US3234114A - Process for the recovery of purified sodium - Google Patents
Process for the recovery of purified sodium Download PDFInfo
- Publication number
- US3234114A US3234114A US208664A US20866462A US3234114A US 3234114 A US3234114 A US 3234114A US 208664 A US208664 A US 208664A US 20866462 A US20866462 A US 20866462A US 3234114 A US3234114 A US 3234114A
- Authority
- US
- United States
- Prior art keywords
- sodium
- electrolyte
- aluminum
- mixture
- cathode
- 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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- 239000011734 sodium Substances 0.000 title claims description 68
- 229910052708 sodium Inorganic materials 0.000 title claims description 63
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 29
- 238000011084 recovery Methods 0.000 title claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 37
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 claims description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001023 sodium amalgam Inorganic materials 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- -1 alkyl radical Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ZXRRHFSTAFVGOC-UHFFFAOYSA-N [AlH3].[K] Chemical compound [AlH3].[K] ZXRRHFSTAFVGOC-UHFFFAOYSA-N 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-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
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
Definitions
- This invention relates to a process for the recovery of purified sodium.
- German Patent No. 1,114,330 discloses a process in which metallic sodium is produced electrolytically with the use of electrolytes of the general formula MeAlR R'.
- Me is sodium or a mixture of sodium and potassium
- R is an alkyl radical
- R is hydrogen
- Readily available and particularly recommended electrolytes for this process are sodium-aluminum tetraethyl alone or in mixture with potassium-aluminum tetraethyl, preferably further modified by addition of a small amount of a sodium or potassium-alkoxy aluminum triethyl.
- anodes which contain sodium metal and cathodes, which are inert to the sodium metal deposited at the cathode. Due to the electrolysis process, sodium metal is dissolved out of the anode material, migrates through the electrolyte and is precipitated as purified metal at the cathode and may be withdrawn at the cathode.
- the temperatures used in this process are preferably elevated sufficiently that the sodium metal is present in liquid form at the cathode and may be withdrawn from the cell in this form.
- the substantial-1y most important application of this electrolytic recovery of sodium is the separation of sodium metal from sodium amalgam which is used as the anode material or for the electrolytic refining of raw sodium to form a particularly pure product.
- the patent mentioned above gives several teachings for the practical performance of such an electrolysis. It is particularly important in practice that the sodium is precipitated in molten form and as a continuous layer at the cathode which consists of a suit-able other metal, e.g. copper. A favorable course of sodium precipitation is established in most cases by electrolyzing for some time on a bright copper plate serving as the cathode. The individual droplets initially precipitated run together to form a continuous sodium film in which the sodium flows down at the cathodes which are preferably vertical or at least inclined.
- a special trick taught by the patent men- 'tioned above is to provide a fabric of insulating mate-rial, e.g.
- electrolytic cells of this type have to meet high requirements with respect to the useful service life.
- the profitableness of the process largely depends on :how often trouble, e.g. by inner short circuits, must be expected.
- the cells must be disassembled completely, the electrolyte and the cathodes must be pun'fied, and it may even be necessary to fill in a fresh electrolyte. Only then the cell will again operate satisfactorily.
- the electrolyte is very sensitive to air, it is obvious that such restoration involves rather disagreeable and costly operations.
- the individual filament of the net of a net cathode is a thread spun from many fibrillae having corresponding capillary interstices which become completely saturated or soaked with electrolyte.
- the portions of electrolyte which are bound in these interstices and subjected to the direct electrolytic decomposition mix only diificultl y with further portions of the electrolyte bath. Thus, it appears that this may involve a serious cause of undesirable troubles.
- the invention consists in the finding that cells for the electrolytic recovery of sodium from an anode material which contains sodium metal, e.g. from sodium amalgam or raw sodium, can be operated for many months without any trouble when using a mixture of sodium-aluminum tetraethyl and sodium-aluminum tetramethyl as the electrolyte.
- the mole ratio of the components of this mixture is preferably about 1:1 but may deviate to both sides by a certain amount.
- the limits are at 30 to mole percent NaAl(CH ).A and 70 to 25 mole percent of NaAl C2H5) 4.
- the conductivity of an exactly equimolar mixture of the two complex compounds at 130 C. is 10 10 ohms cmf i.e. the conductivity is very good.
- the mixture of sodium-aluminum tetramethyl and sodium-aluminum tetraethyl melts at very low temperatures with the unusually low eutectic of 83 C. leading to completely liquid electrolyte mixtures already at temperatures in the neighborhood of C.
- the figure is a plot of melting points for mixtures of NaAlEL and NaAl(CH
- the. electrolytes are preferably mixed with a small amount of the corresponding sodiumalkoxy aluminum trialkyl'compound. A few percent are sufficient so that the conductivity is reduced to an unimportant extent only. This measure reliably protects the cathodically deposited sodium from co-deposition of aluminum.
- the alkoxy triethyl ortrirnethyl compound may be added most conveniently. by adding a corresponding amount of any alcoholto the. mixture .of the two tetraalkyl complexes.
