CN114438541A - Graphene-containing chlorine evolution anode - Google Patents
Graphene-containing chlorine evolution anode Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000460 chlorine Substances 0.000 title claims abstract description 68
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 68
- 239000011248 coating agent Substances 0.000 claims abstract description 141
- 238000000576 coating method Methods 0.000 claims abstract description 141
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 92
- 239000007788 liquid Substances 0.000 claims abstract description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012266 salt solution Substances 0.000 claims abstract description 42
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 35
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 26
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 100
- 239000000243 solution Substances 0.000 claims description 55
- 239000000758 substrate Substances 0.000 claims description 47
- 239000010936 titanium Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 14
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 claims description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- 230000000873 masking effect Effects 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 7
- 230000001172 regenerating effect Effects 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 33
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 6
- 229910052719 titanium Inorganic materials 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 239000003513 alkali Substances 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Organic Chemistry (AREA)
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Abstract
A graphene-containing chlorine evolution anode is characterized in that soluble salts of a ruthenium element, soluble salts of an iridium element and soluble salts of a titanium element are dissolved in water, the concentration of all metals in an aqueous solution is 110 g/L-140 g/L, and according to metal components, the molar ratio of the ruthenium element is 15% -35%, the molar ratio of the iridium element is 10% -30%, and the molar ratio of the titanium element is 35% -55%, so that a salt solution is obtained; and C, adding the graphene aqueous solution into the salt solution obtained in the step B according to the proportion of 0.1-2 g/L, and uniformly mixing by using an ultrasonic mixer to obtain the active coating liquid. The graphene-containing chlorine evolution anode is low in chlorine evolution potential and long in service life, and meanwhile, the anode can improve the chlorine-oxygen potential difference, enhance the selectivity of the electrode and reduce side reactions in the preparation of sodium hydroxide.
Description
Technical Field
The invention relates to the field of sodium hydroxide preparation, in particular to a graphene-containing chlorine evolution anode.
Background
In the existing chlor-alkali electrolysis device, the anode adopts a noble metal coating which is titanium-based and coated with Ru, Ir and Ti, and the production process of the anode prepared by the thermal oxidation method is mature. It is known that the surface of a noble metal coating which is titanium-based and coated with Ru, Ir and Ti has cracks, the cracks are generated by the interaction of mechanical stress generated by different expansion coefficients of a metal oxide coating and the titanium-based and thermal stress generated by cooling an electrode from the furnace temperature to the room temperature, and the cracks have the advantages of increasing the specific surface area of the electrode and increasing the active points of the electrode; the disadvantage is that the oxygen which is the by-product of the operation of the electrolytic cell is easy to diffuse and migrate to the surface of the titanium matrix and form a layer of TiO with the titanium matrix2Passivating the film, thereby causing passivation of the electrode and loss of activity.
Therefore, there is a strong need for an electrode coating that increases the specific surface area while reducing cracking, thereby achieving the goals of reducing chlorine evolution potential and prolonging service life. Meanwhile, the chlorine-oxygen potential difference is improved, the selectivity of the electrode is enhanced, and the side reaction in the preparation of the sodium hydroxide is reduced.
Graphene, as a novel two-dimensional carbon nanomaterial, has good electrical conductivity, has a high electron transfer rate even at room temperature, and is firm and hard. Graphene has gained wide attention in the field of material research by virtue of its excellent electrical, mechanical and thermal properties. After the graphene is added into the coating, the surface appearance is changed, the surface of the coating is honeycomb-shaped, the roughness of the surface of the anode is increased due to the uneven surface characteristics, the number of active points on the surface of the anode is increased, the electrocatalytic activity of the anode is improved, meanwhile, surface cracks are continuous and small, the probability that oxygen reaches a titanium substrate is reduced, and the coating is an ideal additive.
Disclosure of Invention
The invention aims to provide a graphene-containing chlorine evolution anode which is low in chlorine evolution potential, long in service life, capable of improving chlorine-oxygen potential difference, enhancing electrode selectivity and reducing side reactions in sodium hydroxide preparation.
