EP3478876A1 - Electrolyte system for the synthesis of sodium perchlorate - Google Patents
Electrolyte system for the synthesis of sodium perchlorateInfo
- Publication number
- EP3478876A1 EP3478876A1 EP17740454.8A EP17740454A EP3478876A1 EP 3478876 A1 EP3478876 A1 EP 3478876A1 EP 17740454 A EP17740454 A EP 17740454A EP 3478876 A1 EP3478876 A1 EP 3478876A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- anode
- cathode
- platinum
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 229910001488 sodium perchlorate Inorganic materials 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 32
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 19
- 239000011651 chromium Substances 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 13
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- -1 alkali metal dichromate Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- ONTRRWKYBVZWST-UHFFFAOYSA-L disodium chlorate perchlorate Chemical compound [Na+].[Na+].[O-][Cl](=O)=O.[O-][Cl](=O)(=O)=O ONTRRWKYBVZWST-UHFFFAOYSA-L 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 6
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000003071 parasitic effect Effects 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- 229940005989 chlorate ion Drugs 0.000 description 2
- 239000012809 cooling fluid Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UPIXZLGONUBZLK-UHFFFAOYSA-N platinum Chemical compound [Pt].[Pt] UPIXZLGONUBZLK-UHFFFAOYSA-N 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- ZONODCCBXBRQEZ-UHFFFAOYSA-N platinum tungsten Chemical compound [W].[Pt] ZONODCCBXBRQEZ-UHFFFAOYSA-N 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical class [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 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
- C25B1/28—Per-compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
Definitions
- the invention relates in particular to an electrolytic system for the synthesis of sodium perchlorate by electrochemical oxidation of sodium chlorate.
- Ammonium perchlorate (NH 4 ClO 4 ) is used in the space industry as a constituent of propellant shipments and is typically synthesized from sodium perchlorate (NaClO 4 ).
- Sodium perchlorate can, for its part, be obtained by electrochemical oxidation of sodium chlorate (NaClO 3 ).
- the electrochemical oxidation of sodium chlorate to sodium perchlorate is carried out with an electrolytic system comprising an anode and a cathode present in a bath comprising sodium chlorate.
- the oxidation reaction of the chlorate ion at the anode is accompanied by parasitic reactions at the cathode generating for example the formation of chlorine.
- the invention aims specifically to meet the aforementioned need.
- the invention proposes, according to a first aspect, an electrolytic system for the synthesis of sodium perchlorate by electrochemical oxidation of sodium chlorate, said system comprising at least: an electrolyte comprising sodium chlorate,
- an anode present in the electrolyte having an outer surface made of platinum or platinum alloy,
- the cathode present in the electrolyte, the cathode having a metal alloy outer surface having a mass content of chromium of between 5% and 25%, and
- an electric generator connected to the anode and to the cathode.
- the electrolytic system according to the invention implements a specific pair of anode and cathode each having an electrically active outer surface formed of a particular material.
- the electrolytic system according to the invention advantageously makes it possible to dispense with the use of additive dichromate or alkali metal fluoride in the electrolyte while generating a limited quantity of impurities during the electrosynthesis of sodium perchlorate.
- the system according to the invention therefore makes it possible to render superfluous the step of separating sodium perchlorate from the dichromate or fluoride additive and thus to simplify the process for obtaining sodium perchlorate by electrochemical oxidation of sodium chlorate.
- the electrosynthesis of sodium perchlorate by implementing the system according to the invention advantageously has an improved performance compared to existing methods.
- the anode may comprise an electrically conductive substrate covered with a platinum or platinum alloy coating.
- Such a configuration is advantageous insofar as it implements an anode having a limited amount of platinum and therefore reduced cost.
- an anode made entirely of platinum or platinum alloy can be used.
- the metal alloy of the cathode may have a chromium mass content of between 10% and 25%, for example between 10% and 20%.
- the metal alloy of the cathode may be a steel, a nickel alloy or a zirconium alloy.
