CN114438541B - Graphene-containing chlorine-separating anode - Google Patents
Graphene-containing chlorine-separating anode Download PDFInfo
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- CN114438541B CN114438541B CN202011115974.6A CN202011115974A CN114438541B CN 114438541 B CN114438541 B CN 114438541B CN 202011115974 A CN202011115974 A CN 202011115974A CN 114438541 B CN114438541 B CN 114438541B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 claims abstract description 143
- 239000011248 coating agent Substances 0.000 claims abstract description 142
- 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 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 34
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052741 iridium Inorganic materials 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 19
- 238000002156 mixing Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 94
- 239000000243 solution Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 20
- 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
- 239000010410 layer Substances 0.000 claims description 7
- 239000002356 single layer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000034 method 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 15
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 25
- 229910052801 chlorine Inorganic materials 0.000 description 25
- 229910052719 titanium Inorganic materials 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 239000003513 alkali Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 8
- 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
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 7
- 229910017053 inorganic salt Inorganic materials 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 241000270708 Testudinidae Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 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
Classifications
-
- 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)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The graphene-containing chlorine-separating anode comprises the steps that a soluble salt of ruthenium element, a soluble salt of iridium element and a soluble salt of titanium element are dissolved in water, so that the total metal concentration in an aqueous solution is 110 g/L-140 g/L, and according to metal components, the molar ratio of ruthenium element is 15% -35%, the molar ratio of iridium element is 10% -30%, and the molar ratio of titanium element is 35% -55%, so that a salt solution is obtained; and adding a graphene aqueous solution into the salt solution obtained in the step B according to the proportion of 0.1 g/L-2 g/L, and uniformly mixing by using an ultrasonic mixer to obtain the active coating liquid. The graphene-containing chlorine-separating anode has the advantages of low chlorine-separating potential and long service life, and can improve chlorine-oxygen potential difference, enhance electrode selectivity and reduce side reactions in sodium hydroxide preparation.
Description
Technical Field
The invention relates to the field of sodium hydroxide preparation, in particular to a graphene-containing chlorine-separating anode.
Background
In the existing chlor-alkali electrolysis device, the anode adopts titanium base and is coated with noble metal coating of Ru, ir and Ti, and the production process of the anode prepared by the thermal oxidation method is mature. It is known that noble metal coatings of titanium base and coated with Ru, ir, ti have tortoise cracks on the surface, which are caused by the interaction of mechanical stresses generated by the difference in expansion coefficients of the metal oxide coating and the titanium base with thermal stresses generated by the cooling of the electrode from furnace temperature to room temperature,the tortoise crack has the advantages that the specific surface area of the electrode is increased, so that the active points of the electrode are increased; the disadvantage is that the by-product oxygen is easy to diffuse and migrate to the surface of the titanium matrix and form a layer of TiO with the titanium matrix during the operation of the electrolytic cell 2 Passivation film, thereby causing passivation of the electrode and loss of activity.
Thus, there is a great need for an electrode coating that increases specific surface area while reducing cracking, thereby achieving the goals of reducing chlorine evolution potential and extending service life. Meanwhile, the potential difference of chlorine and oxygen is improved, the selectivity of the electrode is enhanced, and side reactions in the preparation of sodium hydroxide are reduced.
Graphene, which is a novel two-dimensional carbon nanomaterial, has good conductivity, and is high in electron transfer speed even at room temperature, and 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 graphene is added into the coating, the surface morphology is changed, the surface of the coating is honeycomb-shaped, the rugged surface characteristic increases the roughness of the surface of the anode, the number of active points of the anode is increased, the electrocatalytic activity of the anode is improved, meanwhile, the surface cracks are continuous, the cracks are fine and small, and the chance that oxygen reaches a titanium matrix is reduced, so that the graphene-based anode is an ideal additive.
Disclosure of Invention
The invention aims to provide a graphene-containing chlorine-separating anode which has low chlorine-separating potential and long service life, can improve the chlorine-oxygen potential difference, enhance the selectivity of an electrode and reduce side reactions in sodium hydroxide preparation.
