EP0105896A1 - Apparatus for continuous production of zinc electroplated sheet. - Google Patents
Apparatus for continuous production of zinc electroplated sheet.Info
- Publication number
- EP0105896A1 EP0105896A1 EP83901324A EP83901324A EP0105896A1 EP 0105896 A1 EP0105896 A1 EP 0105896A1 EP 83901324 A EP83901324 A EP 83901324A EP 83901324 A EP83901324 A EP 83901324A EP 0105896 A1 EP0105896 A1 EP 0105896A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- mercury
- electrolysis cell
- waste
- electrically connected
- 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
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
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
Definitions
- the present invention relates to an industrial technique for the recovery of zinc and possibly other components or constituents of industrial zinciferous waste, for example steel.
- zinciferous waste is meant here any industrial residual product or solutio obtained from industrial residues.
- the invention provides an attractive industrial solution which fills this gap by means of a process characterized in that the zinciferous waste is immersed in a first solution, preferably alkaline, in the presence of a sheet of mercury and an electrically connected electrode. at a positive electrical potential then, by electrolysis, zinc is deposited cathodically from the zinciferous waste to form a zinc amalgam. The zinc amalgam is then separated from the first solution and the zinc amalgam is brought into contact with a second acidic, neutral or complexing solution in the presence of a cathode electrically connected to a negative electrical potential. By electrolysis, the zinc of the amalgam is then redissolved anodically to produce a deposit of pure zinc on the cathode.
- a first solution preferably alkaline
- an electrically connected electrode at a positive electrical potential then, by electrolysis, zinc is deposited cathodically from the zinciferous waste to form a zinc amalgam.
- the zinc amalgam is then separated from the first solution and the zinc amalgam is brought into contact with a second
- the bottom of the tank etan covered with a layer of mercury in forced circulation, extending in the bottom of the two 'compartment through the aforementioned opening 1 , the first compartment containing a first electrolyte in which is immersed an electrode electrically connected to a positive electrical potential, the second compartment containing a second electrolyte in which is immersed one. cathode connected to a negative electrical potential, the sheet of mercury constituting both a mechanical barrier to avoid mixing of the two electrolytes and a selective electrochemical barrier vis-à-vis the ions to be separated.
- the electrolyte contained in the anode compartment is, without this factor being limiting, preferably an alkaline solution, for example a solution of NaOH, and the electrolyte contained in the cathode compartment is an acidic, neutral or complexing solution, for example a zinc sulfa solution or an electroplating bath.
- the electrodes can be connected electrically. ment to the poles of the same source of electrical voltage or to separate sources of electrical voltage.
- the technique according to the invention allows easy recovery of zinc and steel from galvanized sheet waste with in particular the following advantages: a.
- the dissolution and electrolysis reactions are carried out with a very high yield at ordinary temperature and with low energy consumption.
- the equipment required is very simple.
- the consumption of reagents is very low since we simply have to compensate for the losses due to the presence of possible impurities (for example solubillation of traces of aluminum).
- Zinc is obtained in compact mono-crystalline form stable, easily fusible and valuable. It can also be recovered in one of the variants of the procedure in the form of a coating of steel sheets (electrolytic zinc coating). 5 e. Steel free of zinc can be recycled into steel without problems, f. Absence of any problem of discharge of polluting waste gases or dust.
- the technique according to the invention also allows the production of pure zinc recoverable by recovery of various industrial zinciferous waste: residual dust from electrical steelworks (which contain appreciable zinc contents of up to 20% and more), 5 residual dust blast furnaces, galvation attes and even zinc ores leached with soda. This technique thus gives significant added value to all this residual waste.
- An additional advantage of the electrolysis cell according to the invention is that it allows both electrolytic recovery and electro-refining of zinc to be carried out in a single operation.
- this cell makes it possible to produce galvanizing chains capable of working with low-cost starting materials, which provides substantial savings in raw materials.
- Figure 1 is a cross-sectional view of an example cell according to the invention.
- Figure 2 is a top view of the cell of Figure 1.
- the technique according to the invention is based on the technolo called metallurgy of amalgams which consists in using a mercury electrode to extract a metal from an alloy or a compound.
- This technique is implemented in an electrolysis cell as shown for example in the drawings.
- the cell 10 comprises two compartments, 2 separated by a partition 3 and communi ⁇ as between them by an opening 4 formed in the lower part of the partition 3.
