GB2372257A - Extraction of aluminum and titanium - Google Patents

Abstract

The non-suitability and inadequacy of conventional thermal reduction utilising carbon for the extraction of metals such as Titanium, Chromium and Vanadium is a point of focus in this invention principally because the end products are carbides of these metals and not the metals as would be expected.,wherein attention is drawn via this invention of a contemporary process involving the electrolytic extraction of titanium, chromium and vanadium as well as other metals from an electrolytic production cell utilising and comprising a mixture of high and low melting point carbides, hydrides, borides, nitrides, silicates and sulp hides. Aluminium and titanium are obtained by electrolytic extraction using, as electrolyte, a mixture of high and low melting point carbides, the high melting point carbide being either aluminium carbide or titanium carbide and, as anode, graphite and/or carbon. The low melting point carbide may sodium carbide, calcium carbide or selenium carbide. In a further embodiment a metal is produced by reaction of metallic carbides with metallic hydride. Specifically titanium is produced by reaction of titanium carbide with titanium hydride.

Description

IMPROVEMENT IN THERMAL EXTRACTION This work relates to metal extraction-from a number of metal sources by thermal reduction. The thermal reduction of a metal oxide with carbon is frequently the prefered route to a metal on economic grounds. Because the reaction, MO + C- > M + CO PROCEEDS FROM LEFT TO RIGHT with the net production of carbon monoxide, a gas of large entropy, the reaction will become thermodynamically feasible for all metals at some temperature or the other. This is because in the equation > B'= > H'-T > S' the > S term is positive ; thus, provided that T is large enough, > G'becomes negative and hence favourable for the reaction. In practice temperatures of over 2000'C are uneconomical and other methods are used to extract metals that form very stable oxides. Metals that are normally extracted by caron reduction of oxides include lead and zinc.

However, with the-first-row transition elements there is a complication, interstitial compound formation. If titanium(iv) oxide is heated with an excess of carbon, for example, the reaction Ti02 + 3C- > TiC + 2CO proceeds and titanium carbide is the product. For titanium, vanadium and chromium, THIS METHOD CANNOT BE USED. However the latter transition metal can be obtained in IMPURE FORM by this method, for example Mn304 + 4C - > 3Mn + 4CO Co203 + 3C- :' 2Co + SCO Iron is the most important example economically. The reduction of iron oxides by coke in the blast furnace gives'pig iron' which contains about 4. 6% carbon (the solubility limit of carbon in iron). This excess of carbon is removed by oxidation using air or oxygen with the molten metal in a bessemer converter or an open hearth.

Steels rather than pure iron are obtained in this way ; pure iron has no industrial importance. Despite the fact that we have written carbon as the reducing agent in the equations, the effective reducing agent is probably carbon monoxide, the carbon serving to reduce the carbon dioxide produced back to the monoxide, for example CD + FeO - > Fe + C02 C02 + C" 2CO Hydrogen reduction of metal oxides is not cheap or effective as carbon reduction, but when contamination from carbon is undesirable it may be a useful process. Thus pure iron can be obtained by heating high purity Fe203 in hydrogen ; cobalt, molybdenum, and tungsten are similarly obtained free from carbides by, for example, the reaction Co203 + 3H2-- > Co + 2H20 Alternatively, if the temperature for carbon reduction is too high and\or carbon contamination is a problem, reduction by an active metal such as calcium, magnesium, or aluminium can be used. The'thermite'process is used in the extraction of

chromium and of carbon-free ferrovanadium and ferrotitanium Cr203 + 2A12- > 2Cr + Al203 Vanadium is obtained from the oxide by the reduction with silicon or calcium 2V205 + 5Si - > 4V + 5SiO2 In the pyrometallurgical process for extracting copper from sulphide ores, the sulphur in the ores is used as reducing agent oxidised,that is 2Cu2O + Cu2S- > 6Cu + 302 A rather special process is used for refining nickel ; this is known as the MOND OR CARBONYL PROCESS. The impure Nickel obtained by Carbon reduction of NiO is treated with carbon monoxide at 50, and the volatile carbonyl so produced is decomposed to the pure metal at 180' ( Ni + 4CO- > Ni < CO) 4 Pure iron can similarly be obtained by thermal decomposition of Fe(CO)5.

tPLICATONS OF tLLTHEBOVEJMENTIONED.METHODS: 1. With Carbon reduction of the transition metal oxide, complication arises in which interstitial compound formation results. Titanium carbide being the product when titanium oxide is carbon reduced. Method therefore not good for industrial production of Titanium, Vanadium, and Chromium.

With latter transition metals, impure form of the metal is obtained. This method is however perfect for LEAD AND ZINC.

2. Hydrogen reduction is an alternative when situation as in 1. arises. This method is EXPENSIVE and LESS EFFECTIVE THAN CARBON REDUCTION.

