EP0011886A1 - Préparation des acides oxyhalogénés et de leurs sels par électrolyse - Google Patents
Préparation des acides oxyhalogénés et de leurs sels par électrolyse Download PDFInfo
- Publication number
- EP0011886A1 EP0011886A1 EP79200618A EP79200618A EP0011886A1 EP 0011886 A1 EP0011886 A1 EP 0011886A1 EP 79200618 A EP79200618 A EP 79200618A EP 79200618 A EP79200618 A EP 79200618A EP 0011886 A1 EP0011886 A1 EP 0011886A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- unpurified
- calcium
- sea water
- electrolysis
- ions
- 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.)
- Granted
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 18
- 150000003839 salts Chemical class 0.000 title claims abstract description 5
- 239000002253 acid Substances 0.000 title description 2
- 150000007513 acids Chemical class 0.000 title 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000013535 sea water Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical class [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920002472 Starch Polymers 0.000 abstract 1
- 239000008107 starch Substances 0.000 abstract 1
- 235000019698 starch Nutrition 0.000 abstract 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- -1 iron ions Chemical class 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- the invention has for its object to achieve a reduction or control of the formation of deposits on the cathode during the electrolysis of seawater or salt solutions containing contaminating metal ions for the recovery of solutions of chlorine-oxygen acids or their salts, advantages of known methods being used without their disadvantages to have to put up with.
- the invention now consists in operating the electrolysis cell with unpurified sea water or unpurified salt solution until a layer is formed on the electrodes
- Compounds of the contaminating metal ions, in particular calcium and / or magnesium ions are deposited in a sufficient strength and effect a current efficiency of more than 90%, and that then the calcium and / or magnesium ions contained in the unpurified sea water or in the unpurified saline solution by adding sodium hydroxide solution and / or calcium hydroxide and sodium carbonate at a pH of more than 9 precipitates in whole or in part, if necessary separates and feeds the cleaned solution to the electrolysis cell.
- Adequate layer thickness is understood in the sense of the invention to mean a layer thickness which is sufficient to achieve a current efficiency of more than 90%.
- this is fed to the electrolyzer in carrying out the method according to the invention until a sufficient layer thickness is reached.
- the current yield slowly increases over time until values of over 90% are reached. This increase generally takes place over a period of 5 to 30 hours, the cell voltage generally increasing by 0.2 to 0.3 volt with the same current density. After this deposition phase, the cell voltage continues to increase and this increase is 1 to 1.5 volts within 100 to 2000 hours, depending on the concentration of contaminating ions.
- the supply of the unpurified salt solution is switched off by the method according to the invention and the purified salt solution is then fed to the electrolyte.
- the impurities which are predominantly contained in the salt solution in the form of calcium and / or magnesium ions or iron ions, are precipitated by adding sodium hydroxide solution and / or calcium hydroxide and sodium carbonate or soda at a pH of more than 9.
- the magnesium ions are precipitated by the hydroxyl ions of the calcium hydroxide, the calcium ions by the carbonate ions and magnesium hydroxide. Calcium carbonate precipitated.
- the precipitation of the impurities is usually brought about completely. In some cases, depending on the local conditions of the electrolytic cells, it may be sufficient if the majority of the contaminants are precipitated.
- the precipitation products can also remain wholly or partly in the finely divided state in the brine or saline solution.
- impurities of, for example, calcium and magnesium salts in amounts of about 5 mg Ca ++ / 1 and 1 mg Mg ++ / 1 are deposited on the cathodes in the brine and gradually cause a layer to form.
- electrolytic cells are used in the method according to the invention, for example electrolytic cells with alternating vertical anodes and cathodes.
- the electrode spacing is, for example, 2 to 5 mm and the electrolyte with a flow rate of 0.3 to 2 m / s is electrolyzed at a current density of 2 to 25 A / dm 2 .
- the temperature of the electrolyte can be 10 to 50 ° C and the pH can range from 7 to 10.
- the cathodes are made of electrically conductive, wear-resistant metal materials, such as titanium, nickel, or iron and nickel alloys.
- the anode material can be graphite.
- anodes are titanium, niobium or tantalum electrodes coated with noble metal or noble metal oxide or so-called dimensionally stable anodes, in which the electrocatalytic effect is based on mixed oxides of noble metals and film-forming metals, in particular titanium.
- the chlorine reacts with the sodium hydroxide solution to form sodium hypochlorite according to:
- hypochlorous acid Sodium hypochlorite reacts with water to form hypochlorous acid
- reaction (1) or reaction (2) depends on the pH of the environment. At a pH> 5, the entire active chlorine is in the form of hypochlorous acid and hypochlorite ions. The higher the pH value, the greater the proportion of hypochlorite ions.
- the advantages of the method according to the invention can be seen in the fact that a targeted layer formation on the cathodes occurs uniformly in all electrolysis cells of the system.
