the platinum wire was used as the opposite electrode, and the first mercury comparative electrode was used as the reference electrode at 50 mV. /s performs a potential sweep' to measure the potential at a current of ±50 mA/dm2, and determines the potential range based on the reduction and oxidative decomposition potential values. <Quality of sulfuric acid necessary for electrolytic solution preparation> The mass of %% sulfuric acid necessary for producing the electrolytic solution of 1 1 is calculated according to the formula (6), and 98% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) is charged in a measuring bottle. In the middle, ultrapure water was added to prepare a total of 11 electrolytes. C(g) = concentration of electrolyte containing sulfuric acid ions ^ milk) χ sulfuric acid (10) (6) C (g): quality of 98% sulfuric acid required to make 1 1 electrolyte

100145902 22 S 201231730 &lt;Acid concentration&gt; The acid concentration is calculated from the following formula (7) based on the concentration (mol/1) of the electrolyte containing sulfate ions to be produced in the formula (6). Acid concentration = concentration of electrolyte solution containing sulfate ions to be prepared x2 (7) &lt;Measurement of concentration of oxidizing substance&gt; 0.4 ml of oxidizing substance solution prepared in a 100 ml Erlenmeyer flask 'A total of 3 ml of the sample solution was added to the ultrapure water, and 5 ml of a solution of 2 〇〇g/1 prepared by adjusting potassium iodide (manufactured by Wako Pure Chemical Industries Co., Ltd.) with ultrapure water was used. The iodine is colored, and the conical flask is filled with nitrogen and sealed with ruthenium rubber. After being left for 3 minutes in this state, the sodium thiosulfate solution of 〇·〇2 m〇i/i is added dropwise (Wako Pure Chemical Industries, Ltd.) (manufactured)) until the sample solution becomes colorless. The number of times of measurement was measured three times for each sample, and the average value was used, and the concentration of the oxidizing substance was calculated by the following formula (8). Total concentration of oxidizing substances = _ drop amount (^) χΝ 02 Ο 3 concentration (0.02W &quot;) ... (8) Sample amount (w /) X Ν 3 ^ 2 〇 3 quantitative coefficient (2) &lt;oxidation The current efficiency of the substance is calculated by calculating the concentration of the lut material f of the produced oxidizing substance solution by the concentration measurement of the oxidizing substance, and calculating the current efficiency by the following formula (9). Current efficiency (%) = increase in the amount of sexual substances (expansion / &quot;) x anolyte amount (/) x 1 〇〇 ___ --- (9) t solution "W / pure disulfuric acid reaction electron number (2) touch 85 <Formation of a diamond layer by a hot filament CVD> The conductive diamond electrode of the present invention is produced by the following method. Using 100145902 23 201231730 single crystal Si as a conductive substrate, the surface of the substrate was polished and cleaned, and the core was adhered by diamond particles, and then placed in the apparatus. Hydrogen, decane, Ar+ succinic acid was used as the guiding gas, and the gas was allowed to flow into the device at a rate of 5 liters/min. while maintaining the pressure inside the device at 6 〇T rr, the wire was applied. Electric power was applied to raise the temperature to 23 Torr. Hey. At this time, the substrate temperature was 8 〇〇 Shi Pengyiyi vinegar was introduced into the apparatus by bubbling Ar in a container filled with liquid tartaric acid triacetate. By changing the R traffic, the position of the job is changed. The film thickness is changed by changing the film formation time. &lt;Example 1&gt; A conductive diamond electrode having an electrolysis area of 1 to 2 was used for both the anode and the cathode, and the electrolytic cell 2 (4) shown in Fig. 1 1 was used to form the sulfuric acid of Fig. 2_1. Electrolytic device, the surface of the anolyte and the catholyte are respectively circulated and electrolyzed. The characteristics of the electrode prepared by the process of the sulphur oxidizing solution are as follows! Shown. Electric = The cathode is made of the electrode, and the electrolytic sulfuric acid is used under the conditions of the separator and the following conditions and the following conditions: (Package 2: 2:7, adding ultrapure water and diluting into a total of u, made). 々 electrolyte, which uses 300 ml as yang 100145902