The graphene-containing chlorine-separating anode is prepared by the following steps:
A. preparing a soluble salt of ruthenium element, a soluble salt of iridium element and a soluble salt of titanium element;
B. dissolving soluble salts of ruthenium element, iridium element and titanium element in water to ensure that the total metal concentration in the water solution is 110g/L to 140g/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, so as to obtain a salt solution;
C. adding graphene aqueous solution into the salt solution obtained in the step B, wherein the proportion of graphene is 0.1 g/L-2 g/L, and stirring the salt solution by using an ultrasonic mixer to uniformly mix the salt solution to obtain an active coating liquid;
D. pickling a metal matrix of the chlorine-evolving anode containing titanium element, and removing an oxide layer on the surface of the metal matrix of the chlorine-evolving 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. continuously coating a layer of active coating liquid on the newly formed active coating on the metal substrate obtained in the step E, then carrying out heat treatment on the metal substrate coated with the coating liquid under the oxygen-containing atmosphere, wherein the heat treatment temperature is 400-550 ℃, the heat treatment time is 30-100 minutes, and a new active coating is regenerated on the outer surface of the previously formed active coating, then continuously carrying out heat treatment on the metal substrate coated with the coating liquid under the oxygen-containing atmosphere, the heat treatment temperature is 400-550 ℃, the heat treatment time is 30-100 minutes, and a new active coating is regenerated on the outer surface of the previously formed active coating, and the steps are repeated circularly 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, performing sintering heat treatment on the metal substrate 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-separating anode.
Preferably, the total metal concentration in the aqueous solution in the step B is 120g/L to 135g/L, and 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% according to metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.2 g/L-1.5 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 380-430 ℃ and the heat treatment time is 35-80 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F 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 125g/L to 130g/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 metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.25 g/L-1.0 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 400-420 ℃, and the heat treatment time is 35-80 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F is 480-500 ℃ and the heat treatment time is 35-80 minutes.
The number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment in the step F is 6 to 12, and the single-layer coating amount of the active coating is 1.3g/m 2 —2.7g/m 2 。
And (C) 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 126g/L to 128g/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% according to metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.35 g/L-0.6 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 405-415 ℃, and the heat treatment time is 45-70 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F is 480-500 ℃ and the heat treatment time is 45-70 minutes.
The number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment in the step F is 7-10 times, and the single-layer coating amount of the active coating is 1.5g/m 2 —2.2g/m 2 。
And (C) sintering heat treatment time in the step (G) is 260-280 minutes.
Preferably, the soluble inorganic salt of ruthenium element is RuCl 3 Or RuN 4 O 10 The soluble inorganic salt of iridium element is IrCl 4 Or Ir (NO) 3 ) 4 The soluble inorganic salt of titanium element is TiCl 4 Or Ti (NO) 3 ) 4 。
The graphene-containing chlorine-separating anode is prepared by dissolving soluble salts of ruthenium, iridium and titanium in water to ensure that the total metal concentration in an aqueous solution is 110 g/L-140 g/L, wherein the molar ratio of ruthenium is 15% -35%, the molar ratio of iridium is 10% -30% and the molar ratio of titanium is 35% -55% according to metal components, so as to obtain a salt solution; adding graphene aqueous solution into the salt solution obtained in the step B according to the proportion of 0.1 g/L-2 g/L, and uniformly mixing by using an ultrasonic mixer to obtain 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 existing chlorine alkali anode is 1.110V, and the chlorine evolution potential of the graphene-containing chlorine evolution anode is 20mV lower than that of the existing chlorine alkali chlorine evolution anode; the chlorine-oxygen potential difference of the graphene-containing chlorine-separating anode is 421mV, the chlorine-oxygen potential difference of the existing anode for chlor-alkali is 380mV, and the chlorine-oxygen potential difference of the graphene-containing chlorine-separating anode is 41mV higher than that of the existing anode for chlor-alkali; after the existing anode strengthening life detection for chlor-alkali, the coating residual quantity is 76.3%, and after the graphene-containing chlorine-separating anode is subjected to strengthening life detection, the coating residual quantity is 85.5%, and is improved by 9.2%. Therefore, the graphene-containing chlorine-separating anode has the characteristics of low chlorine-separating potential and long service life, and can improve the chlorine-oxygen potential difference, enhance the electrode selectivity and reduce side reactions in sodium hydroxide preparation.
