US2846383A - Process of manufacturing perchloric acid by anodic oxidation of chlorine - Google Patents
Process of manufacturing perchloric acid by anodic oxidation of chlorine Download PDFInfo
- Publication number
- US2846383A US2846383A US669547A US66954757A US2846383A US 2846383 A US2846383 A US 2846383A US 669547 A US669547 A US 669547A US 66954757 A US66954757 A US 66954757A US 2846383 A US2846383 A US 2846383A
- Authority
- US
- United States
- Prior art keywords
- perchloric acid
- chlorine
- manufacturing
- anode
- acid
- 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.)
- Expired - Lifetime
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims description 74
- 239000000460 chlorine Substances 0.000 title claims description 24
- 229910052801 chlorine Inorganic materials 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title description 20
- 238000000034 method Methods 0.000 title description 16
- 230000003647 oxidation Effects 0.000 title description 5
- 238000007254 oxidation reaction Methods 0.000 title description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 229910052697 platinum Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- -1 platinum metals Chemical class 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
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
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
Definitions
- U. S. Patent 1,271,633 describes a method of producing perchloric acid by electrolysis from strongly diluted hydrochloric acid to 1 N).
- the resulting perchloric acid is very dilute (about 30 grams per liter) (compare the table on page 2 of the American patent) and the current consumption required is very high.
- the consumption of current in the best case is 37.8 kwh.;v and the current used is direct current which corresponds to a consumption of 3 phase current (at 80% efiiciency of the rectifier) of 47.3 kwh. per kilogram of 100% perchloric acid.
- the reason for the high current consumption is the low conductivity of the dilute acid used which causes a comparatively high cell potential.
- that method is not suitable for the commercial production of perchloric acid and the perchlorate and has not been so used (see the Chemical Age of November 13, 1943).
- the cathode material is preferably graphite, silver, platinum, copper or alloys of these three metals.
- the most suitable anode material is platinum and also the platinum metals and the alloys thereof.
- the method is carried out by cooling an aqueous 10% to 60% solution, preferably 25% to 40% solution of perchloric acid, outside of the electrolyte cell to a low temperature, preferably to 0 C., and saturating the solution with chlorine.
- This solution is passed through the anode zone of the cell wherein part of the chlorine is oxidized and returned by means of a pump into the chlorine saturating zone where it is recooled in addition to being again saturated with chlorine.
- the described method produces an acid with a considerable content of perchloric acid which contains only 2-3 grams of chlorine per liter. After evaporatingthe excess of water this content of chlorine disappears and there remains a 60% perchloric acid of the highest purity.
- the method permits, at least in principle, the use of a cell without separation of the anode space and the cathodespace for the anodic oxidation of the chlorine.
- the electrochemical yield is higher when access of the cathodically produced hydrogen to the anode is prevented.
- the reason for this phenomenon is presumably that the evolved hydrogen reduces the solubility of the chlorine in the electrolyte.
- the cathode space or zone may be adequately separated by a diaphragm or a thin tautly stretched web of synthetic material, preferably of polyvinyl chloride which, influences the potential of the cell only to an insignificant extent.
- Example 1 A perchloric acid containing an appropriate quantity of HClO is fed by means of a pump from a supply container 2 to a cooler 3. The acid is cooled in the cooler to the desired temperature and then conducted through the saturator 4 in which it is saturated with chlorine. It is then fed into the anode space or compartment of cell 5 in which part of the dissolved chlorine is oxidized to perchloric acid at the platinum anode. The acid is recycled into the container 2 from the anode space. Part of the anolyte passes into the cathode space or compartment through the polyvinyl chloride fabric separator to an extent such that the impoverishment of the catholyte occurring due to the migration of the C10 ions to the anode is just balanced.
- the flow into the cathode space is controlled by regulating the run off. After withdrawing off from the cathode run-off, the quantity of perchloric acid which has been produced in the cell, the remainder flows back into the container 2 and thus goes back into the circulating system.
- the concentration of the perchloric acid was 40.5%.
- Example 2 The anodic oxidation of chlorine to perchloric acid was carried out, in accordance with the general procedure above described, by introducing a aqueous solution of perchloric acid containing dissolved elemental chlorine into the electrolytic cell. The oxidation was carried out at a current density of amperes/drn. The potential was 4.02 volts. The temperature of the solution of chlorine was 1 C.
- Method of manufacturing perchloric acid which comprises anodically oxidizing, at a temperature of about 0 C., elemental chlorine dissolved in an aqueous solution of perchloric acid wherein the perchloric acid is present in an approximate concentration of 10 percent to 60 percent.
- anode is a member of the group consisting of platinum, platinum metals, and alloys thereof
- the cathode is a member of the group consisting of graphite, silver, copper, platinum and alloys of said metals.
- Method of manufacturing perchloric acid which comprises anodically oxidizing, at a temperature of about 0 C., elemental chlorine dissolved in an aqueous solution of perchloric acid wherein the perchloric acid is present in an approximate concentration of 25 percent to 40 percent.