S 24 201231730 Extreme solution, using the remaining 300 ml as the catholyte. The acid concentration was calculated according to the formula (7) and found to be 18.4 mol/l. Cell current: 100 A Current density: 100 A/dm2 Electrolysis time: 20 minutes Anode volume: 3 00 ml Electrolyte temperature: 28 °C Cooling water temperature: 15 °C Anode fluid flow rate: 1 1/min Catholyte flow :1 1/min Anolyte: 4.2 mol/1 sulfuric acid Catholyte: 4.2 mol/1 sulfuric acid separator: (POREFLON (registered trademark) manufactured by Sumitomo Electric FinePolymer Co., Ltd.) Results of the obtained oxidizing substance solution Table 6 and below are shown. Using the produced oxidizing substance solution, titration was carried out according to the concentration measurement method of the above oxidizing substance, and as a result, the solution became colorless after dropwise addition of 44.00 ml of 〇2 mow sodium thiosulfate solution. Then, the measurement was repeated twice by the same method, and the results were 44 〇〇, 44 (10), and (5), respectively. Let the average value of the equals hit ml, and calculate the concentration of the oxidizing substance by 1/1 according to the formula (8). In addition, the concentration of the oxidizing substance was used; the nasal current efficiency was 53%. °10100145902 25 201231730 &lt;Example 2~l〇&gt; As a general example 2~1 〇, by changing the flow rate of the A, the flow rate of the trimethyl valerate and the film formation time' will be as shown in Table 2 An oxidizing substance solution was obtained in the same manner as in Example 1 except that the electrode of the conductive diamond film thickness, the potential range, the enthalpy, and the irrigating degree was changed to the anode. The results of the obtained oxidizing substance solution are shown in Tables 6 and 7. &lt;Examples 11 to 14&gt; The oxidizing substance solution was obtained by the same method as in Example i except that the sulfate ion concentration and the acid concentration in the electrolytic solution were changed as described in Tables 2 to 3. The results of the solution of the substance are shown in Tables 7 to 8. &lt;Examples 15 to 16 &gt; The amount of anolyte in the electrolyte and the current value/anode dU were changed as described above, and the electrolysis area (10) was used for both the anode and the cathode: (4), 2 (2), 2 The electrolytic cell with the diaphragm shown in the second shows the sulfuric acid electrolysis plant, and does not carry out the mascara coating and the early (four) nuclear oxygen recording (four), in addition to the same method to obtain the oxygen tilting material. The results of the obtained oxidizing substance solution are shown in Table 8. <Examples 17 to 24> Except for M, the same as Example 1 was used. 100145902 26 201231730 The method was carried out to obtain an oxidizing substance solution. The results of the obtained oxidizing substance solution are shown in Tables 8 to 9. &lt;Example 25&gt; An oxidizing substance solution was obtained in the same manner as in Example 1 except that ruthenium was used for the base material. The results of the obtained oxidizing substance solution are shown in Table 9. 1) From the results of Examples 1 to 4, the narrower the potential range, and the intensity at a wave number of 1300 cnT1 in A=Raman spectrum analysis and the intensity at a wave number of 1500 cnT1 in B=Raman spectrum analysis. The smaller the A/B ratio, the higher the current efficiency of the oxidizing substance and the lower the electrolysis cell voltage. On the other hand, in the second embodiment, the electrode after the durability test of the electrode was visually confirmed, and it was confirmed that the peeling of the conductive diamond film was extremely small. 2) From the results of Examples 5 and 6, it is understood that the thinner the thickness of the conductive diamond layer, the higher the current efficiency of the oxidizing substance and the lower the electrolytic cell voltage, as compared with the results of Example 1. The reason is considered to be: the thinner the conductive diamond layer, the narrower the potential range, the ratio of the intensity at 1300 cnT1 in the A=Raman spectrum analysis to the intensity at 1500 cm_1 in the B=Raman spectrum analysis. The smaller A/B becomes. On the other hand, in Example 6, the sixth embodiment was lower in the current efficiency of the oxidizing substance and higher in the electrolytic cell voltage than in the results of Example 1. 