Other details and features of the graphene-containing chlorine evolving anode of the present invention will become apparent upon reading the examples described in detail below.
Drawings
FIG. 1 is a scanning electron microscope image of a graphene-containing chlorine-evolving anode of the present invention;
fig. 2 is a scanning electron microscope image of a conventional chlor-alkali anode.
Detailed Description
The graphene-containing chlorine-separating anode is prepared by the following steps:
A. preparing a soluble salt of ruthenium element, a soluble salt of iridium element and a soluble salt of titanium element;
B. dissolving soluble salts of ruthenium element, iridium element and titanium element in water to ensure that the total metal concentration in the water solution is 110g/L to 140g/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, so as to obtain a salt solution;
C. adding graphene aqueous solution into the salt solution obtained in the step B, wherein the proportion of graphene is 0.1 g/L-2 g/L, and stirring the salt solution by using an ultrasonic mixer to uniformly mix the salt solution to obtain an active coating liquid;
D. pickling a metal matrix of the chlorine-evolving anode containing titanium element, and removing an oxide layer on the surface of the metal matrix of the chlorine-evolving 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. continuously coating a layer of active coating liquid on the newly formed active coating on the metal substrate obtained in the step E, then carrying out heat treatment on the metal substrate coated with the coating solution in an oxygen-containing atmosphere, wherein the heat treatment temperature is 400-550 ℃, the heat treatment time is 30-100 minutes, a new active coating is regenerated on the outer surface of the previously formed active coating, then, continuously carrying out heat treatment on the metal substrate coated with the coating solution in the oxygen-containing atmosphere, the heat treatment temperature is 400-550 ℃, the heat treatment time is 30-100 minutes, and a new active coating is regenerated on the outer surface of the previously formed active coating, and the cycle is repeated 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, performing sintering heat treatment on the metal substrate 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-separating anode.
As a further improvement of the invention, the total metal concentration in the aqueous solution in the step B is 120g/L to 135g/L, and 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% according to metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.2 g/L-1.5 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 380-430 ℃ and the heat treatment time is 35-80 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F 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 125g/L to 130g/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 metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.25 g/L-1.0 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 400-420 ℃, and the heat treatment time is 35-80 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F is 480-500 ℃ and the heat treatment time is 35-80 minutes.
And in the step F, the outer surface of the metal substrate is coated with the active coating liquid and subjected to heat treatment for 6-12 times, and the single-layer coating amount of the active coating is 1.3g/m < 2 > -2.7 g/m < 2 >.
And (C) 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 126g/L to 128g/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% according to metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.35 g/L-0.6 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 405-415 ℃, and the heat treatment time is 45-70 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F is 480-500 ℃ and the heat treatment time is 45-70 minutes.
And in the step F, the outer surface of the metal substrate is coated with the active coating liquid and subjected to heat treatment for 7-10 times, and the single-layer coating amount of the active coating is 1.5g/m < 2 > -2.2 g/m < 2 >.
And (C) sintering heat treatment time in the step (G) is 260-280 minutes.
As a further improvement of the present invention, the soluble inorganic salt of the above ruthenium element is RuCl3 or RuN4O10, the soluble inorganic salt of the iridium element is IrCl4 or Ir (NO 3) 4, and the soluble inorganic salt of the titanium element is TiCl4 or Ti (NO 3) 4.
The mass percentages of the ruthenium element, the iridium element and the titanium element in the active coating according to the metal components can be detected by an x-ray fluorescence tester.