- a sheet of mercury 5 which extends in the two compartments 1 and 2 through the opening 4 and which is maintained in forced circulation by a pump 11.
- the first compartment " 1 contains an electrolyte 6 in which is immersed an electrode 7 electrically connected to a source of potential positive electric + V.
- the electrode 7 consists of a conveyor chain circulating in the electrolytic bath at a certain distance above the sheet of mercury and is intended to carry the hazardous waste to be treated.
- the electrolyte 6 is preferably but without this factor being limiting, an alkaline solution, for example a NaOH solution.
- the anode electrode 7 could also be a rotating basket for example, which would immerse the waste to be treated in the electrolyte 6. In other embodiments, the anode electrode could be provided so as not to carry the zinciferous waste to be treated.
- the zinciferous waste to be treated is immersed in the trolyte ele 6 of the anode compartment 1.
- the waste is either directly metallic waste (galvanized sheets, galvanizing rods) or -a zinciferous solution obtained by chemical treatment of dust. aci ries, blast furnace sludge or zinc ores by "example. ,
- the mercury pool 5 operates as the cathode.
- zinc is deposited cathodically and amalgamates with mercury.
- the nature of the anodic reaction in compartment 1 can be judiciously selected by the arrangement of this compartment 5 depending on the nature of the waste to be treated.
- an anodic steel electrode is chosen, immersed in a NaOH solution. Electrochemical dissolution of the zinc then takes place in the trolyte ele.
- the anodic reaction causes oxygen to be released.
- Table 25 Table the zinc of industrial residues such as steelworks dust, blast furnace sludge, galvanizing mattes, galvanized sheet waste for example.
- electrolysis in an alkaline medium makes it possible to eliminate the problems associated with the evolution of hydrogen which does not manifest itself with the same acuity as in an acid medium due to the high pH.
- the zinc amalgam formed in compartment 1 passes into cathode compartment 2 with the mercurial blanket 5 5 in circulation.
- the compartment 2 contains a proper electrolytic consisting of a solution of acid, neutral
- ⁇ MP complexing according to the applications.
- a cathode 9 electrically connected to a negative electric pot -V.
- the electrolyte 8 is for example a solution of zinc sulfate in which an aluminum cathode is immersed.
- the zinc of the amalgam ée redis anodically sustained in the electrolyte 8 and the dissolved zinc is deposited on the cathode 9 in a pure, stable and non-oxidizable mono-crystalline form, which has an interesting value.
- the cathode compartment may also 'be an electrolytic galvanizing compartment.
- an electroplating bath is chosen for the electrolyte (alkaline cyanide bath or acid bath for example) and the support of the steel to be galvanized is used as the cathode. zinc is then deposited directly on the steel in the form of a galvanizing coating.
- the electrolytic cell according to the invention thus makes it possible to constitute a particularly economical direct galvanizing station thanks to the use of zinc recovered from zinciferous waste. Note that the electrolysis cell eliminates the presence of sludge in the cathode compartment.
- a remarkable feature of the lectrolys cell according to the invention is that the sheet of mercury 5 plays the role of a bipolar electrode which is permeable to amalgamable elements such as zinc, lead, bismuth, tin for example contained in the compartment anode 1 and which is impermeable to ions and. solvent.
- the mercury sheet thus constitutes both a mechanical barrier preventing the mixing of the two electrolytic solutions 6 and 8 and a selective electrochemical barrier with respect to the ions to be separated.
- the electrolytic solution 8 of the cathode compartment does not become contaminated with impurities and elements more electropositive than zinc which lower the hydrogenated overvoltage.
- Another remarkable feature of the electrolysis cell according to the invention is its possibility of also and elegantly carrying out an electrorefining of the zi or of any other element exhibiting analogous properties.
- Any impurities in the electrolytic bath dissolve in the mercury at the same time as the zinc, since they are more electropositive than the latter and can be amalgamated with the mercury.
- the impurities precipitate in the form of sludge or remain in solution without interfering: this is the case with aluminum for example.
- the selective properties of the bipolar mercury electrode therefore explain that the electrolysis cell according to the invention allows the electro-refining of zinc.
- the mercury charged with amalgamated impurities can be regenerated continuously, for example by electrolysis in an auxiliary cell, in order to extract the amalgamated elements therefrom before being recycled.