3) From the results of Examples 7 to 10, it is understood that the higher the boron concentration, the higher the current efficiency of the oxidizing substance, and the higher the concentration of the oxidized 100145902 27 201231730, the higher the electrolysis, compared with the results of Example 1 The lower the tank voltage. The reason is considered to be: ♦ the higher the boron concentration, the narrower the potential range 'A=the intensity of the wave number in the Raman spectrum analysis at 13〇〇cm·1 and the wave number in the B=Raman spectrum analysis 1500 cm·1 The ratio of the strength of the lower one becomes smaller. On the other hand, in the example 10, the electrode after the endurance test of the electrode was visually confirmed, and it was confirmed that the peeling of the conductive diamond film was extremely small. 4) From the results of the examples 11 and 12, it is understood that the lower the sulfate ion concentration, the lower the current efficiency as compared with the result of the first embodiment. The reason is considered to be that the lower the sulfuric acid ion concentration, the less the reactants. Further, it can be seen that the electrolysis cell voltage is higher as compared with the result of the first embodiment. The reason is considered to be that the acid concentration is lowered and the electric conductivity is lowered. From the results of Examples 13 and 14, it is understood that the higher the acid concentration, the lower the current efficiency as compared with the results of Example 1. The reason is considered to be that the higher the acid concentration, the more easily the oxidizing substance decomposes. Further, it is understood that the higher the sulfate ion concentration, the higher the electrolytic cell voltage as compared with the result of Example 1. The reason is considered to be that the sulfate ion concentration is high, the viscosity is high, the gas detachment is deteriorated, the bubble ratio is increased, the conductivity of the electrolyte is lowered, and the electrolytic cell voltage is increased. The result of the current efficiency is 5). As can be seen from the results of Examples 15 to 18, the larger the oxidizing substance is, the more the oxidizing substance is higher than the example X = current value / anolyte amount (A / 1). The more the electrolyte with a higher degree of oxidizing material can be obtained. On the other hand, the larger the χ = current value / anolyte amount (A / 1), the higher the cell voltage. The reason is considered to be: the gas is filled in the electrolytic waste to make the electrolytic cell 100145902

S 28 201231730 Voltage rises. In Examples 17 and 18, the electrolytic cell voltage was good, but the current efficiency was low. 6) From the results of Examples 19 to 20, it is understood that the current efficiency of the oxidizing substance is lower when the current is at a lower degree (A/dm2) than the result of the Example 与, and at the same time, the oxidizing property is obtained. The substance concentration becomes lower. On the other hand, as is clear from the results of Examples 21 and 22, when the current density (A/dm2) 4 is two, the current efficiency of the oxidizing substance is higher than that of the results of Example 1, but the electrolytic cell ink rises. . The reason is considered to be that the gas generated is filled in the electrolytic cell because of the high current density. 7) As a result of the application of Example 23, when the amount of electric power per unit volume is lower than that of the results of Example 则, the current efficiency of the oxidizing substance is increased, and at the same time, the concentration of the oxidizing substance is lowered. On the other hand, as is clear from the results of Example 24, when the amount of electricity per unit volume is increased, the current efficiency of the oxidizing substance is lowered, and the concentration of the oxidizing substance is increased. 