According to the invention, on the basis of Ru, ir and Ti titanium-based anodes in the conventional 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 rugged surface characteristics increase the surface roughness of an electrode, the number of the surface active points of the anode is increased, the electrocatalytic activity of the electrode is improved, the chlorine evolution potential is effectively reduced, the chlorine-oxygen potential difference is further improved, the selectivity of the electrode is enhanced, the side reaction in sodium hydroxide preparation is reduced, and the surface cracks are thin and small. Therefore, compared with the Ru, ir and Ti titanium-based anode in the existing chlor-alkali electrolysis device, the chlorine-separating anode has three advantages: (1) lower chlorine evolution potential; (2) greater selectivity; (3) longer lifetime.
Example 1
Preparing a coating liquid: adding titanium tetrachloride into ruthenium trichloride solution, and then adding iridium tetrachloride to make the atomic percentage content of Ru: 20-35%, ir: 15-30%, ti: 35-55%, adding a small amount of hydrochloric acid, wherein the total metal concentration reaches 131g/L, and finally adding a graphene aqueous solution into the solution in which ruthenium trichloride, iridium tetrachloride and titanium tetrachloride are dissolved according to the proportion that the graphene content in the solution is 0.2 g/L-0.5 g/L, and uniformly mixing by using an ultrasonic instrument to obtain the active coating liquid.
Coating and baking: uniformly coating the active coating liquid on a pretreated metal substrate made of a titanium pull net, wherein the first time at 400-450 ℃ and the heat treatment time at 30-80 minutes; the second time to the last time at 470 ℃ to 550 ℃ and the heat treatment time is 30 minutes to 60 minutes; the steps are repeated in sequence, so that the coating quantity is more than or equal to 16g/m 2 And (3) sintering at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine-separating anode.
The graphene-containing chlorine-separating anode is used for electrolyzing NaCl, and is electrolyzed in a NaCl solution with the temperature of 90 ℃ and the mol/L of 3.5, and the current density is 4KA/m 2 Chlorine evolution potential at time 1.090V (VS SCE); at 0.5mol/L H 2 SO 4 Electrolysis in solution with a current density of 4KA/m 2 The oxygen evolution potential is 1.511V, and the chlorine-oxygen potential difference is 421mV; at 95℃and a current density of 25KA/m 2 The solution is electrolyzed in 12mol/L NaOH solution for 4 hours, and the coating residue is 85.5 percent.
Example 2
Preparing a coating liquid: adding titanium tetrachloride into ruthenium trichloride solution, and then adding iridium tetrachloride to make the atomic percentage content of Ru: 20-35%, ir: 15-30%, ti: 35-55%, adding a small amount of hydrochloric acid, wherein the total metal concentration reaches 131g/L, and finally adding a graphene aqueous solution into the solution in which ruthenium trichloride, iridium tetrachloride and titanium tetrachloride are dissolved according to the proportion that the graphene content in the solution is 0.25g/L, and uniformly mixing by using an ultrasonic instrument to obtain the active coating liquid.
Coating and baking: uniformly coating the active coating liquid on a pretreated metal substrate made of a titanium pull net, wherein the first time at 400-450 ℃ and the heat treatment time at 30-80 minutes; the second time to the last time at 470 ℃ to 550 ℃ and the heat treatment time is 30 minutes to 60 minutes; the steps are repeated in sequence, so that the coating quantity is more than or equal to 16g/m 2 And (3) sintering at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine-separating anode.
The graphene-containing material is preparedThe chlorine-separating anode is used for electrolyzing NaCl at 90 ℃ in 3.5mol/L NaCl solution with current density of 4KA/m 2 Chlorine evolution potential at time 1.092V (VS SCE); at 0.5mol/L H 2 SO 4 Electrolysis in solution with a current density of 4KA/m 2 The oxygen evolution potential is 1.513V, and the chlorine-oxygen potential difference is 421mV; at 95℃and a current density of 25KA/m 2 The solution was electrolyzed in a 12mol/L NaOH solution for 4 hours, and the residual amount of the coating was 87.2%.