The graphene-containing chlorine evolution anode is prepared by the following steps:
A. preparing soluble salts of ruthenium element, iridium element and titanium element;
B. dissolving soluble salts of ruthenium element, soluble salts of iridium element and soluble salts of titanium element in water to enable the concentration of all metals in the water solution to be 110 g/L-140 g/L, wherein the molar ratio of the ruthenium element is 15% -35%, the molar ratio of the iridium element is 10% -30% and the molar ratio of the titanium element is 35% -55% according to metal components, and obtaining a salt solution;
C. adding a graphene aqueous solution into the salt solution obtained in the step B, wherein the ratio of graphene is 0.1-2 g/L, and then stirring the salt solution by using an ultrasonic mixer to uniformly mix the salt solution to obtain an active coating masking liquid;
D. acid cleaning is carried out on the metal matrix of the chlorine evolution anode containing titanium element, and an oxide layer on the surface of the metal matrix of the chlorine evolution anode is removed;
E. coating the active coating liquid obtained in the step C on the metal substrate treated in the step D, then carrying out heat treatment on the metal substrate coated with the coating liquid in an oxygen-containing atmosphere, wherein the heat treatment temperature is 350-450 ℃, the heat treatment time is 30-100 minutes, and an active coating is generated on the outer surface of the metal substrate;
F. e, continuously coating a layer of active coating liquid on the metal substrate obtained in the step E to the newly generated active coating, then carrying out heat treatment on the metal substrate coated with the coating liquid in an oxygen-containing atmosphere at the heat treatment temperature of 400-550 ℃, the heat treatment time of 30-100 minutes, regenerating a new active coating on the outer surface of the previously generated active coating, then continuously carrying out heat treatment on the metal substrate coated with the coating liquid in the oxygen-containing atmosphere at the heat treatment temperature of 400-550 ℃, the heat treatment time of 30-100 minutes, regenerating a new active coating on the outer surface of the previously generated active coating, and repeating the steps until the coating amount of the active coating on the surface of the metal substrate is more than or equal to 16g/m2；
G. And F, carrying out sintering heat treatment on the metal matrix obtained in the step F, wherein the sintering heat treatment temperature is 400-550 ℃, and the sintering heat treatment time is 200-300 minutes, so as to obtain the graphene-containing chlorine evolution anode.
Preferably, the total metal concentration in the aqueous solution in the step B is 120 g/L-135 g/L, and the salt solution is obtained according to the metal components, wherein the molar ratio of the ruthenium element is 20% -30%, the molar ratio of the iridium element is 15% -25%, and the molar ratio of the titanium element is 40% -50%;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.2-1.5 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 380-430 ℃, and the heat treatment time is 35-80 minutes;
and in the step F, the heat treatment temperature for the metal substrate coated with the coating solution is 450-520 ℃, and the heat treatment time is 35-80 minutes.
Preferably, the total metal concentration in the aqueous solution in the step B is 125 g/L-130 g/L, wherein the molar ratio of ruthenium element is 23% -27%, the molar ratio of iridium element is 18% -22%, and the molar ratio of titanium element is 43% -47% according to the metal components, so as to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.25-1.0 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 400-420 ℃, and the heat treatment time is 35-80 minutes;
and in the step F, the heat treatment temperature for heat treatment of the metal substrate coated with the coating solution is 480-500 ℃, and the heat treatment time is 35-80 minutes.
In the step F, the number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment is 6-12, and the single-layer coating amount of the active coating is 1.3g/m2—2.7g/m2。
The sintering heat treatment time in the step G is 250-300 minutes.