8) From the results of Example 25, it can be seen that the current efficiency of the oxidizing substance is good when the substrate material becomes 铌 compared with the result of Example i, and at the same time, the concentration of the oxidizing substance is good, but the durability test of the electrode The visual observation of the surface of the electrode was confirmed to be slightly peeled off. &lt;Comparative Examples 1 to 4&gt; By changing the flow rate of the xenon, the flow rate of the cyanuric acid triacetate, and the film formation time, the electrode of the conductive diamond film thickness and the potential range as described in Table 5 was used for the anode. In addition to this and the examples! The same method was used to obtain oxygen 100145902 29 201231730 7 substance solution. The results of the obtained oxidizing substance solution are shown in Table 1, the current efficiency of the electrolytic cell voltage and the oxidizing substance, and the result was confirmed by visual observation of the electrode surface after the durability test of the electrode. To the extent where the film is mostly peeled off. In Comparative Example 2, in the visual observation of the surface of the electrode after the durability test of the electrode, the deterioration of the film was not confirmed, but the voltage of the electrolytic cell in the electrolysis process became south, and the oxidizing substance obtained by the drought was obtained. The current efficiency of the solution is low. In Comparative Example 3, the electrolytic cell voltage and current efficiency were excellent, but it was confirmed that the film was largely peeled off by visual observation of the electrode surface after the electrode durability test. In Comparative Example 4, no deterioration of the film was observed in the visual observation of the surface of the electrode after the long-term test of the electrode, but the voltage of the electrolytic cell during the electrolysis was changed, and the current of the solution containing the oxidizing substance was obtained. Less efficient. In Comparative Example 5, the electrode was deteriorated during the electrolysis, and the powder of carbon was visually observed in the electrolytic solution, thereby interrupting the electrolysis. 100145902 30 201231730 Table 1 Electrolysis conditions Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Anode and cathode film material Conductive diamond substrate material Conductivity 矽 Diamond layer thickness (/zm) 10 10 10 10 1.5 23 Potential range (V) 2.63 2.12 3.40 2.80 2.12 3.30 A/B 4.50 1.80 6.20 6.30 1.58 6.00 Shed concentration (ppm) 3000 3000 3000 3000 3000 3000 Sulfate ion concentration in electrolyte (mol/1) 4.2 4.2 4.2 4.2 4.2 4.2 Acid concentration in the electrolyte (mol/l) 8.4 8.4 8.4 8.4 8.4 8.4 Anode volume (ml) 300 300 300 300 300 300 Electrolytic area (dm2) 1.000 1.000 1.000 1.000 1.000 1.000 Current value (A) 100 100 100 100 100 100 Current density (A/dm2) 100 100 100 100 100 100 Current value / anolyte volume (A/1) 333 333 333 333 333 333 Electrolysis time (min) 20 20 20 20 20 20 Electricity per unit volume ( xl〇4As/l) 40 40 40 40 40 40 Separator use Table 2 Electrolysis conditions Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Anode and cathode film material Conductive diamond substrate material Conductive diamond Layer thickness (//m) 10 10 10 10 10 10 Potential range (V) 3.50 3.20 2.60 2.15 2.63 2.63 A/B 6.00 5.50 3.20 1.62 4.50 4.50 Boron concentration (ppm) 700 1200 5000 7000 3000 3000 Sulfate ion concentration in electrolyte (mol/1) 4.2 4.2 4.2 4.2 1.9 2.5 Acid concentration in electrolyte (mol/1) 8.4 8.4 8.4 8.4 3.8 5.0 Anode volume (ml) 300 300 300 300 300 300 Electrolytic area (dm2) 1.000 1.000 1.000 1.000 1.000 1.000 Current value (A) 100 100 100 100 100 100 Current density (A/dm2) 100 100 100 100 100 100 Current value / anolyte volume (A/1) 333 333 333 333 333 333 Electrolysis time (min) 20 20 20 20 20 20 Per unit volume Electric quantity (x1〇4As/1) .40 40 40 40 40 40 Separator use 31 ' &gt; 100145902 Example 13 Example 14 Example 〖5|Implementation of the 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 Therefore, the anode and cathode diamond layer thickness (βϊή) 10 10 10 10 10 10 Potential range (V) 2.63 2.63 2.63 2.63 2.63 2.63 Α/Β 4.50 4.50 4.50 4.50 4.50 4.50 3000 3000 3000 3000 3000 3000 Sulfate ion concentration in the electrolyte ( Mol/1) 8.5 16.0 4.2 4.2 4.2 4.2 Acid concentration in the solution (mol/1) 17.0 32.0 1 8.4 8.4 8.4 8.4 Anode volume (ml) 300 300 11 20 1000 1200 Electrolytic area (dm2) 1.000 1.000 1.000 1.000 1.000 1.000 Current value (A) 100 100 100 100 100 100 Current density (A/dm2) 100 100 100 100 100 100 Current value / Anode volume (A/1) 333 333 9091 5000 100 83 Electrolysis time (min) 20 20 0.7 1.3 66.7 80.0 Electricity per unit volume (x104As /1) 40 40 40 40 40 40 Separator use 201231730 Table 3 Electrolysis conditions Table 4 Electrolysis conditions Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Anode and cathode film materials Diamond substrate