- the temperatures to be maintained during el ctrolysis must range above the melting point of sodium. Most preferred are temperatures: between about 100 and 120 C., but temperatures up to about 160 C. may be used.
- i.e. sodium-aluminum tetramethyl may, for example, be
- mixture according to the invention comprising sodiumaluminum te'traethyl and sodium-aluminum;tetrarnethyl in a mole ratio of.4: 3..
- the reaction mixture isprocessed in a manner analogous'to that described in Example 5.;
- the contents of the autoclave, while still liquid, i.e. at a temperature above 90 C., are siphoned into a dry 2 liter flask filled with an inert gas.
- the reaction product is a liquid system comprising two phases.
- the upper layer is paraflin oil which is substantially free from organometallic compounds and siphoned oil from the lower phase.
- the lower layer is a mixture of NaAl(CH and NaAl (C H in a mole ratio of 1:1 which solidifies at 80 C. with formation of crystals. The yield of this mixture is 650 gms. (95% of the theoretical).
- EXAMPLE 8 Into a 10 liter vessel with stirrer, there are placed a suspension of 1 kg. aluminum grit and a mixture of AlEt Cl and AlMe Cl in a molar ratio of 1:1 in amount sufficient that the mixture is still well stirrable. The reaction vessel is heated to 1051l5 C. and an equimolar mixture of ethyl chloride and methyl chloride in liquid form (from an inverted stock bottle) is introduced through a capillary extending down to the bottom of the vessel. It is also possible to introduce ethyl chloride and methyl chloride in equal amounts separately through two capillaries. The addition of the alkyl halides is effected at a rate suflicient that the temperature is maintained between 105 C. and 115 C.
- Alkyl chloride in amount of between 350 and 7 grams is taken up within one hour. 3 kgs. of the mixture of alkyl halides and all of the aluminum charged are reacted within about 6 hours.
- the conversion of the resultant mixture of methyl and ethyl aluminum sesquichlorides into Al(CH Cl and Al(C H Cl or Al(CH (C H )Ol is effected as follows: 425 gms. of sodium are molten in a second liter reaction vessel.
- the reaction mixture of the alkyl aluminum sesquichloridex is allowed to drop onto the sodium at about 110 C. While stirring. After all of the mixture has been added, stirring is continued for about 30 minutes. Following this, the resultant is distilled oil from the sodium chloride and aluminum at a bath temperature which must be increased to 200 C. towards the end of the distillation.
- the complex mixture NaA-l(CI-l NaAl(C H is prepared in a manner analogous to that of Example 1 by allowing the reaction mixture having the composition Al(CH )(C H )Cl and obtained in Example 8 to drop onto the corresponding amount of molten sodium. There is obtained the 1:1 molar mixture NaAl (CI-1 NaAl(C H in a good yield.
- the electrolytic cell used consists of a cylindrical and internally enamelled steel kettle which contains at the bottom raw sodium to be refined as a melt. Suspended in the kettle is a cylinder of enamelled sheet steel of somewhat smaller diameter, which is open at both ends and has horizontally tightened across the lower opening a wide-meshed glass fiber fabric having a mesh size of 1 to 3 mm. The net is arranged at a distance of 3 to 5 mm. above the surface of the liquid sodium. Arranged closely above the net is a net of copper or iron wire as the cathode.
- the electrolysis temperature is 150 C.
- a mixture of sodium-aluminum tetraethyl and tetramethyl in a 1:2 molar ratio is used as the electrolyte.
- the level of the molten electrolyte must be above the upper edge of the suspended cylinder, so that the sodium deposited at the cathode is surrounded by the electrolyte from above and below.
- An electrode current density of 20 a./dm. can be maintained at a terminal voltage of 1.1 v.
- the cathodically formed sodium collects above the glass fiber net and may be drained from this space from time to time. Care is taken by the addition of raw sodium during the electrolysis that the distance between the anode and cathode is kept constant.
- test runs were operated for more than six months.
- test runs effected with electrolytes containing only ethyl groups had to be discontinued after 3 to 4 weeks due to troubles in the sodium deposition.
- the same difierence is suitability of the electrolyte systems was also found in test runs which were elfected for an extended period of time with the use of sodium amalgam as the anode (see Example 10 below).
- the yield of sodium is 23 grams per 26.8 ampereshours, and 23 grams of Na were dissolved anodic-ally by the same amount of current.
- the yield is EXAMPLE 10
- the procedure is the same as that described in Example 9, except that the same volume of 1% sodium is substituted for the molten raw sodium.
- Electrolysis is effected at C. with a current density of 30 -a./dm. at a terminal voltage of 1.7 v.
- the sodium deposited at the cathode collects as a continuous liquid layer above the net of glass fiber fabric.
- a greater electrolyte stock is recirculated through the electrolytic cell while maintaining the liquid in the electrolytic cell at a constant level.
- EXAMPLE 11 The procedure is the same as that described in Example 10 except that an electrolyte mixture of NaAl(C H and NaAl(CH in a 1:1 molar ratio is used. A terminal voltage of about 1.5 to 1.7 v. is required at a current density of 20 a./dm.