Preferably, the total metal concentration in the aqueous solution in the step B is 126 g/L-128 g/L, wherein the molar ratio of ruthenium element is 24% -26%, the molar ratio of iridium element is 19% -21%, and the molar ratio of titanium element is 44% -46% based on the metal components, so as to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.35-0.6 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 405-415 ℃, and the heat treatment time is 45-70 minutes;
and in the step F, the heat treatment temperature for heat treatment of the metal substrate coated with the coating solution is 480-500 ℃, and the heat treatment time is 45-70 minutes.
In the step F, the number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment is 7-10, and the single-layer coating amount of the active coating is 1.5g/m2—2.2g/m2。
The sintering heat treatment time in the step G is 260-280 minutes.
Preferably, the soluble inorganic salt of ruthenium element is RuCl3Or RuN4O10The soluble inorganic salt of iridium element is IrCl4Or Ir (NO)3)4The soluble inorganic salt of titanium element is TiCl4Or Ti (NO)3)4。
The graphene-containing chlorine evolution anode is characterized in that soluble salts of ruthenium, iridium and titanium are dissolved in water, the concentration of all metals in an aqueous solution is 110-140 g/L, and the molar ratio of the ruthenium is 15-35%, the molar ratio of the iridium is 10-30% and the molar ratio of the titanium is 35-55% according to metal components, so that a salt solution is obtained; adding a graphene aqueous solution into the salt solution obtained in the step B according to the proportion of 0.1-2 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid, wherein the chlorine evolution potential of the graphene-containing chlorine evolution anode prepared by using the active coating liquid is 1.090V, the chlorine evolution potential of the conventional chlorine alkali-containing anode is 1.110V, and the chlorine evolution potential of the graphene-containing chlorine evolution anode is reduced by 20mV compared with that of the conventional chlorine alkali-containing chlorine evolution anode; the chlorine-oxygen potential difference of the graphene-containing chlorine evolution anode is 421mV, the chlorine-oxygen potential difference of the conventional anode for chlor-alkali is 380mV, and the chlorine-oxygen potential difference of the graphene-containing chlorine evolution anode is increased by 41mV compared with the chlorine-oxygen potential difference of the conventional anode for chlor-alkali; after the existing anode for chlor-alkali is subjected to strengthened life detection, the residual quantity of the coating is 76.3 percent, while after the graphene-containing chlorine evolution anode is subjected to strengthened life detection, the residual quantity of the coating is 85.5 percent and is improved by 9.2 percent. Therefore, the graphene-containing chlorine evolution anode has the characteristics of low chlorine evolution potential, long service life, capability of improving the chlorine-oxygen potential difference, enhancement of the selectivity of the electrode and reduction of side reactions in the preparation of sodium hydroxide.
Further details and features of the graphene-containing chlorine evolving anode of the present invention will become apparent from a reading of the examples detailed below.
Drawings
FIG. 1 is a scanning electron microscope image of a chlorine evolution anode containing graphene according to the present invention;
FIG. 2 is a scanning electron micrograph of a conventional chlor-alkali anode.
