Title of Invention | "A PROCESS FOR THE MANUFACTURE OF A NOVEL CERMET ANODE USEFUL FOR ECO-FRIENDLY ELECTROLYTIC EXTRACTION OF METALS FROM FUSED SALTS" |
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Abstract | A PROCESS FOR THE MANUFACTURE OF A NOVEL CERMET ANODE USEFUL FOR ECO-FRIENDLY ELECTROLYTIC EXTRACTION OF METALS FROM FUSED SALT The present invention relates to a process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals, such as aluminum, from fused salts. The process provides a novel cermet anode which consists of compositions of mixed oxides of transition and rare earth metals in combination with metal powders, without any binders, and is amenable to high-pressure compacting and high temperature sintering methods. The novel cermet anode manufactured by the process of the present invention is thermally stable at 1000° C, is chemically inert and non-consumable in a cryolite melt and does not contaminate the cathode product, has low and high anodic over voltages for oxygen and fluorine evolution, respectively, and is dense and resistant to oxidation. |
Full Text | The present invention relates to a process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals from fused salts. Metals, which are less noble than hydrogen in the emf series, have necessarily to be electro-won from fused salts. Even other reduction processes may not be economically viable for production such as in the case of metals like aluminium, titanium, Be, Ca, Mg, Na. Hence, electrolytic route becomes necessary for the extraction of such metals. Further, an eco-friendly electrolytic extraction of such metals is definitely needed. The novel cermet anode of the present invention will be particularly useful for eco-friendly electrolytic extraction of metals such as aluminum. The aluminium metal presently is manufactured by the Hall-Heroult process by the electrolysis of aluminia - cryolite melt between consumable carbon anode and carbon block cathode at temperatures ranging from 950 to 980° C. During the electrolysis aluminium metal is pooled to the cathode at the bottom and carbon dioxide, (COz) is liberated at the carbon anode. The evolution of CO2 - a green house gas is by the inherent consumption of anode carbon according to the following reaction: 2 AI203 + 3 C - 4 Al + 3 C02 Theoretically 334 Kg of carbon only is required for one ton of aluminium but in practice about 500 kg is consumed, liberating 2 tons of C02 to the atmosphere. The use of carbon as anode for aluminium electrolysis has the following disadvantages: 1. Liberation of carbon dioxide, a green house gas with harmful effects. 2. The carbon must be very high purity, free from silicon, sulphur, vanadium. 3. Frequent lowering and adjustment of the anode to maintain optimum anode - cathode distance. 4. Turbulance and unsteady voltage conditions resulting higher voltage and higher energy consumption. 5. Process is labour intensive and environmentally hazardous. 6. Necessity of a separate anode shop. Reference may be made to U.S.Patent 3930967 (1976) in which electrodes made from SnO2, SbaOa and CuO were used for aluminum production. The main drawback is that very low current density ranging from 0.001 to 0.025 A/cm2 only has been applied. Reference may be made to another U.S Patent No.4057480 (1977), wherein mixed materials of SnO2, Fe20s, CoO, ZnO are used as inert anodes for aluminium electrolysis. The drawback being the contamination of the cathode product with excess tin. In a Japanese patent No.1461155 (1977), oxygen ion conducting anodes are disclosed in which both spinel and perovskite structures containing ZrOz as major constituent have been tested. The trial run faced many operational difficulties,, Electrolysis with anodes fabricated from oxides of Fe, Co, Ni, Zn, Sn, Y and Cu powder up to 0 - 30% is given in U.S patent 6126799 (2001). The problem encountered was the contamination and high wear rate of the electrodes. Work on similar lines with cermet anodes incorporating Ag powders have been patented in Canada pat 2317596, (2001). The difficulty with the electrolysis being dissolution of the electrode and contamination of the aluminum metal produced. Reference may be made to a paper by T.R.AIcorn etal, "Light metals 1993" (Ed) Subodh.K.Das Minerals, Metals and Materials Society, Warrendale PA (1993) P. 433-443, in which operational results of a pilot cell test with inert anode has been published. The drawbacks are the instability of the electrode materials and tested up to a current density of 0.5 A/cm2 only. In a paper by J.S.Gregg etal., Light Metals, 1993 (Ed) Suboth.K.Das, Minerals, Metals and Materials Society, Warrendale P.A. (1993) P.455-464, have discussed the testing of copper - nickel ferrite / NiO with or without cerium oxide coating for electrowinning of aluminium. The high energy cost due to low conductivity of the anode was attributed as the main drawback. The main object of the present invention is