3. Reduction by an active metal can be used. Used for Chromium, vanadium and copper.

4. Carbonylation (MONDS' PROCESS) of impure metal purifies it if pure metal is needed. Perfect for nickel.

IMPROVEMENT IN EXTRACTION FROM OXIDE BY THERMAL MEANS : From the above, it is evident that there is no major means of producing titanium, vanadium and chromium on a large scale using carbon reduction of the metal oxide because metal carbides are formed. Carbides are of course, useless as engineering materials.

This work primarily targets METAL CARBIDES as one of the reagents necessary for producing the above mentioned metals and any other metals for that matter, ON A RELATIVELY LARGE SCALE capable of industrial application.

These work considers five major routes proposed for producing these metals. Some of which are more attractive than others purely on economic and other reasons as will be discussed.

The first two routes proposed are: 1. METAL OXIDE + METAL CARBIDE -) 2METAl + CO 2. METAL CARBIDE + HYDROGEN METAL + METHANE These two reactions are improvements on'state of the art' methodologies as explained below : In the FIRST reaction, it is well-known that carbon reduction of metal oxide for the metals mentioned above does NOT yield a

pure metal as it is in the case of lead and/or zinc, but the METAL CARBIDES.

In alliance with the method for producing say copper, in which the sulphur in the ores is used as a reducing agent after half the copper has been oxidised, it occurred to me that the same principles could be applied to solve the production problem for carbide-free titanium, vanadium, and chromium and any other metal so desired, and the end product would be carbidefree assuming of course that the reaction comes to completion, involving a reaction whereby the carbide (as source of carbon) is used as a reducing agent after half the titanium has been oxidised.

In addition, if suitable protective atmosphere like argon is used in conjunction with the above, to protect against interstiality with respect to oxygen, this will instaneously offer an alternative method to KROLLS process for producing titanium and will be MUCH MORE CHEAPER. In addition, it offers a comparable process to MONDS'for producing the initial impure (if not pure) metal.

An advantage of the process is that in addition, carbon monoxide is produced, an entropy driven gas, the reaction will become feasible at one temperature or the other.

The product metal can then be further purified by the carbonylation process (MINDS') if it is deemed necessary.

For titanium, it is expected that a titanium carbonyl complex would be formed and since hexacarbonyl campes is unstable, it is thought that this will dissociate to give a pure titanium metal by a process similar to bonds', this offering a parallel comparison to Na/Mg reduction of titanium chloride.

For vanadium and chromium, a stable carbonyl complex is known to form and a process similar to Monds'can lead to purification of metal if so desired.

In the SECOND reaction, the simplest case of producing a metal would be, as exemplified by titanium would be: Ti02 + H2- > Ti + H20 We of course know that this reaction does not proceed because titanium oxide has a very large energy of formation. Titanium carbide has considerably less energy of formation and hydrogen reduction should, it is expected, inevitably take place at some temperature.

Another embodiment of this work relates to metal hydride reduction of the metal oxide. This is also in alliance with the copper extraction process referred to earlier. With

reference to titanium, TiC2 + 2TiH2 3Ti-'-2H20 Titanium hydride would have to made and since this is not possible by hydrogen reduction of the oxide, it is evident at this stage that only direct reaction of Titanium and hydrogen would give the hydride. This would therefore be a slightly expensive process to start with, in so as long the starting material is concerned but once the process is in operation, and titanium metal is been made this can be followed by

hydrogen combination at elevated temporabur'n (400C'), Lh above reaction should become visible.. thermal nt'cem.

X i-4 a 4 a- < X m t d lH'i Ci P F"iP i D r f t. ) r l , aS t$at. y < x : i. t rc > re% q ; aizrl J t n < -, < \mrif ! ou'h tha e : < 'J'.'. iufn hydride r'BChK'Ljon u- !'. : iLaruLtf) < ! i- :..'..-' i'--, < l)" (. ? < -uJy < \ ?)'-'. < 'L : i. < "c.''abl' ? proc'ss ? ; and jL i'-. t'tO) :) H' < t H-. < -'. L C < r cstE a) al : :"t ? iG J waar i j s l sle r) t~'ant : 2 he d : i. < ;' !'. ingutshmg'factor her : i. & , th ? ; \rtfju' !. rLt'y o- !'' fm-.'t' !. pci. nohhsr impJiatio a' !' he wor JSi Lhe ntur u TiC and .'th & 'r mtal carbide in general. Titanium carbide possess cr Li e p o,-r, e s s jjh'/'-tiCt : e\nd chemical properties which indicates that it is "essentially" ionic and it follows that if it could bo solvated and/or established in a molten state or otherwise, there is greater implication for the possibility of electrolysis of metal carbide for the production of a metal.