- the concentration of sodium chlorate in the electrolyte may be greater than or equal to 0.1 mol / L. In in particular, the concentration of sodium chlorate in the electrolyte may be greater than or equal to 0.5 mol / L.
- the concentration of sodium chlorate in the electrolyte may for example be between 0.5 mol / L and Cs where Cs denotes the saturation concentration of sodium chlorate in the electrolyte, and for example be between 0.5 mol. and 5 mol / L.
- the electrolyte may be free of fluoride or alkali metal dichromate.
- the system may comprise a first chamber in which the electrolyte, the anode and the cathode are present and a second chamber, distinct from the first chamber, in which the electrolyte is present, the system being able to further comprising an electrolyte circulation circuit configured to flush the electrolyte between the first and second chambers.
- the invention provides a process for the manufacture of sodium perchlorate comprising a step of electrochemical oxidation of sodium chlorate to sodium perchlorate by implementing a system as described above.
- the current density imposed during the electrochemical oxidation can be between 1000 A / m 2 and 20000 A / m 2 , for example between 1000 A / m 2 and 5000 A / m 2 .
- FIG. 1 schematically represents an example of a system according to the invention
- FIGS. 2 and 3 schematically represent anode structures that can be used in the system of FIG. 1,
- FIGS. 4 and 5 schematically represent cathode structures that can be used in the system of FIG. 1;
- FIG. 6 is a graph obtained experimentally comparing the formation kinetics of sodium perchlorate obtained by implementing a system according to the invention with that obtained by implementing a system outside the invention, and
- FIG. 7 is a graph obtained experimentally comparing the gas flow rates generated during the use of a system according to the invention and a system outside the invention.
- FIG. 1 shows schematically an example of electrolytic system 1 according to the invention.
- This system 1 is configured to manufacture sodium perchlorate by electrochemical oxidation of sodium chlorate.
- the System 1 comprises a first chamber 3 in which a liquid electrolyte is present.
- the electrolyte 10 comprises sodium chlorate.
- the concentration of sodium chlorate in the electrolyte 10, before initiation of the electrochemical oxidation may be greater than or equal to 0.1 mol / L, for example 0.5 mol / L and for example be between 0, 5 mol / L and 5 mol / L.
- the electrolyte 10 may be an aqueous electrolyte.
- the electrolyte 10 is, moreover, free of fluoride or alkali metal dichromate.
- the electrolyte 10 is devoid of the following compounds: sodium fluoride (NaF), potassium fluoride (KF), sodium dichromate (Na 2 Cr 2 O 7 ) and potassium dichromate (K 2 Cr 2 O 7 ) .
- the system 1 further comprises an anode 15 and a cathode 17 which are each present in the electrolyte 10 in the first chamber 3.
- the electrochemical oxidation of sodium chlorate to obtain sodium perchlorate is intended to be carried out in the first room 3.
- the anode 15 has an outer surface, corresponding to its active surface, platinum or platinum alloy. This outer surface is present in the electrolyte 10.
- the outer surface of the anode 15 may be pure platinum.
- the outer surface of the anode 15 may be platinum alloy selected from the following alloys: platinum-rhodium alloys, platinum-iridium alloys and platinum-tungsten alloys.
- FIG. 2 illustrates the structure of an exemplary anode 15 usable in the system 1 of FIG. 1.
- the anode 15 comprises an electrically conductive substrate 28 covered with a coating 26 in platinum or platinum alloy.
- the coating 26 defines the outer surface Si of the anode 15.
- the substrate 28 is formed of a material different from that constituting the coating 26.
- the material forming the substrate 28 may for example comprise titanium, zirconium, hafnium, vanadium, niobium, tantalum, palladium, molybdenum or an alloy thereof.
- the material forming the substrate 28 may for example be chosen from: titanium, zirconium, hafnium, vanadium, niobium, tantalum, palladium, molybdenum and their alloys.
- the material forming the substrate 28 may still be graphite.
- the thickness ei of the coating 26 may for example be greater than or equal to 0.5 ⁇ , and for example be between 1 ⁇ m and 5 ⁇ m.
