US3497432A - Process for reducing the hydrogen content in chlorine gas produced by alkali-metal chloride electrolysis - Google Patents
Process for reducing the hydrogen content in chlorine gas produced by alkali-metal chloride electrolysis Download PDFInfo
- Publication number
- US3497432A US3497432A US673987A US3497432DA US3497432A US 3497432 A US3497432 A US 3497432A US 673987 A US673987 A US 673987A US 3497432D A US3497432D A US 3497432DA US 3497432 A US3497432 A US 3497432A
- Authority
- US
- United States
- Prior art keywords
- alkali
- mercury
- metal
- hydrogen
- metal chloride
- 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
Links
- 238000000034 method Methods 0.000 title description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 18
- 239000001257 hydrogen Substances 0.000 title description 16
- 229910052739 hydrogen Inorganic materials 0.000 title description 16
- 229910001514 alkali metal chloride Inorganic materials 0.000 title description 10
- 238000005868 electrolysis reaction Methods 0.000 title description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 description 40
- 239000002184 metal Substances 0.000 description 40
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 26
- 229910052753 mercury Inorganic materials 0.000 description 26
- 229940041669 mercury Drugs 0.000 description 26
- 150000002739 metals Chemical class 0.000 description 16
- 229910000497 Amalgam Inorganic materials 0.000 description 12
- 239000012267 brine Substances 0.000 description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 229910052738 indium Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 8
- 239000011133 lead Substances 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 239000011135 tin Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910000765 intermetallic Inorganic materials 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 150000001844 chromium Chemical class 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- -1 i.e. Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 244000138502 Chenopodium bonus henricus Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C25B1/36—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode cells
Definitions
- the invention lies in the finding that copper, zinc, tin, lead or indium are capable of forming an intermetallic compound with the so-called troublesome metals, i.e., chromium, germanium, tungsten, nickel, cobalt, etc., the intermetallic compound being soluble in mercury, unlike the troublesome metal, thereby preventing their concentration at the mercury cathode surface and thus reducing or eliminating the evolution of hydrogen.
- troublesome metals i.e., chromium, germanium, tungsten, nickel, cobalt, etc.
- This invention relates to a process for reducing the hydrogen content in chlorine gas produced by alkali metal chloride electrolysis.
- this invention relates to a process for reducing or eliminating evolution of hydrogen at the mercury cathode in the amalgam process of alkali metal chloride electrolysis.
- the salt brines that are used in the electrolysis procedure are first subjected to a preliminary purification, which consists of a precipitation treatment with alkali carbonate and barium carbonate.
- a preliminary purification which consists of a precipitation treatment with alkali carbonate and barium carbonate.
- the precipitation of the calcium ions is necessary because in their presence iron exhibits a troublesome effect.
- the fine barium sulfate that precipitates not only removes the sulfate ions which are generally considered responsible for the oxidative ablation of the anodes, but also most of the above-mentioned troublesome metals. However, small amounts of troublesome metals still remain in the brine and are the cause of the evolution of hydrogen at the mercury cathode.
- the metals which are suitable for use in accordance with the invention for forming the intermetallic compounds can also be added in the form of their soluble salts, e.g., as chlorides, to the alkali brine.
- the metals which can be used for formation of mercury-soluble intermetallic compounds include copper, zinc, tin, lead and indium.
- Me represents a troublesome metal that is reduced to the metal at the mercury cathode.
- Me represents a metal that is easily soluble in mercury. It is apparent that the speed of reactions 2 and 2a determines the amount of hydrogen evolution. That is to say, if the speed of the reactions 2 and 2a are greater than that of reaction 1, the troublesome metal is immediately dissolved in the mercury as a binary compound and exerts no effect on the evolution of hydrogen. If the speed of the reactions 2 and 2a is less than that of reaction 1, the troublesome metal, depending on how much of it is in the brine, can concentrate at the mercury surface and thus give rise to the formation of hydrogen.
- Example 1 was modified to the extent that copper amalgam was used instead of zinc amalgam. In this case, also, no hydrogen gas was developed when chromium salts were added to the brine in excess of the concentration mentioned in Example 1.