Example 3
Preparing a coating liquid: adding titanium tetrachloride into ruthenium trichloride solution, and then adding iridium tetrachloride to make the atomic percentage content of Ru: 20-35%, ir: 15-30%, ti: 35-55%, adding a small amount of hydrochloric acid, wherein the total metal concentration reaches 131g/L, and finally adding a graphene aqueous solution into the solution in which ruthenium trichloride, iridium tetrachloride and titanium tetrachloride are dissolved according to the proportion that the graphene content in the solution is 0.5g/L, and uniformly mixing by using an ultrasonic instrument to obtain the active coating liquid.
Coating and baking: uniformly coating the active coating liquid on a pretreated metal substrate made of a titanium pull net, wherein the first time at 400-450 ℃ and the heat treatment time at 30-80 minutes; the second time to the last time at 470 ℃ to 550 ℃ and the heat treatment time is 30 minutes to 60 minutes; the steps are repeated in sequence, so that the coating quantity is more than or equal to 16g/m 2 And (3) sintering at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine-separating anode.
The graphene-containing chlorine-separating anode is used for electrolyzing NaCl, and is electrolyzed in a NaCl solution with the temperature of 90 ℃ and the mol/L of 3.5, and the current density is 4KA/m 2 The time-resolved chlorine potential 1.089V (VS SCE); at 0.5mol/L H 2 SO 4 Electrolysis in solution with a current density of 4KA/m 2 Oxygen evolution potential is 1.508V, chlorine oxygen potential difference is 419mV; at 95℃and a current density of 25KA/m 2 The solution was electrolyzed in a 12mol/L NaOH solution for 4 hours, and the residual amount of the coating was 88.1%.
Comparative example 1
Preparing a coating liquid: adding titanium tetrachloride into ruthenium trichloride solution, and then adding iridium tetrachloride to make the atomic percentage content of Ru: 20-35%, ir: 15-30%, ti: 35-55%, adding a small amount of hydrochloric acid, and obtaining the active coating liquid, wherein the total metal concentration reaches 131 g/L.
Coating and baking: uniformly coating the active coating liquid on a pretreated metal substrate made of a titanium pull net, wherein the first time at 400-450 ℃ and the heat treatment time at 30-80 minutes; the second time to the last time at 470 ℃ to 550 ℃ and the heat treatment time is 30 minutes to 60 minutes; the steps are repeated in sequence, so that the coating quantity is more than or equal to 16g/m 2 And (3) sintering at the heat treatment temperature of 400-550 ℃ for 250-300 minutes to obtain the graphene-containing chlorine-separating anode.
The chlorine-separating anode without graphene is used for electrolyzing NaCl, and is electrolyzed in a NaCl solution with the temperature of 90 ℃ and the mol/L of 3.5, and the current density is 4KA/m 2 Chlorine evolution potential at time 1.110V (VS SCE); at 0.5mol/L H 2 SO 4 Electrolysis in solution with a current density of 4KA/m 2 The oxygen evolution potential is 1.490V, and the chlorine-oxygen potential difference is 341mV; at 95℃and a current density of 25KA/m 2 The solution was electrolyzed in a 12mol/L NaOH solution for 4 hours, and the residual amount of the coating was 76.3%.