material conductivity 矽铌 diamond layer thickness (/m) 10 10 10 10 10 10 10 Potential range (V) 2.63 2.63 2.63 2.63 2.63 2.63 2.63 A/B 4.50 4.50 4.50 4.50 4.50 4.50 4.50 Moment (pprr〇 3000 3000 3000 3000 3000 3000 3000 Sulfate ion concentration in electrolyte (mol/D 4.2 4.2 4.2 4.2 4.2 4.2 4.2 Acid concentration in electrolyte (mol/1) 8.4 8.4 8.4 8.4 8.4 8.4 8.4 Anode volume (ml) 300 300 300 300 300 300 300 Electrolytic area (dm2 ) 1.000 1.000 1.000 1.000 1.000 1.000 1.000 Current value (A) 20 50 200 280 100 100 100 Current density (A/dm2) 20 50 200 280 100 100 100 Current value / anolyte volume (A/1) 67 167 667 933 333 333 333 Electrolysis time (min) 100 40 10 7.1 1.0 50 20 Electricity per unit volume (X l〇4As/n 40 40 40 40 2 100 40 Separator use 100145902 32 201231730 Table 5 Electrolysis conditions------ Comparative example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Anode and Cathode Film Material Conductive Diamond Carboniferous Substrate Material Tele-Ray Shi Xi • Diamond Layer Thickness (um) 10 10 0.8 26 - 3.60 1.90 Potential Range (V) 1.97 3.90 1.99 A/B 2.00 7.20 1.49 6.30 Butterfly concentration (rmm) 3000 3000 3000 3000 - 4.2 4.2 Sulfate ion concentration in electrolyte (mol/1) 4.2 4.2 4.2 Acid concentration in electrolyte 廑imol/1) 8.4 8.4 8.4 8.4 8.4 Anode fluid volume (ml) 300 300 300 300 300 Electrolytic area (dm2) 1.000 1.000 1.000 1 1.000 1.000 Current value (A) 100 100 100 100 100 100&quot;&quot;&quot;&quot; 100 ..... Current density (A/dm2) 100 100 100 ~ 333 333 Lei Zixin / Yang Luoqiu / Π 3 33 333 333 Electrolysis time fmin, 20 20 20 20 20 Electricity per unit volume (xl〇4As/l) 40 40 40 40 40 One diaphragm use ____ Table 6 Experimental results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Current efficiency % 53 55 49 50 56 40 11/: Oxidizing substance concentration (m〇l/l) 1.10 1.14 1.02 1.04 1.04 1.1〇1 1 电解 Cell voltage m 10.200 9.800 10.800 10.790 9.620 11.2 UU durability 〇 △ 〇〇 △ KJ Table 7 Experimental results Example 12 Example 7 Current efficiency % Oxidizing substance concentration (m〇l / l) A cell voltage (v) 38 0.79 ΤΓόόό ^ Example 41 - 0.85109 〇 〇~ Example 9 54 1.12 9.800 〇Example 10 55 1.14 9.500 Example 11 30 0.62 10.400 42 0.87 10.300 &quot;&quot;δ&quot;- Table 8 Experimental Results Current Efficiency % Oxidizing Material Concentration Cell Voltage fV) Durability Implementation Example 13 51 1.06 11.300 0 Example 14 35 0.73 12.900 〇Example 15 55 1.14 12.100 〇Example 16 54 1.12 11.800 〇Example 17 50 1.04 10.200 把例 Example 49 1.02 10.200 〇100145902 33 201231730 Table 9 Experiment Example 1 23 ^Examples ^ 24 25 . Example 19 Example 20 Example 21 Example 22 Current efficiency % 46 49 54 55 97 34 53 Oxidizing substance concentration (mol/1) 0.95 1.02 1.12 1.14 0.05 1.76 1.10 Cell voltage (V) 6.400 7.902 13.200 15.000 10.200 10.200 10.300 Durability 〇〇〇〇〇〇 Δ Table 10 Experimental results Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Current efficiency % 54 33 54 32 Serious deterioration Non-electrolytic oxidizing substance concentration (mol/1) 1.12 0.68 1.12 0.66 Cell voltage (V) 10.000 12.800 9.800 12.500 Durability X 〇X 〇 (industrial availability) If the diamond electrode by the present invention is used, especially The anode in sulfuric acid electrolysis has an effect of stably generating an oxidizing substance, and this effect can be improved when used as a cathode in sulfuric acid electrolysis. Further, the conductive diamond electrode of the present invention can also be used as another anode and cathode for electrolysis. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a general view showing an example of an electrolytic cell used in the sulfur electrolysis method and the sulfuric acid electrolytic cracking of the present invention. Fig. 2-i is a general view showing an example of the sulfuric acid electrolysis method and the sulfuric acid electrolysis according to the present invention. Fig. 2-2 is an overall view of another example of the mechanical electrolysis method and the collision electrolysis apparatus of the invention. [Main component symbol description] 100145902