- EXAMPLE 3 No hydrogen gas was developed when chromium salts were added to the brine as set out in Examples 1 and 2 when an indium amalgam (indium content 0.01 molepercent) was used instead of zinc or copper amalgam.
- Process for the reduction or elimination of hydrogen development at the mercury cathode in the amalgam process of alkali-metal chloride electrolysis which takes place due to the presence in the alkali brine of at least one metal impurity which comprises incorporating at least one metal selected from the group consisting of copper, zinc, tin, lead and indium capable of forming an intermetallic mercury-soluble compound with said metal impurity into the mercury in an amount of 0.001 to 0.5 mole-percent.
- the step for reducing or eliminating hydrogen development at the mercury cathode due to the presence of at least one metal impurity in the alkali rbrine which comprises incorporating into the mercury at least one metal selected from the group consisting of copper, zinc, tin, lead and indium capable of forming an intermetallic mercury-soluble compound with the metal impurity in an amount of 0.001 to 0.5 mole-percent.
- a mercury cathode for use in the amalgam process of alkali metal chloride electrolysis having incorporated therein 0.001 to 0.5 mole-percent of a metal selected from the group consisting of copper, Zinc, tin, lead and indium capable of forming an intermetallic mercury-soluble compound with a metal selected from the group consisting of tungsten, nickel, cobalt, molybdenum, vanadium, arsenic, antimony, beryllium, magnesium, titanium, Zirconium, calcium, barium, aluminum, iron, chromium, and germanium.
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)
- Electrolytic Production Of Metals (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED0051266 | 1966-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3497432A true US3497432A (en) | 1970-02-24 |
Family
ID=7053272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US673987A Expired - Lifetime US3497432A (en) | 1966-10-10 | 1967-10-09 | Process for reducing the hydrogen content in chlorine gas produced by alkali-metal chloride electrolysis |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3497432A (de) |
| AT (1) | AT274857B (de) |
| BE (1) | BE704860A (de) |
| CH (1) | CH492640A (de) |
| DE (1) | DE1567931B2 (de) |
| GB (1) | GB1146805A (de) |
| NL (1) | NL6713704A (de) |
| NO (1) | NO117917B (de) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3091579A (en) * | 1960-03-02 | 1963-05-28 | Electrochemical Processes Inc | Electrochemical process and apparatus with purification of mercury |
| US3114686A (en) * | 1959-06-19 | 1963-12-17 | Ici Ltd | Process for the production of electrolytic products by the electrolysis of brine andapparatus therefor |
-
1966
- 1966-10-10 DE DE1567931A patent/DE1567931B2/de active Pending
-
1967
- 1967-10-03 CH CH1377567A patent/CH492640A/de not_active IP Right Cessation
- 1967-10-06 AT AT907067A patent/AT274857B/de active
- 1967-10-09 GB GB46033/67A patent/GB1146805A/en not_active Expired
- 1967-10-09 NL NL6713704A patent/NL6713704A/xx unknown
- 1967-10-09 US US673987A patent/US3497432A/en not_active Expired - Lifetime
- 1967-10-09 NO NO170046A patent/NO117917B/no unknown
- 1967-10-09 BE BE704860D patent/BE704860A/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3114686A (en) * | 1959-06-19 | 1963-12-17 | Ici Ltd | Process for the production of electrolytic products by the electrolysis of brine andapparatus therefor |
| US3091579A (en) * | 1960-03-02 | 1963-05-28 | Electrochemical Processes Inc | Electrochemical process and apparatus with purification of mercury |
Also Published As
| Publication number | Publication date |
|---|---|
| AT274857B (de) | 1969-10-10 |
| BE704860A (de) | 1968-02-15 |
| NO117917B (de) | 1969-10-13 |
| GB1146805A (en) | 1969-03-26 |
| CH492640A (de) | 1970-06-30 |
| DE1567931B2 (de) | 1974-06-12 |
| NL6713704A (de) | 1968-04-11 |
| DE1567931A1 (de) | 1970-10-01 |
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