As can be seen from the comparison of the examples and the comparative examples, the chlorine evolution potential of the graphene-containing chlorine evolution anode is 1.090V, the chlorine evolution potential of the existing chlorine alkali anode is 1.110V, and the chlorine evolution potential of the graphene-containing chlorine evolution anode is 20mV lower than that of the existing chlorine alkali chlorine evolution anode; the chlorine-oxygen potential difference of the graphene-containing chlorine-separating anode is 421mV, the chlorine-oxygen potential difference of the existing anode for chlor-alkali is 380mV, and the chlorine-oxygen potential difference of the graphene-containing chlorine-separating anode is 41mV higher than that of the existing anode for chlor-alkali; after the existing anode strengthening life detection for chlor-alkali, the coating residual quantity is 76.3%, and after the graphene-containing chlorine-separating anode is subjected to strengthening life detection, the coating residual quantity is 85.5%, and is improved by 9.2%. Therefore, the graphene-containing chlorine-separating anode has the characteristics of low chlorine-separating potential and long service life, and can improve the chlorine-oxygen potential difference, enhance the electrode selectivity and reduce side reactions in sodium hydroxide preparation.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (4)
1. The graphene-containing chlorine-separating anode is characterized by being prepared by the following steps:
A. preparing a soluble salt of ruthenium element, a soluble salt of iridium element and a soluble salt of titanium element;
B. dissolving soluble salts of ruthenium element, iridium element and titanium element in water to ensure that the total metal concentration in the water solution is 110g/L to 140g/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, so as to obtain a salt solution;
C. adding graphene aqueous solution into the salt solution obtained in the step B, wherein the proportion of graphene is 0.1 g/L-2 g/L, and stirring the salt solution by using an ultrasonic mixer to uniformly mix the salt solution to obtain an active coating liquid;
D. pickling a metal matrix of the chlorine-evolving anode containing titanium element, and removing an oxide layer on the surface of the metal matrix of the chlorine-evolving 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. continuously coating a layer of active coating liquid on the newly generated active coating on the metal substrate obtained in the step E, 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 400-550 ℃, the heat treatment time is 30-100 minutes, and a new active coating is generated on the outer surface of the active coating generated in the previous time, and then continuously coating the metal substrate coated with the coating liquid in the oxygen-containing atmosphereThe metal matrix of the coating solution is subjected to heat treatment at the temperature of 400-550 ℃ for 30-100 minutes, and a new active coating is regenerated on the outer surface of the active coating generated in the previous time, and the process is repeated in a circulating way until the coating amount of the active coating on the surface of the metal matrix is more than or equal to 16g/m 2 ；
G. F, performing sintering heat treatment on the metal substrate 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-separating anode;
the soluble salt of ruthenium element is RuCl 3 Or RuN 4 O 10 The soluble salt of iridium element is IrCl 4 Or Ir (NO) 3 ) 4 The soluble salt of titanium element is TiCl 4 Or Ti (NO) 3 ) 4 。
2. The chlorine-separating anode containing graphene according to claim 1, wherein the total metal concentration in the aqueous solution in the step B is 120g/L to 135g/L, and 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% in terms of metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.2 g/L-1.5 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 380-430 ℃ and the heat treatment time is 35-80 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F is 450-520 ℃ and the heat treatment time is 35-80 minutes.
3. The chlorine-separating anode containing graphene according to claim 2, wherein the total metal concentration in the aqueous solution in the step B is 125g/L to 130g/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% in terms of metal components, so as to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.25 g/L-1.0 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 400-420 ℃, and the heat treatment time is 35-80 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F is 480-500 ℃ and the heat treatment time is 35-80 minutes;
the number of times of coating the active coating liquid on the outer surface of the metal substrate and carrying out heat treatment in the step F is 6 to 12, and the single-layer coating amount of the active coating is 1.3g/m 2 —2.7g/m 2 ；
And (C) sintering heat treatment time in the step (G) is 250-300 minutes.
4. The chlorine-evolving anode containing graphene according to claim 3, wherein the total metal concentration in the aqueous solution in the step B is 126g/L to 128g/L, wherein the molar ratio of ruthenium element is 24% to 26%, the molar ratio of iridium element is 19% to 21%, and the molar ratio of titanium element is 44% to 46%, based on the metal component, to obtain a salt solution;
adding graphene into the salt solution obtained in the step B according to the proportion of 0.35 g/L-0.6 g/L, and uniformly mixing by using an ultrasonic mixer to obtain an active coating liquid;
the heat treatment temperature of the metal matrix coated with the coating solution in the step E is 405-415 ℃, and the heat treatment time is 45-70 minutes;
the heat treatment temperature of the metal matrix coated with the coating solution in the step F is 480-500 ℃ and the heat treatment time is 45-70 minutes;
the number of times of coating the active coating liquid on the outer surface of the metal matrix and performing heat treatment in the step F is 7From 10 times, the single-layer coating amount of the active coating is 1.5g/m 2 —2.2g/m 2 ；
And (C) sintering heat treatment time in the step (G) is 260-280 minutes.
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