Description
g- 1958 w. MULLER 2,846,383
PROCESS OF MANUFACTURING PERCHLORIC ACID BY ANODIO oxnmron OF CHLORNE Filed July 2, 1957 CHLORINE H2O M PRODUCTION INVENTOR. WILHELM \MULLER BY HOMM ATTORNEYS United States Patent PROCESS OF MANUFACTURING PERCHLORIC ACID BY AN ODIC OXIDATION OF CHLORINE Wilhelm Miiller, Darmstadt, Germany, assignor to E. Merck Aktiengesellschaft Darmstadt, Darmstadt, Germany, a German corporation Application July 2, 1957, Serial No. 669,547
Claims priority, application Germany July 5, 1956 6 Claims. (Cl. 204-82) The method of producing perchloric acid as heretofore known is very involved and cumbersome in that; first, sodium chlorate is produced from common salt by electrolysis; and then the sodium chlorate, after isolation in concentrated solution is oxidized on platinum electrodes. By reacting the sodium perchlorate with concentrated hydrochloric acid, the perchlorate is converted into sodium chloride and free perchloric acid. The technical perchloric acid thus obtained contains, after separation of the sodium chloride, still small residues of sodium perchlorate in addition to other impurities contained in the starting material. The perchloric acid can be liberated from the residual sodium perchlorate only by distillation.
U. S. Patent 1,271,633 describes a method of producing perchloric acid by electrolysis from strongly diluted hydrochloric acid to 1 N). The resulting perchloric acid is very dilute (about 30 grams per liter) (compare the table on page 2 of the American patent) and the current consumption required is very high. According to the examples of the American patent the consumption of current in the best case is 37.8 kwh.;v and the current used is direct current which corresponds to a consumption of 3 phase current (at 80% efiiciency of the rectifier) of 47.3 kwh. per kilogram of 100% perchloric acid. The reason for the high current consumption is the low conductivity of the dilute acid used which causes a comparatively high cell potential. As a result, that method is not suitable for the commercial production of perchloric acid and the perchlorate and has not been so used (see the Chemical Age of November 13, 1943).
It has now been found that a highly economical method is achieved if one does not start with hydrochloric acid, but with elemental chlorine which is dissolved in a 10% to 60%, preferably 25 to 40%, aqueous solution of perchloric acid; and anodically oxidizes the elemental chlorine in such solution directly to perchloric acid.
The cathode material is preferably graphite, silver, platinum, copper or alloys of these three metals. 'The most suitable anode material is platinum and also the platinum metals and the alloys thereof.
The use of comparatively concentrated perchloric acid as an electrolyte permits the operation of an electrolytic cell with comparatively low potential whereby the resulting product is obtained in a high concentration.
In detail the method is carried out by cooling an aqueous 10% to 60% solution, preferably 25% to 40% solution of perchloric acid, outside of the electrolyte cell to a low temperature, preferably to 0 C., and saturating the solution with chlorine. This solution is passed through the anode zone of the cell wherein part of the chlorine is oxidized and returned by means of a pump into the chlorine saturating zone where it is recooled in addition to being again saturated with chlorine. The reaction:
requires water which is added to the circulating system continuously or discontinuously to maintain the concenice 2 tration of the circulating acid at the most favorable level. The produced acid is continuously withdrawn from the circulation system when leaving the cell. The most favorable current densities are between 20 and 30 amp./dm. and the most favorable potentials, 3.9 to 4.1 volts as appears from the following table:
, 7 Current Platinum Poten- Electro- Consumpinvesttial in chemical tion per ment per Current density, Volts Yield Kilogram 250 kiloamp./dm. H0104 grams of (Watts) H0104, 60% per day With this method there is practically no loss of anode metal as the evolved perchloric acid contains but traces of these metals. If, for instance platinum is used as anode metal, the platinum of the anode which is dissolved during the electrolysis deposits at the cathode and can be recovered therefrom.
The described method produces an acid with a considerable content of perchloric acid which contains only 2-3 grams of chlorine per liter. After evaporatingthe excess of water this content of chlorine disappears and there remains a 60% perchloric acid of the highest purity.
As the perchloric acid at the cathode does not undergo any change during theelectrolysis, the method permits, at least in principle, the use of a cell without separation of the anode space and the cathodespace for the anodic oxidation of the chlorine. However, it has been found that the electrochemical yield is higher when access of the cathodically produced hydrogen to the anode is prevented. The reason for this phenomenon is presumably that the evolved hydrogen reduces the solubility of the chlorine in the electrolyte. It has been found that the cathode space or zone may be adequately separated by a diaphragm or a thin tautly stretched web of synthetic material, preferably of polyvinyl chloride which, influences the potential of the cell only to an insignificant extent.