S 34 201231730 1 anolyte discharge port 2 catholyte discharge port 3 anode chamber 4 cathode chamber 5 anode feed terminal 6 cathode feed terminal 7 anolyte supply port 8 catholyte supply port 9 porous PTFE diaphragm 10 conductive diamond anode 11 conductivity Substrate 12 Conductive Diamond Cathode 13 Conductive Substrate 14 Sealing Material 15 Cooling Jacket 16 Cooling Water Discharge Port 17 Cooling Water Supply Port 18 Anolyte Supply Line 19 Anolyte Supply Pump 20 Flow Meter 21 Electrolyzer 22 Flow Meter 100145902 35 201231730 23 Anode Liquid circulation/discharge pump 24 Oxidizing substance solution discharge line 25 Anomatic liquid circulation line 26 Anode side gas-liquid separator 27 Production gas discharge port 28 Catholyte supply line 29 Catholyte supply pump 30 Flow meter 31 Flow meter 32 Catholyte circulation / Discharge pump 33 Catholyte discharge line 34 Catholyte circulation line 35 Cathode side gas-liquid separator 36 Generate gas discharge port 37 Cooling water circulation line 100145902 36 s

Claims (1)

201231730 VII. Patent application scope: L type conductive diamond electrode, comprising: a conductive substrate and a conductive diamond layer coated on the surface of the conductive substrate, and 丄) the thickness of the conductive diamond layer is 1~25 //m, . 2) The potential range satisfies the formula (1), • The ratio of the diamond component A to the non-diamond component B (A/B) obtained by the 杈-manner spectrum analysis satisfies the formula (2), 2·1 Potential range 5 v ...(1) A/B^6 5 (2) Wave number in A Raman spectroscopy analysis intensity under 13〇〇cm·1 B-wave number in Raman spectroscopy The strength under cm-1. 2. The conductive diamond electrode of claim 1, wherein the conductive diamond layer comprises a shed of 1 〇〇〇 to 6000 ppm. 3. The conductive diamond electrode according to claim 1 or 2, wherein the conductive substrate is a tantalum substrate. 4. A method for electrolyzing sulfuric acid, which is divided into an anode chamber and a cathode chamber by a separator to provide a conductive diamond anode in the anode chamber, and a cathode is provided in the cathode: from the outside to the anode chamber and The cathode (4) is separately supplied with an electrolyte containing sulfuric acid ions for electrolysis, and the anode in the anode chamber is formed into an oxidizing substance in the liquid, and is characterized in that: in use, the conductive material of any one of the first to third patent ranges is used. The diamond electrode is used as the conductive diamond electrode', and the electrolyte containing the sulfate ion is made into a solution containing a concentration of 2 to 14 watts (4) 100145902 37 201231730. 5. The sulfuric acid electrolysis method according to claim 4, wherein the electrolyte containing sulfate ions is made into a solution containing an acid having a concentration of 4 to 28. 6. A sulfuric acid (four) device, which is divided into an anode chamber and a cathode chamber by a separator (four), a conductive diamond anode is disposed in the anode chamber, a cathode is disposed in the cathode chamber, and is supplied from the outside to the anode chamber and the cathode chamber respectively. An electrolytic diamond electrode comprising any of the anolyte solutions in the anode chamber is electrolyzed by an electrolytic solution containing a sulfate ion, and the conductive diamond electrode according to any one of the first to third aspects of the patent range is used as the above. As the conductive diamond electrode, a separator containing a fluororesin-based cation or a hydrophilized porous fluororesin film is used as the separator. 7. A method for solving sulfuric acid f, wherein the storage is divided into an anode chamber and a cathode chamber by a separator, and a conductive diamond anode is disposed in the anode chamber, and a cathode is provided in the cathode: a cathode is supplied from the outside to the anode chamber and the cathode chamber. The electrolytic solution containing the sulfuric acid ion is electrolyzed, and the anodic electricity in the anode chamber is formed into an oxidizing substance in the liquid, and the conductive diamond electrode according to any one of the first to third aspects of the patent scope is used as the above-mentioned Conductive diamond electrode, and electrolyzing the above electrolyte containing sulfuric acid under the conditions satisfying the formulas (3) and (4), 100^X^ 10000 ..·(3) 25&lt;Υ&lt;250 ...μ, 100145902 38 201231730 X = current value / anolyte amount (A / l) Y = current density (A / dm2). 8. The method for electrolyzing sulfuric acid according to item 7 of the patent application, which is to electrolyze a solution containing sulfuric acid ions under the condition of the formula (5), 18000SZS 1080000 ... (5) 'Z=electric quantity per unit volume (C/l ) = current value X electrolysis time / anolyte amount (A. s / 1). &quot; 100145902 39