Detailed Description
The graphene-containing chlorine evolution anode is prepared by the following steps:
A. preparing soluble salts of ruthenium element, iridium element and titanium element;
B. dissolving soluble salts of ruthenium element, soluble salts of iridium element and soluble salts of titanium element in water to enable the concentration of all metals in the water solution to be 110 g/L-140 g/L, wherein the molar ratio of the ruthenium element is 15% -35%, the molar ratio of the iridium element is 10% -30% and the molar ratio of the titanium element is 35% -55% according to metal components, and obtaining a salt solution;
C. adding a graphene aqueous solution into the salt solution obtained in the step B, wherein the ratio of graphene is 0.1-2 g/L, and then stirring the salt solution by using an ultrasonic mixer to uniformly mix the salt solution to obtain an active coating masking liquid;
D. pickling the metal matrix of the chlorine evolution anode containing titanium element to remove an oxide layer on the surface of the metal matrix of the chlorine evolution anode;
E. coating the active coating liquid obtained in the step C on the metal substrate treated in the step D, then carrying out heat treatment on the metal substrate coated with the coating liquid in an oxygen-containing atmosphere, wherein the heat treatment temperature is 350-450 ℃, the heat treatment time is 30-100 minutes, and an active coating is generated on the outer surface of the metal substrate;
F. e, continuously coating a layer of active coating liquid on the metal substrate obtained in the step E to the newly generated active coating, then carrying out heat treatment on the metal substrate coated with the coating liquid in an oxygen-containing atmosphere at the heat treatment temperature of 400-550 ℃ for 30-100 minutes, regenerating a new active coating on the outer surface of the previously generated active coating, then continuously carrying out heat treatment on the metal substrate coated with the coating liquid in the oxygen-containing atmosphere at the heat treatment temperature of 400-550 ℃ for 30-100 minutes, regenerating a new active coating on the outer surface of the previously generated active coating, and repeating the steps until the coating amount of the active coating on the surface of the metal substrate is more than or equal to 16g/m 2;
G. and F, carrying out sintering heat treatment on the metal matrix obtained in the step F, wherein the sintering heat treatment temperature is 400-550 ℃, and the sintering heat treatment time is 200-300 minutes, so as to obtain the graphene-containing chlorine evolution anode.
As a further improvement of the invention, the concentration of all metals in the aqueous solution in the step B is 120 g/L-135 g/L, wherein the molar ratio of ruthenium element is 20% -30%, the molar ratio of iridium element is 15% -25%, and the molar ratio of titanium element is 40% -50%, based on the metal components, so as to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.2-1.5 g/L, and then uniformly mixing by using an ultrasonic mixer to obtain an active coating solution;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 380-430 ℃, and the heat treatment time is 35-80 minutes;
and in the step F, the heat treatment temperature for the metal substrate coated with the coating solution is 450-520 ℃, and the heat treatment time is 35-80 minutes.
As a further improvement of the invention, the total metal concentration in the aqueous solution in the step B is 125 g/L-130 g/L, and the molar ratio of ruthenium element is 23% -27%, the molar ratio of iridium element is 18% -22%, and the molar ratio of titanium element is 43% -47% according to the metal components, so as to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.25-1.0 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 400-420 ℃, and the heat treatment time is 35-80 minutes;
and in the step F, the heat treatment temperature for heat treatment of the metal substrate coated with the coating solution is 480-500 ℃, and the heat treatment time is 35-80 minutes.
And in the step F, the number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment is 6-12, and the single-layer coating amount of the active coating is 1.3g/m 2-2.7 g/m 2.
The sintering heat treatment time in the step G is 250-300 minutes.
As a further improvement of the invention, the total metal concentration in the aqueous solution in the step B is 126 g/L-128 g/L, wherein the molar ratio of ruthenium element is 24% -26%, the molar ratio of iridium element is 19% -21%, and the molar ratio of titanium element is 44% -46% based on the metal components, so as to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.35-0.6 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 405-415 ℃, and the heat treatment time is 45-70 minutes;
and in the step F, the heat treatment temperature for heat treatment of the metal substrate coated with the coating solution is 480-500 ℃, and the heat treatment time is 45-70 minutes.
And in the step F, the number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment is 7-10, and the single-layer coating amount of the active coating is 1.5g/m 2-2.2 g/m 2.
The sintering heat treatment time in the step G is 260-280 minutes.
As a further improvement of the invention, the soluble inorganic salt of ruthenium element is RuCl3 or RuN4O10, the soluble inorganic salt of iridium element is IrCl4 or Ir (NO3)4, and the soluble inorganic salt of titanium element is TiCl4 or Ti (NO3) 4.
The mass percentages of the ruthenium element, the iridium element and the titanium element in the active coating layer according to the metal components can be detected by an X-ray fluorescence tester.