- the anode 15 as illustrated in FIG. 2 can be obtained by electrolytic deposition of platinum or a platinum alloy on the substrate 28.
- an anode 115 entirely made of platinum or a platinum platinum alloy.
- This anode 115 defines an outer surface S2.
- the implementation of an anode 15 having the structure illustrated in Figure 2 is advantageous insofar as it has a reduced cost.
- the cathode 17 has, for its part, an outer surface, corresponding to its active surface, metal alloy having a mass content of chromium of between 5% and 25%. This outer surface is present in the electrolyte 10.
- the metal alloy of the cathode may have a chromium mass content of between 10% and 25%, for example between 10% and 20%.
- the metal alloy of the cathode 17 may be a stainless steel, for example 316L stainless steel, a nickel alloy or a zirconium alloy.
- FIG. 4 illustrates the structure of an exemplary cathode 17 that can be used in the system 1 of FIG. 1.
- the cathode 17 consists entirely of a metal alloy with a mass content in chromium of between 5% and 25% (massive metal alloy cathode with a mass content in chromium of between 5% and 25%).
- This cathode 17 defines an outer surface S 3 .
- the coating 118 defines the outer surface S 4 of the cathode 117.
- the substrate 119 is formed of a material different from that constituting the coating 118.
- the system 1 illustrated in FIG. 1 furthermore comprises an electric generator 20 connected to the anode 15 and to the cathode 17.
- the anode 15 is connected via the conductor 16 to the positive terminal 18 of the generator 20.
- cathode 17 is connected via the driver
- the system 1 further comprises a second chamber 5, separate from the first chamber 3, wherein the liquid electrolyte is present.
- the presence of this second chamber 5 is optional.
- the second chamber 5 is in communication with the first chamber 3.
- the electrolyte 10 is intended to flow between the first 3 and second 5 chambers during the electrochemical oxidation.
- the system 1 comprises a circulation circuit of the electrolyte 7 which comprises in the illustrated example:
- the second channel 8 connecting an outlet 5s of the second chamber 5 to an inlet of the pump 9, the second channel 8 can, as illustrated, be provided with a valve 13, and
- a third channel 11 connecting an output of the pump 9 to an inlet 3e of the first chamber 3.
- the electrolyte 10 flows between the first 3 and second 5 chambers according to the path shown by the arrows F1. During its circulation, the electrolyte 10 passes through the first channel 12, the second channel 8 and the third channel 11.
- the second chamber is maintained at a substantially constant temperature by a thermostat 23 in which a temperature control fluid circulates (arrows F2).
- the thermostat 23 may for example maintain the temperature of the second chamber at about 20 ° C.
- the system 1 may further include a condenser 25 for condensing at least a portion of the vapors produced during the electrochemical oxidation.
- a cooling fluid circulates in the refrigerant 25 to achieve this condensation (arrows F3).
- the cooling fluid is for example, before heat exchange, at a temperature of -5 ° C.
- the circulation of the electrolyte 10 between the first 3 and second 5 chambers is first initiated by actuation of the pump 9.
- a potential difference is then imposed between the anode 15 and the cathode 17 using the generator which electrochemical oxidation of sodium chlorate to sodium perchlorate in the first chamber 3.
- Electrochemically, sodium perchlorate is synthesized according to the overall reaction:
- the electrolyte 10 can flow continuously. It is possible to impose a flow rate of the electrolyte in the circuit 7 of between 250 liters / hour and 350 liters / hour, for example.
- the current density imposed during the electrochemical oxidation can be between 1 kA / m 2 and 20 kA / m 2 , for example between 1 kA / m 2 and 5 kA / m 2 .
- sodium perchlorate is obtained using a system without the second chamber 5. In the latter case, there is not necessarily movement of the electrolyte in the system.
- the experimental setup that was used is of the type shown in Figure 1.
- the assembly was equipped with a flow meter at the output of refrigerant which quantifies the flow rate (in liters per hour: L / h) and the amount of gas produced during the electrolysis.