- the thin passive layer of a certain thickness deposited according to the invention prevents an excessive reduction of the hypochlorite ions, thus increases the yield of hypochlorite and makes cell cleaning unnecessary or reduces it to a very considerable extent.
- FIG. 1 shows the efficiency of hypochlorite cells as a function of the running time.
- a plant with 8 cells connected in series was operated with sea water at 28 ° C. at a rate of 20 m 3 / h.
- the current strength was slowly increased from 500 A to 5000 A over a total of 30 hours.
- the voltage rose from 25 to 35 V.
- the content of active chlorine in the form of NaOCl rose from 0.2 g / l to 2.8 g / l in the same period.
- the current yield ran according to the diagram in FIG. 1, ie without the addition of precipitation chemicals, the current yield would asymptotically approach the value of 100%, but at the same time the voltage would rise and the Pollution increase, so that after 2000 hours at the latest the plant would have to be shut down with acid washing.
Landscapes
- 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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782850575 DE2850575A1 (de) | 1978-11-22 | 1978-11-22 | Verfahren zur elektrolytischen gewinnung von chlorsauerstoffsaeuren bzw. deren salze |
| DE2850575 | 1978-11-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0011886A1 true EP0011886A1 (fr) | 1980-06-11 |
| EP0011886B1 EP0011886B1 (fr) | 1981-11-11 |
Family
ID=6055302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79200618A Expired EP0011886B1 (fr) | 1978-11-22 | 1979-10-25 | Préparation des acides oxyhalogénés et de leurs sels par électrolyse |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4238302A (fr) |
| EP (1) | EP0011886B1 (fr) |
| JP (1) | JPS5573882A (fr) |
| BR (1) | BR7907561A (fr) |
| DE (2) | DE2850575A1 (fr) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064514A (en) * | 1990-03-30 | 1991-11-12 | Olin Corporation | Apparatus for the production of chloric acid |
| US5616234A (en) * | 1995-10-31 | 1997-04-01 | Pepcon Systems, Inc. | Method for producing chlorine or hypochlorite product |
| US7611280B2 (en) * | 2003-12-16 | 2009-11-03 | Harco Laboratories, Inc. | EMF sensor with protective sheath |
| US20130248375A1 (en) * | 2012-03-02 | 2013-09-26 | Miox Corporation | Waste to Product On Site Generator |
| CN111039474A (zh) * | 2019-12-26 | 2020-04-21 | 西安泰金工业电化学技术有限公司 | 一种电厂循环水处理系统及方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1406874A (fr) * | 1963-11-05 | 1965-07-23 | Casson And Crane | Perfectionnements à la préparation de peroxyde de chlore |
| US4088550A (en) * | 1977-05-25 | 1978-05-09 | Diamond Shamrock Corporation | Periodic removal of cathodic deposits by intermittent reversal of the polarity of the cathodes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3799849A (en) * | 1972-06-26 | 1974-03-26 | Hooker Chemical Corp | Reactivation of cathodes in chlorate cells |
| FR2244708B1 (fr) * | 1973-09-25 | 1977-08-12 | Ugine Kuhlmann | |
| US3974051A (en) * | 1975-05-07 | 1976-08-10 | Diamond Shamrock Corporation | Production of hypochlorite from impure saline solutions |
| US4085014A (en) * | 1977-04-21 | 1978-04-18 | Diamond Shamrock Corporation | Elimination of impurities from sea water cell feed to prevent anode deposits |
-
1978
- 1978-11-22 DE DE19782850575 patent/DE2850575A1/de not_active Withdrawn
-
1979
- 1979-10-25 DE DE7979200618T patent/DE2961328D1/de not_active Expired
- 1979-10-25 EP EP79200618A patent/EP0011886B1/fr not_active Expired
- 1979-11-05 US US06/091,312 patent/US4238302A/en not_active Expired - Lifetime
- 1979-11-21 BR BR7907561A patent/BR7907561A/pt unknown
- 1979-11-22 JP JP15191779A patent/JPS5573882A/ja active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1406874A (fr) * | 1963-11-05 | 1965-07-23 | Casson And Crane | Perfectionnements à la préparation de peroxyde de chlore |
| US4088550A (en) * | 1977-05-25 | 1978-05-09 | Diamond Shamrock Corporation | Periodic removal of cathodic deposits by intermittent reversal of the polarity of the cathodes |
Also Published As
| Publication number | Publication date |
|---|---|
| BR7907561A (pt) | 1980-07-08 |
| DE2961328D1 (en) | 1982-01-14 |
| DE2850575A1 (de) | 1980-06-04 |
| JPS5573882A (en) | 1980-06-03 |
| EP0011886B1 (fr) | 1981-11-11 |
| US4238302A (en) | 1980-12-09 |
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