According to the invention, on the basis of a Ru, Ir and Ti titanium-based anode in the existing chlor-alkali electrolysis device, the microstructure of an anode coating is improved by adding graphene, the surface of the coating is honeycomb-shaped, as shown in figure 1, the uneven surface characteristic increases the surface roughness of the electrode, increases the number of active points on the surface of the anode, improves the electrocatalytic activity of the electrode, effectively reduces the chlorine evolution potential, further improves the chlorine-oxygen potential difference, enhances the selectivity of the electrode, reduces the side reaction in the preparation of sodium hydroxide, has fine and small surface cracks, and can slow down the contact of oxygen and the titanium-based body while effectively increasing the active area compared with the deep and large cracks on the surface of the existing Ti-based precious metal coating coated with Ru, Ir and Ti as shown in figure 2, so that the service life of the electrode is prolonged. Therefore, compared with the existing titanium-based anode of Ru, Ir and Ti in the chlor-alkali electrolysis device, the chlorine evolution anode has three advantages: (1) lower chlorine evolution potential; (2) stronger selectivity; (3) longer service life.
Example 1
Preparing a coating solution: adding titanium tetrachloride into a ruthenium trichloride solution, and then adding iridium tetrachloride to ensure that the atomic percentage content of the iridium trichloride solution is Ru: 20-35%, Ir: 15-30%, Ti: 35-55 percent of the total metal concentration reaches 131g/L, and finally adding a graphene aqueous solution into the solution dissolved with ruthenium trichloride, iridium tetrachloride and titanium tetrachloride according to the proportion that the graphene content in the solution is 0.2 g/L-0.5 g/L, and uniformly mixing the solution by using an ultrasonic instrument to obtain the active coating liquid.
Coating and baking: uniformly brushing the active coating masking liquid on a pretreated metal matrix prepared by a titanium expanded wire, wherein the first time is 400-450 ℃, and the heat treatment time is 30-80 minutes; the heat treatment time from the second time to the last time is between 470 and 550 ℃ and is between 30 and 60 minutes; the steps are repeated in sequence to ensure that the coating amount is more than or equal to 16g/m2And sintering the mixture at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine evolution anode.
The graphene-containing chlorine evolution anode is used for electrolyzing NaCl in a 3.5mol/L NaCl solution at 90 ℃ and the current density is 4KA/m2Time-evolution chlorine potential 1.090v (vs sce); at 0.5mol/L H2SO4Electrolysis in solution with current density of 4KA/m2The time-evolution oxygen potential is 1.511V, and the chlorine-oxygen potential difference is 421 mV; at 95 ℃ and with a current density of 25KA/m2And the residual amount of the coating is 85.5 percent after electrolysis in 12mol/L NaOH solution for 4 hours.
Example 2
Preparing a coating solution: adding titanium tetrachloride into a ruthenium trichloride solution, and then adding iridium tetrachloride to ensure that the atomic percentage content of the iridium trichloride solution is Ru: 20-35%, Ir: 15-30%, Ti: 35-55 percent of the total metal concentration reaches 131g/L, and finally adding a graphene aqueous solution into the solution dissolved with ruthenium trichloride, iridium tetrachloride and titanium tetrachloride according to the proportion that the graphene content in the solution is 0.25g/L, and uniformly mixing the solution by using an ultrasonic instrument to obtain the active coating liquid.
Coating and baking: uniformly coating the active coating masking liquid on a pretreated metal substrate made of a titanium expanded metal, wherein the first heat treatment time is 30-80 minutes at 400-450 ℃; the heat treatment time from the second time to the last time is between 470 and 550 ℃ and is between 30 and 60 minutes; the steps are repeated in sequence to ensure that the coating amount is more than or equal to 16g/m2And sintering at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine evolution anode.
The graphene-containing chlorine evolution anode is used for electrolyzing NaCl in a 3.5mol/L NaCl solution at 90 ℃, and the current density is 4KA/m2Time-evolution chlorine potential 1.092v (vs sce); at 0.5mol/L H2SO4Electrolysis in solution with current density of 4KA/m2The time oxygen evolution potential is 1.513V, and the chlorine-oxygen potential difference is 421 mV; at 95 ℃ and with a current density of 25KA/m2And the residual amount of the coating is 87.2 percent after electrolysis in 12mol/L NaOH solution for 4 hours.