- the electrolytic system included a stainless steel cathode (316L steel having a chromium content of 18%). Two separate anode materials were tested. A first test according to the invention was carried out with a Ti / Pt anode having a titanium substrate coated with a platinum coating. A second test outside the invention was carried out with a Ti / PbO 2 anode having a titanium substrate coated with a coating of lead dioxide.
- Table 1 below and Figure 6 highlight the advantages conferred by the system according to the invention. It is found that the efficiency and the formation kinetics of sodium perchlorate are improved thanks to the system according to the invention in comparison with the system outside the invention using a Ti / PbO 2 anode.
- chlorate ion and perchlorate ion material were determined by ion chromatography during the tests carried out.
- the current yield (Rdtcurrent) of the reaction is calculated as the ratio of the feedstock used for the oxidation of chlorate ions to perchlorate ions and the total load applied to the system.
- I xt in the above formula ⁇ 4- denotes the number of moles of perchlorate ions at the end of synthesis
- F is the Faraday constant (96485 Cmol 1 )
- I the imposed current (A)
- t the electrolysis time (s).
- the progress of the synthesis (Av) is in turn determined by making the ratio between the number of moles of chlorate ions consumed and the number of moles of initial chlorate ions.
- the electrolytic system included a Ti / Pt anode.
- Two separate cathode materials were tested.
- a first test according to the invention was carried out with a stainless steel cathode (316L steel having a mass content of chromium of 18%).
- a second test outside the invention was carried out with a steel cathode devoid of chromium.
- the other experimental conditions are the same as in Example 1. In this example, a current density of about 1900 A / m 2 was imposed.
- the invention thus proposes an electrolytic system implementing a specific pair of anode and cathode making it possible to improve the synthesis yield of sodium perchlorate while avoiding the use of additive dichromate or metal fluoride alkaline in the electrolyte.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1656234A FR3053362B1 (en) | 2016-06-30 | 2016-06-30 | ELECTROLYTIC SYSTEM FOR THE SYNTHESIS OF SODIUM PERCHLORATE WITH ANODE WITH EXTERNAL SURFACE OF PLATINUM OR ALLOY OF PLATINUM AND CATHODE WITH EXTERNAL SURFACE OF METALLIC ALLOY COMPRISING CHROME |
PCT/FR2017/051755 WO2018002543A1 (en) | 2016-06-30 | 2017-06-29 | Electrolyte system for the synthesis of sodium perchlorate |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3478876A1 true EP3478876A1 (en) | 2019-05-08 |
Family
ID=57137056
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17740454.8A Withdrawn EP3478876A1 (en) | 2016-06-30 | 2017-06-29 | Electrolyte system for the synthesis of sodium perchlorate |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3478876A1 (en) |
JP (1) | JP2019524991A (en) |
FR (1) | FR3053362B1 (en) |
WO (1) | WO2018002543A1 (en) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1168149A (en) * | 1955-12-14 | 1958-12-04 | Pennsylvania Salt Mfg Co | Electrolytically obtained perchlorates |
AU3227093A (en) * | 1991-12-12 | 1993-07-19 | Olin Corporation | Process for producing lithium perchlorate |
JP5360196B2 (en) * | 2009-03-26 | 2013-12-04 | 株式会社Ihi | Method and apparatus for producing perchlorate |
-
2016
- 2016-06-30 FR FR1656234A patent/FR3053362B1/en not_active Expired - Fee Related
-
2017
- 2017-06-29 JP JP2018568909A patent/JP2019524991A/en active Pending
- 2017-06-29 EP EP17740454.8A patent/EP3478876A1/en not_active Withdrawn
- 2017-06-29 WO PCT/FR2017/051755 patent/WO2018002543A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
FR3053362A1 (en) | 2018-01-05 |
WO2018002543A1 (en) | 2018-01-04 |
JP2019524991A (en) | 2019-09-05 |
FR3053362B1 (en) | 2018-07-27 |
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