to provide a process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals from fused salts. Another object of the present invention is to provide a process for the manufacture of a novel cermet anode which consists of compositions without any binders and is amenable to high-pressure compacting and high temperature sintering methods. Yet another object of the present invention is to provide a process for the manufacture of a novel cermet anode which is thermally stable at 1000° C. Still another object of the present invention is to provide a process for the manufacture of a novel cermet anode which is chemically inert and nonconsumable in a cryolite melt and should not contaminate the cathode product. Still yet another object of the present invention is to provide a process for the manufacture of a novel cermet anode which has high electrical conductivity. A further another object of the present invention is to provide a process for the manufacture of a novel cermet anode which has low and high anodic over voltages for oxygen and fluorine evolution, respectively. A still further object of the present invention is to provide a process for the manufacture of a novel cermet anode which is dense and resistant to oxidation. Another object of the present invention is to provide a process for the manufacture of a novel cermet anode which should be cheap and amenable for fabrication by the existing techniques. Still another object of the present invention is to provide a process for the manufacture of a novel cermet anode which will be particularly useful for ecofriendly electrolytic extraction of metals such as aluminum from alumina in molten cryolite. Yet another object of the present invention is to provide a process for the manufacture of a novel cermet anode which can substitute the consumable carbon anodes of the Hall Heroult cell with non-consumable cermet anodes for a trouble free and environmentally clean production of aluminium from alumina by electrolysis. In the present invention there is provided a process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals, such as aluminum, from fused salts. The process provides a novel cermet anode which consists of compositions of mixed oxides of transition and rare earth metals in combination with metal powders, without any binders, and is amenable to high-pressure compacting and high temperature sintering methods. The novel cermet anode manufactured by the process of the present invention is thermally stable at 1000° C, is chemically inert and non-consumable in a cryolite melt and does not contaminate the cathode product, has low and high anodic over voltages for oxygen and fluorine evolution, respectively, and is dense and resistant to oxidation. Accordingly, the present invention provides a process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals from fused salts, which comprises mixing intimately 80 to 90 wt.% dry powders of oxides of one or more of the metals selected from Cu, Ni, Co, Fe, Zn, Al, Ti, Cr, Ce, La, Nb, and 10 to 20 wt. % metal powders selected from Au, Ag, Bi, Sb, Cu, Ni, Zn, either alone or in combination, to obtain a dry blend of powder composition, compacting the dry blend to obtain green compacts, sintering the green compacts at a temperature of up to 1400°C under normal atmospheres, allowing the sintered compact to cool and fixing current leads to obtain a novel cermet anode. In an embodiment of the present invention the intimate mixing to obtain a dry blend of powder composition of metal oxide powders and meta! powders is carried out by known methods. In another embodiment of the present invention the size reduction and size analysis of metallic oxides and metal powders is effected by known ceramic technology methods. In yet another embodiment of the present invention the dry blend of powder composition optionally consists of binders. In still another embodiment of the present invention the compacting of the dry blend is done, in sizes ranging from 5 -12 cm diameter and 5 -12 cm height, in a hydraulic press to obtain green compacts. In still yet another embodiment of the present invention the sintering of the green compacts is carried out in a furnace, such as an electric furnace, at a temperature of up to 1400°C, with a holding schedule of the order of several hours at intermediate temperatures. The novelty of the present invention is that it provides a process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals from fused salts. The novel cermet anode of the present invention consists of compositions without any binders and is amenable to highpressure compacting and high temperature sintering methods. The novel cermet anode manufactured by the process of the present invention is thermally stable at 1000° C, is chemically inert and non-consumable in a cryolite melt and does not contaminate the cathode product, has low and high anodic over voltages for oxygen and fluorine evolution, respectively, and is dense and resistant to oxidation. The above noted novel features have been made possible due to the nonobvious inventive steps of the present invention which comprises mixing intimately 80 to 90 wt.