A more detailed description of the invention will become evident from the following examples when read in connection with the accompanying drawing:
Example 1 A perchloric acid containing an appropriate quantity of HClO is fed by means of a pump from a supply container 2 to a cooler 3. The acid is cooled in the cooler to the desired temperature and then conducted through the saturator 4 in which it is saturated with chlorine. It is then fed into the anode space or compartment of cell 5 in which part of the dissolved chlorine is oxidized to perchloric acid at the platinum anode. The acid is recycled into the container 2 from the anode space. Part of the anolyte passes into the cathode space or compartment through the polyvinyl chloride fabric separator to an extent such that the impoverishment of the catholyte occurring due to the migration of the C10 ions to the anode is just balanced. The flow into the cathode space is controlled by regulating the run off. After withdrawing off from the cathode run-off, the quantity of perchloric acid which has been produced in the cell, the remainder flows back into the container 2 and thus goes back into the circulating system.
The. water which is consumed during the electrolysis and water withdrawn due to the production of perchloric acid is also returned into the collecting container 2 and thence into the circulation system.
The completely pure acid which contains only minute quantities of dissolved chlorine (about 2 grams per liter) is concentrated to 60% whereby it is entirely stripped of free chlorine.
Numerical-example Cell potential-3.92 volt Strength of current1 250 ampere Density of current-20 amperes/dm.
Temperature of the solution as it enters the cell was I "emperature in the anode space 2 C.
The concentration of the perchloric acid was 40.5%.
Anode: platinum, Cathode: silver Period of time (operating)-24 hours Yieldl0.877 gr. HClO l%=l8.l28 gr. perchloric acid 60% Current efiiciency69.3
Example 2 The anodic oxidation of chlorine to perchloric acid was carried out, in accordance with the general procedure above described, by introducing a aqueous solution of perchloric acid containing dissolved elemental chlorine into the electrolytic cell. The oxidation was carried out at a current density of amperes/drn. The potential was 4.02 volts. The temperature of the solution of chlorine was 1 C.
Example 3 It will be understood that the foregoing description of the invention and the examples set forth are merely illustrative of the principles thereof. Accordingly the appended claims are to be construed as defining the invention within the full spirit and scope thereof.
, I claim:
1. Method of manufacturing perchloric acid which comprises anodically oxidizing, at a temperature of about 0 C., elemental chlorine dissolved in an aqueous solution of perchloric acid wherein the perchloric acid is present in an approximate concentration of 10 percent to 60 percent.
2. Method in accordance with claim 1 wherein the current density is about 20 to amp./dm.
3. Method in accordance with claim 1 wherein a diaphragm is interposed between the anode and the cathode.
4. Method in accordance with claim 1 wherein a synthetic fabric is interposed between the anode and the cathode.
5. Method in accordance with claim 1 wherein the anode is a member of the group consisting of platinum, platinum metals, and alloys thereof, and the cathode is a member of the group consisting of graphite, silver, copper, platinum and alloys of said metals.
6. Method of manufacturing perchloric acid which comprises anodically oxidizing, at a temperature of about 0 C., elemental chlorine dissolved in an aqueous solution of perchloric acid wherein the perchloric acid is present in an approximate concentration of 25 percent to 40 percent.
References Cited in the file of this patent UNITED STATES PATENTS 2,772,229 Karr Nov. 27, 1956
Claims (1)
1. METHOD OF MANUFACTURING PERCHLORIC ACID WHICH COMPRISES ANODICALLY OXIDIZING, AT A TEMPERATURE OF ABOUT 0*C., ELEMENTAL CHLORINE DISSOLVED IN AN AQUEOUS SOLUTION OF PERCHLORIC ACID WHEREIN THE PERCHLORIC ACID IS
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEM31017A DE1031288B (en) | 1956-07-05 | 1956-07-05 | Process for the production of perchloric acid by anodic oxidation of chlorine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2846383A true US2846383A (en) | 1958-08-05 |
Family
ID=7301123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US669547A Expired - Lifetime US2846383A (en) | 1956-07-05 | 1957-07-02 | Process of manufacturing perchloric acid by anodic oxidation of chlorine |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2846383A (en) |
| CH (1) | CH350639A (en) |
| DE (1) | DE1031288B (en) |
| FR (1) | FR1166086A (en) |
| GB (1) | GB818335A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409770A (en) * | 2013-08-01 | 2013-11-27 | 株洲市强盛电极有限公司 | Perchlorate electrolyzer and electrolytic process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2772229A (en) * | 1953-07-13 | 1956-11-27 | Pennsylvania Salt Mfg Co | Preparation of perchlorates |
-
1956
- 1956-07-05 DE DEM31017A patent/DE1031288B/en active Pending
-
1957
- 1957-02-06 FR FR1166086D patent/FR1166086A/en not_active Expired
- 1957-02-09 CH CH350639D patent/CH350639A/en unknown
- 1957-05-28 GB GB16958/57A patent/GB818335A/en not_active Expired
- 1957-07-02 US US669547A patent/US2846383A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2772229A (en) * | 1953-07-13 | 1956-11-27 | Pennsylvania Salt Mfg Co | Preparation of perchlorates |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409770A (en) * | 2013-08-01 | 2013-11-27 | 株洲市强盛电极有限公司 | Perchlorate electrolyzer and electrolytic process |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1166086A (en) | 1958-11-03 |
| CH350639A (en) | 1960-12-15 |
| DE1031288B (en) | 1958-06-04 |
| GB818335A (en) | 1959-08-12 |
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