Example 3
Preparing a coating solution: adding titanium tetrachloride into a ruthenium trichloride solution, and then adding iridium tetrachloride to ensure that the atomic percentage content of the iridium tetrachloride is Ru: 20-35%, Ir: 15-30%, Ti: 35-55 percent of the total metal concentration reaches 131g/L, and finally adding a graphene aqueous solution into the solution dissolved with ruthenium trichloride, iridium tetrachloride and titanium tetrachloride according to the proportion that the graphene content in the solution is 0.5g/L, and uniformly mixing the solution by using an ultrasonic instrument to obtain the active coating liquid.
Coating and baking: uniformly brushing the active coating masking liquid on a pretreated metal matrix prepared by a titanium expanded wire, wherein the first time is 400-450 ℃, and the heat treatment time is 30-80 minutes; the heat treatment time from the second time to the last time is between 470 and 550 ℃ and is between 30 and 60 minutes; the steps are repeated in sequence to ensure that the coating amount is more than or equal to 16g/m2And sintering at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine evolution anode.
The graphene-containing chlorine evolution anode is used for electrolyzing NaCl in a 3.5mol/L NaCl solution at 90 ℃, and the current density is 4KA/m2Time-evolution chlorine potential 1.089v (vs sce); at 0.5mol/L H2SO4Electrolysis in solution with current density of 4KA/m2The time oxygen evolution potential is 1.508V, and the chlorine-oxygen potential difference is 419 mV; at 95 ℃ and with a current density of 25KA/m2And the residual amount of the coating is 88.1 percent after electrolysis in 12mol/L NaOH solution for 4 hours.
Comparative example 1
Preparing a coating solution: adding titanium tetrachloride into a ruthenium trichloride solution, and then adding iridium tetrachloride to ensure that the atomic percentage content of the iridium trichloride solution is Ru: 20-35%, Ir: 15-30%, Ti: 35-55%, adding a small amount of hydrochloric acid, and obtaining the active coating masking liquid when the concentration of the total metal reaches 131 g/L.
Coating and baking: uniformly brushing the active coating masking liquid on a pretreated metal matrix prepared by a titanium expanded wire, wherein the first time is 400-450 ℃, and the heat treatment time is 30-80 minutes; the heat treatment time from the second time to the last time is between 470 and 550 ℃ and is between 30 and 60 minutes; the steps are repeated in sequence to ensure that the coating amount is more than or equal to 16g/m2And sintering at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine evolution anode.
The chlorine-separating anode without graphene is used for electrolyzing NaCl in 3.5mol/L NaCl solution at 90 ℃ and with the current density of 4KA/m2Time-evolution chlorine potential 1.110V (VS SCE); at 0.5mol/L H2SO4Electrolysis in solution with current density of 4KA/m2The time oxygen evolution potential is 1.490V, and the chlorine-oxygen potential difference is 341 mV; at 95 ℃ and with a current density of 25KA/m2And electrolyzing in 12mol/L NaOH solution for 4 hours to obtain the coating residual amount of 76.3 percent.