- the electrodes can be connected to the positive and negative poles of the same electric voltage source.
- the two compartments can however also be connected to different sources of electrical potential, which makes it possible to separately regulate the operation of the two reactions in the anode and cathode compartments, the electrochemical yields of the two reactions not generally being equal.
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)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Dans une cuve d'électrolyse (10) comportant deux compartiments (1, 2) qui contiennent chacun un électrolyte distinct (6, 8) et dont le fond est couvert d'une nappe de mercure (5) jouant le rôle d'une électrode bipolaire, le zinc des déchets zincifères plongés dans l'électrolyte du premier compartiment (1) se dépose cathodiquement sur le mercure (5) pour former un amalgame de zinc. Le zinc de cet amalgame se redissout ensuite anodiquement dans le second compartiement (2) en produisant un dépôt cathodique de zinc pur. L'électrode bipolaire de mercure sert à la fois de barrière mécanique entre les électrolytes et de barrière électrochimique vis-à-vis des ions à séparer et du solvant, l'électrolyte (8) du second compartiment (2) se trouvant ainsi préservé de toute contamination par des impuretés.In an electrolysis cell (10) comprising two compartments (1, 2) which each contain a separate electrolyte (6, 8) and the bottom of which is covered with a sheet of mercury (5) acting as an electrode bipolar, the zinc of the zinciferous waste immersed in the electrolyte of the first compartment (1) is deposited cathodically on the mercury (5) to form an amalgam of zinc. The zinc of this amalgam then redissolves anodically in the second compartment (2) producing a cathodic deposit of pure zinc. The bipolar mercury electrode serves both as a mechanical barrier between the electrolytes and as an electrochemical barrier against the ions to be separated and the solvent, the electrolyte (8) of the second compartment (2) thus being preserved from any contamination by impurities.
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83901324T ATE25859T1 (en) | 1982-04-19 | 1983-04-15 | EQUIPMENT FOR CONTINUOUS PRODUCTION OF ELECTRICAL GALVANIZED SHEET METAL. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE207865 | 1982-04-19 | ||
BE0/207865A BE892897A (en) | 1982-04-19 | 1982-04-19 | Recovering constituents of galvanised steel scrap - by electrolytic de-galvanising in alkaline electrolyte |
BE210551 | 1983-04-14 | ||
BE210551 | 1983-04-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0105896A1 true EP0105896A1 (en) | 1984-04-25 |
EP0105896B1 EP0105896B1 (en) | 1987-03-11 |
Family
ID=25653104
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83901324A Expired EP0105896B1 (en) | 1982-04-19 | 1983-04-15 | Apparatus for continuous production of zinc electroplated sheet |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0105896B1 (en) |
JP (1) | JPS59500871A (en) |
DE (1) | DE3370166D1 (en) |
IT (1) | IT1194207B (en) |
WO (1) | WO1983003627A1 (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE746852C (en) * | 1940-04-04 | 1944-08-28 | Duisburger Kupferhuette | Process for processing zinc waste |
DE1558763A1 (en) * | 1967-11-06 | 1970-07-16 | Schoelzel Dr Karl | Process for the electrochemical deposition of metals from solutions of their compounds |
US4056450A (en) * | 1975-06-30 | 1977-11-01 | M & T Chemicals Inc. | Continuous detinning system |
FR2397472A2 (en) * | 1977-07-13 | 1979-02-09 | Seprez | Zinc recovery from galvanising bath dross - which is dissolved electrolytically, followed by electrolytic winning of the zinc |
-
1983
- 1983-04-15 EP EP83901324A patent/EP0105896B1/en not_active Expired
- 1983-04-15 JP JP58501538A patent/JPS59500871A/en active Pending
- 1983-04-15 DE DE8383901324T patent/DE3370166D1/en not_active Expired
- 1983-04-15 WO PCT/BE1983/000009 patent/WO1983003627A1/en active IP Right Grant
- 1983-04-19 IT IT20679/83A patent/IT1194207B/en active
Non-Patent Citations (1)
Title |
---|
See references of WO8303627A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP0105896B1 (en) | 1987-03-11 |
JPS59500871A (en) | 1984-05-17 |
IT1194207B (en) | 1988-09-14 |
IT8320679A0 (en) | 1983-04-19 |
DE3370166D1 (en) | 1987-04-16 |
WO1983003627A1 (en) | 1983-10-27 |
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