% dry powders of oxides of one or more of the metals selected from Cu, Ni, Co, Fe, Zn, Al, Ti, Cr, Ce, La, Nb, and 10 to 20 wt. % metal powders selected from Au, Ag, Bi, Sb, Cu, Ni, Zn, either alone or in combination, to obtain a dry blend of powder composition, compacting the dry blend to obtain green compacts, sintering the green compacts at a temperature of up to 1400°C under normal atmospheres. The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention. Example -1 A cermet anode having composition containing 85 wt.% mixture of NiO, Fe203, Nb2O5 and 15 wt.% combination of metal powders of Cu, Bi was compacted and used in an eco-friendly electrolyser. The electrolyser was operated with molten aluminum over carbon block cathodes containing cryolite with excess aluminum fluoride and 8 wt% of alumina as electrolyte at a constant current density of 0.50 A/cm2. Continuous electrolysis was carried out at 950°C, for 180 hrs at an interelectrode distance of 3.5cm. Aluminum metal was produced at an energy consumption of 13.4 kwh/ kg of aluminum. Example - 2 An electrolytic cell for the production of aluminum metal was operated with cermet anode of composition 80 wt.% mixture of NiO, Fe2O3, Ce2O3 and 20 wt % combination of metal powders of Bi plus Cu, in a cryolite electrolyte containing 6 wt % of AI2C«3 maintained at a temperature of 980° C and an inter-electrode distance of 4 cm at a current density of 0.80 A/cm2. Pure aluminum was deposited to cathode at a current efficiency of 82%. The purity of the metal obtained was 99 4 wt % with the impurities of Fe = 0.15 wt %, Ni = 0.04 wt % and Cu = 0.04 wt %. Example - 3 An eco-friendly electrolyser consisting of non-consumable cermet anodes made by ceramic technology containing 90 wt % of mixture of Fe2O3, NiO and La2O3 and 10 wt % of a combination of metal powders of Ni, Cu and Sb, carbon block cathode, and molten cryolite electrolyte was operated at a current density of 1.0 A/cm2 at a temperature of 960° C for 140 hrs. to obtain primary aluminum at the cathode and pure oxygen at the anode at a current efficiency of 85%. The metal so obtained was of 99.2% purity with the impurities Cu 0.05 wt %, Fe 0.20wt % and Ni 0.05 wt %. From the above examples it is confirmed that the novel cermet anode manufactured by the process of the present invention is stable and not consumed during the electrolysis and can be a suitable substitute for carbon of We claim: 1. A process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals from fused salts, which comprises mixing intimately 80 to 90 wt.% dry powders of oxides of one or more of the metals selected from Cu, Ni, Co, Fe, Zn, Al, Ti, Cr, Ce, La, Nb, and 10 to 20 wt. % metal powders selected from Au, Ag, Bi, Sb, Cu, Ni, Zn, either alone or in combination, to obtain a dry blend of powder composition, compacting the dry blend to obtain green compacts, sintering the green compacts at a temperature of up to 1400°C under normal atmospheres, allowing the sintered compact to cool and fixing current leads to obtain a novel cermet anode. 2. A process as claimed in claim 1-3, wherein the dry blend of powder composition optionally consists of binders. 3. A process as claimed in claim 1-5, wherein the sintering of the green compacts is carried out in a furnace, such as an electric furnace, at a temperature of up to 1400°C, with a holding schedule of the order of several hours at the temperature ranging between 950°C to 980°C. 4. A process for the manufacture of a novel cermet anode useful for eco-friendly electrolytic extraction of metals from fused salts, substantially as herein described with reference to the examples. |
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34-DEL-2003-Abstract-(27-01-2009).pdf
34-DEL-2003-Claims-(27-01-2009).pdf
34-DEL-2003-Correspondence-Others-(27-01-2009).pdf
34-del-2003-correspondence-others.pdf
34-del-2003-corresponence-po.pdf
34-del-2003-description (complete).pdf
34-DEL-2003-Form-1-(27-01-2009).pdf
34-DEL-2003-Form-18-(27-01-2009).pdf
Patent Number | 228350 | ||||||||||||
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Indian Patent Application Number | 34/DEL/2003 | ||||||||||||
PG Journal Number | 08/2009 | ||||||||||||
Publication Date | 20-Feb-2009 | ||||||||||||
Grant Date | 02-Feb-2009 | ||||||||||||
Date of Filing | 10-Jan-2003 | ||||||||||||
Name of Patentee | COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH | ||||||||||||
Applicant Address | RAFI MARG, NEW DELHI-110 001, INDIA. | ||||||||||||
Inventors:
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PCT International Classification Number | C25C 1/00 | ||||||||||||
PCT International Application Number | N/A | ||||||||||||
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