The comparison between the examples and the comparative examples shows that the chlorine evolution potential of the graphene-containing chlorine evolution anode is 1.090V, the chlorine evolution potential of the conventional chlorine alkali anode is 1.110V, and the chlorine evolution potential of the graphene-containing chlorine evolution anode is reduced by 20mV compared with that of the conventional chlorine alkali chlorine evolution anode; the chlorine-oxygen potential difference of the graphene-containing chlorine evolution anode is 421mV, the chlorine-oxygen potential difference of the conventional anode for chlor-alkali is 380mV, and the chlorine-oxygen potential difference of the graphene-containing chlorine evolution anode is increased by 41mV compared with the chlorine-oxygen potential difference of the conventional anode for chlor-alkali; after the existing anode for chlor-alkali is subjected to strengthened life detection, the residual quantity of the coating is 76.3 percent, while after the graphene-containing chlorine evolution anode is subjected to strengthened life detection, the residual quantity of the coating is 85.5 percent and is improved by 9.2 percent. Therefore, the graphene-containing chlorine evolution anode has the characteristics of low chlorine evolution potential, long service life, capability of improving the chlorine-oxygen potential difference, enhancement of the selectivity of the electrode and reduction of side reactions in the preparation of sodium hydroxide.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (5)
1. The graphene-containing chlorine evolution anode is characterized by being prepared by the following steps:
A. preparing soluble salts of ruthenium element, iridium element and titanium element;
B. dissolving soluble salts of ruthenium element, soluble salts of iridium element and soluble salts of titanium element in water to enable the concentration of all metals in the water solution to be 110 g/L-140 g/L, wherein the molar ratio of the ruthenium element is 15% -35%, the molar ratio of the iridium element is 10% -30% and the molar ratio of the titanium element is 35% -55% according to metal components, and obtaining a salt solution;
C. adding a graphene aqueous solution into the salt solution obtained in the step B, wherein the ratio of graphene is 0.1-2 g/L, and then stirring the salt solution by using an ultrasonic mixer to uniformly mix the salt solution to obtain an active coating masking liquid;
D. pickling the metal matrix of the chlorine evolution anode containing titanium element to remove an oxide layer on the surface of the metal matrix of the chlorine evolution anode;
E. coating the active coating liquid obtained in the step C on the metal substrate treated in the step D, then carrying out heat treatment on the metal substrate coated with the coating liquid in an oxygen-containing atmosphere, wherein the heat treatment temperature is 350-450 ℃, the heat treatment time is 30-100 minutes, and an active coating is generated on the outer surface of the metal substrate;
F. e, continuously coating a layer of active coating liquid on the metal substrate obtained in the step E to the newly generated active coating, then carrying out heat treatment on the metal substrate coated with the coating liquid in an oxygen-containing atmosphere at the heat treatment temperature of 400-550 ℃, the heat treatment time of 30-100 minutes, regenerating a new active coating on the outer surface of the previously generated active coating, then continuously carrying out heat treatment on the metal substrate coated with the coating liquid in the oxygen-containing atmosphere at the heat treatment temperature of 400-550 ℃, the heat treatment time of 30-100 minutes, regenerating a new active coating on the outer surface of the previously generated active coating, and repeating the steps until the coating amount of the active coating on the surface of the metal substrate is more than or equal to 16g/m2；
G. And F, carrying out sintering heat treatment on the metal matrix obtained in the step F, wherein the sintering heat treatment temperature is 400-550 ℃, and the sintering heat treatment time is 200-300 minutes, so as to obtain the graphene-containing chlorine evolution anode.
2. The graphene-containing chlorine evolution anode according to claim 1, characterized in that the total metal concentration in the aqueous solution in the step B is 120g/L to 135g/L, wherein the molar ratio of the ruthenium element is 20% to 30%, the molar ratio of the iridium element is 15% to 25%, and the molar ratio of the titanium element is 40% to 50%, based on the metal components, to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.2-1.5 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 380-430 ℃, and the heat treatment time is 35-80 minutes;
and in the step F, the heat treatment temperature for the metal substrate coated with the coating solution is 450-520 ℃, and the heat treatment time is 35-80 minutes.
3. The graphene-containing chlorine evolution anode according to claim 2, characterized in that the total metal concentration in the aqueous solution in the step B is 125g/L to 130g/L, wherein the molar ratio of ruthenium element is 23% to 27%, the molar ratio of iridium element is 18% to 22%, and the molar ratio of titanium element is 43% to 47%, based on the metal components, to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.25-1.0 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 400-420 ℃, and the heat treatment time is 35-80 minutes;
and in the step F, the heat treatment temperature for heat treatment of the metal substrate coated with the coating solution is 480-500 ℃, and the heat treatment time is 35-80 minutes.