- a process for the recovery of purified sodium which comprises passing an electrolysis current between a cathode and an anode through an electrolyte containing a mixture of sodium aluminum tetramethyl and sodium aluminum tetraethyl, said anode being a sodium metal containing electrode and said cathode being inert to the cathodically deposited sodium, to electrolyze sodium from the anode and deposit sodium at the cathode, the sodium electrolyzed at the anode replacing in the electrolyte sodium deposited at the cathode, and recovering the purified sodium so formed.
- said electrolyte comprises from 30 to 75 mole percent of NaAl(CH and from 70 to 25 mole percent of NaAl(C H 3.
- said electrolyte comprises about equivalent amount of NaAl(CH and NaAl(C H 4.
- said electrolyte additionally contains small amounts of a corresponding alkoxy complex compound.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEZ8838A DE1146258B (de) | 1961-06-30 | 1961-06-30 | Metallorganischer Elektrolyt hoher Leitfaehigkeit zur kathodischen Abscheidung von Natrium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3234114A true US3234114A (en) | 1966-02-08 |
Family
ID=7620645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US208664A Expired - Lifetime US3234114A (en) | 1961-06-30 | 1962-06-27 | Process for the recovery of purified sodium |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3234114A (de) |
| DE (1) | DE1146258B (de) |
| GB (1) | GB961373A (de) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775270A (en) * | 1970-01-14 | 1973-11-27 | K Ziegler | Process for the electrolytic refining of potassium |
| WO2002088434A1 (en) * | 2001-04-30 | 2002-11-07 | Alumiplate Incorporated | Aluminium electroplating formulations |
| EP1371653A1 (de) * | 2002-06-13 | 2003-12-17 | Crompton GmbH | Verfahren zur Herstellung von Alkalitetraalkylaluminaten und deren Verwendung |
| US20040140220A1 (en) * | 2002-04-30 | 2004-07-22 | Fischer Juergen K S | Aluminium electroplating formulations |
| EP1518946A1 (de) * | 2003-09-27 | 2005-03-30 | Aluminal Oberflächtentechnik GmbH & Co. KG | Electrolyt zur galvanischen Abscheidung von Aluminium |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2849349A (en) * | 1955-06-13 | 1958-08-26 | Ziegler | Process for the electrolytic deposition of aluminium |
| US2952589A (en) * | 1956-04-09 | 1960-09-13 | Karl Ziegler | Purification of aluminum |
| GB864393A (en) * | 1958-02-13 | 1961-04-06 | Ziegler Karl | Process for the production of lead tetraalkyls |
| US2985568A (en) * | 1954-11-26 | 1961-05-23 | Ziegler | Electrolytic process for the production of metal alkyls |
| US3028323A (en) * | 1959-12-24 | 1962-04-03 | Ethyl Corp | Manufacture of organolead products |
-
1961
- 1961-06-30 DE DEZ8838A patent/DE1146258B/de active Pending
-
1962
- 1962-06-22 GB GB24117/62A patent/GB961373A/en not_active Expired
- 1962-06-27 US US208664A patent/US3234114A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2985568A (en) * | 1954-11-26 | 1961-05-23 | Ziegler | Electrolytic process for the production of metal alkyls |
| US2849349A (en) * | 1955-06-13 | 1958-08-26 | Ziegler | Process for the electrolytic deposition of aluminium |
| US2952589A (en) * | 1956-04-09 | 1960-09-13 | Karl Ziegler | Purification of aluminum |
| GB864393A (en) * | 1958-02-13 | 1961-04-06 | Ziegler Karl | Process for the production of lead tetraalkyls |
| US3028323A (en) * | 1959-12-24 | 1962-04-03 | Ethyl Corp | Manufacture of organolead products |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775270A (en) * | 1970-01-14 | 1973-11-27 | K Ziegler | Process for the electrolytic refining of potassium |
| WO2002088434A1 (en) * | 2001-04-30 | 2002-11-07 | Alumiplate Incorporated | Aluminium electroplating formulations |
| US20040140220A1 (en) * | 2002-04-30 | 2004-07-22 | Fischer Juergen K S | Aluminium electroplating formulations |
| US7250102B2 (en) | 2002-04-30 | 2007-07-31 | Alumiplate Incorporated | Aluminium electroplating formulations |
| EP1371653A1 (de) * | 2002-06-13 | 2003-12-17 | Crompton GmbH | Verfahren zur Herstellung von Alkalitetraalkylaluminaten und deren Verwendung |
| EP1518946A1 (de) * | 2003-09-27 | 2005-03-30 | Aluminal Oberflächtentechnik GmbH & Co. KG | Electrolyt zur galvanischen Abscheidung von Aluminium |
| WO2005059207A1 (de) * | 2003-09-27 | 2005-06-30 | Aluminal Oberflächentechnik Gmbh & Co. Kg | Elektrolyt zur galvanischen abscheidung von aluminium |
Also Published As
| Publication number | Publication date |
|---|---|
| GB961373A (en) | 1964-06-17 |
| DE1146258B (de) | 1963-03-28 |
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