In the step F, the number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment is 6-12, and the single-layer coating amount of the active coating is 1.3g/m2—2.7g/m2。
The sintering heat treatment time in the step G is 250-300 minutes.
4. The graphene-containing chlorine evolution anode according to claim 3, characterized in that the total metal concentration in the aqueous solution in the step B is 126 g/L-128 g/L, wherein the molar ratio of ruthenium element is 24% -26%, the molar ratio of iridium element is 19% -21%, and the molar ratio of titanium element is 44% -46%, based on the metal components, to obtain a salt solution;
in the step C, adding graphene into the salt solution obtained in the step B according to the proportion of 0.35-0.6 g/L, and then uniformly mixing the graphene and the salt solution by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature for the metal substrate coated with the coating solution in the step E is 405-415 ℃, and the heat treatment time is 45-70 minutes;
and in the step F, the heat treatment temperature for heat treatment of the metal substrate coated with the coating solution is 480-500 ℃, and the heat treatment time is 45-70 minutes.
In the step F, the number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment is 7-10, and the single-layer coating amount of the active coating is 1.5g/m2—2.2g/m2。
The sintering heat treatment time in the step G is 260-280 minutes.
5. The graphene-containing chlorine evolving anode according to any one of claims 1 to 4, characterized in that said soluble inorganic salt of elemental ruthenium is RuCl3Or RuN4O10The soluble inorganic salt of iridium element is IrCl4Or Ir (NO)3)4The soluble inorganic salt of titanium element is TiCl4Or Ti (NO)3)4。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562078A (en) * | 2014-12-24 | 2015-04-29 | 蓝星(北京)化工机械有限公司 | Electrode for electrolysis, preparation method of electrode and electrolytic bath |
| CN104746097A (en) * | 2015-04-28 | 2015-07-01 | 中国船舶重工集团公司第七二五研究所 | Preparation method of graphene-doped metallic oxide anode |
| CN107974692A (en) * | 2017-12-01 | 2018-05-01 | 青岛双瑞海洋环境工程股份有限公司 | Graphene modified metal-oxide anode material and preparation process |
| CN108048862A (en) * | 2017-11-16 | 2018-05-18 | 江苏安凯特科技股份有限公司 | A kind of analysis chlorine anode and preparation method thereof |
| CN109518168A (en) * | 2018-12-14 | 2019-03-26 | 广西大学 | A kind of preparation method of the active titanium-matrix electrode plate of high steady coating |
| CN110129822A (en) * | 2019-06-24 | 2019-08-16 | 蓝星(北京)化工机械有限公司 | Electrode and preparation method thereof is precipitated in chlorine |
-
2020
- 2020-10-19 CN CN202011115974.6A patent/CN114438541B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562078A (en) * | 2014-12-24 | 2015-04-29 | 蓝星(北京)化工机械有限公司 | Electrode for electrolysis, preparation method of electrode and electrolytic bath |
| CN104746097A (en) * | 2015-04-28 | 2015-07-01 | 中国船舶重工集团公司第七二五研究所 | Preparation method of graphene-doped metallic oxide anode |
| CN108048862A (en) * | 2017-11-16 | 2018-05-18 | 江苏安凯特科技股份有限公司 | A kind of analysis chlorine anode and preparation method thereof |
| CN107974692A (en) * | 2017-12-01 | 2018-05-01 | 青岛双瑞海洋环境工程股份有限公司 | Graphene modified metal-oxide anode material and preparation process |
| CN109518168A (en) * | 2018-12-14 | 2019-03-26 | 广西大学 | A kind of preparation method of the active titanium-matrix electrode plate of high steady coating |
| CN110129822A (en) * | 2019-06-24 | 2019-08-16 | 蓝星(北京)化工机械有限公司 | Electrode and preparation method thereof is precipitated in chlorine |
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