This of course would be good news considering the fact that titanium tetrachloride is covalent, and electrolysis of this salt, is not possible. Electrolysis of titanium hexachloride might prove useful. A more elaborate explanation is discussed later.

With processes discussed so far, I envisage the possibility

of : 1. Ti02 + TiC- > 2Ti + CO/CO2 2. NiO + NiC 2Ni CO 3. 2V205 + 5VC -) 9V + 5cd2/10CO and others for the carbide reduction of the oxide.

It might also be possible to obtain the metal by : 1. TiC + 2H2- > Ti + CH4 2.Cr4C3+6H2- > 4Cr+3CH4 and many more. One major disadvantage of hydrogen reduction is that this will be a slightly expensive process.

Advantages of producing titanium on a large scale is much sought after for many a reasons as will be listed below. The most economical method would have been carbon reduction of the oxide, this is not used as titanium has a large affinity for atmospheric oxygen and carbon. Above method offers ; a solution.

The quest for less expensive method like the one proposed above has been much sought after. It would invalidate the popular and more expensive Krolls'process which utilises carbon and chlorine reacting with titanium oxide to produce titanium chloride and then either sodium or magnesium reduction of the chloride to get the pure metal, process also requiring the use of argon as a protective atmosphere due to interstitial compound formation with nitrogen and hydrogen, and an electric arc.

Problem foreseen include the nature of the reagents itself.

Titanium carbides are very stable and and Titanium oxide has a very high energy of formation. It is therefore expected that the first proposed process would be a very high temperature process if the two reagents will indeed react and reation come to a completion. The question that springs to mind here is : Will the reaction go ? A practical solution is provided as follows: In alliance with the copper extraction reaction referred to, it is expected that the starting point would be to use carbon as a reducing agent until a point is reached corresponding to half the titanium been oxidised to titanium carbide and then the reaction should then proceed at such a temperature without much ado because the carbide is at a thermodynamically favoured state. With this method, problem of carbide formation is avoided, there is no problem of getting rid of any excess carbon and if atmospheric protection is used, problem of interstiality is also solved.

With the second proposed process, it is hoped that the reaction will proceed as TiC has less energy of formation compared to Ti02 even though the carbide is very stable.

Otherwise, it is hoped that for some less stable metal carbide, the process would become useful at some particular temperature.

It is also hoped that the"essentially and/or moderately ionic"nature of : titanium carbide, titanium hydride, titanium boride, titanium nitride and titanium silicate will make, viable the possible prospect of ELECTROLYTIC EXTRACTION of titanium either in the molten form of its fused salts or otherwise (e. g in the purification of impure titanium assuming the suitable existence of a good titanium electrolytic solution). While reference here is made to titanium, it should be borne in mind that processes described below applies to any metal capable of forming "essentially and/or moderately"ionic carbides, hydrides, boride, nitride, and silicate. It is quite clear from literature, that titanium nitride and titanium borides are REFRACTORY like the metal titanium itself and therefore electrolysis of these compounds in molten form would be technically impossible due to lack of fLlsion/decomposition characteristics. Electrolysis therefore referred to above, is for compounds other than those of refractorable characteristics.

A good reference to be made here, is the suitability of and/or application of DOWNS'PROCESS or a DOWNS'-LIKE PROCESS as a model plant set-up for the above extraction. For those not familiar with the technicalities of the DOWNS'process, a brief outlay is hereby explained.

Downs'process is used industrially for the extraction of Sodium in which sodium chloride is electrolysed in the molten condition. As the melting point of the salt is high (about 800'C), calcium chloride is added to lower the melting point ; it becomes about bOO'C. The Downs'cell has an outer iron shell, lined with firebrick. A diaphragm of iron gauze screes the carbon anode from the ring-shaped iron cathode that surrounds it. Chlorine escapes via the hood. Sodium collects in the inverted trough, placed over the cathode, rises up the pipe, and is tapped off through the iron vessel. Sodium chloride produces ions Na+ and Cl-.

At the cathode At the anode

Na+ + e-== Na Cl"= > Cl-)-e (a reduction) (an oxidation) Then : Cl + Cl == > C12 Chlorine is a valuable by-product of the process.

In the titanium application of the above process, as with the Downs'process equivalent, it may also be necessary that a metal carbide of low melting temperature be mixed with the desired metal carbide if the latter is one requiring a very large melting temperature that will make the process uneconomical and therefore unpracticable.

With emphasis on titanium extraction from titanium carbide, it should be stated that titanium carbide has a melting point of 3140 +/-90'C and as this would be unpracticable-from an economical point of view, it is therefore necessary to lower the above temperature considerable to below 2000'C and the choice of metal carbide of lower melting temperature include: ALUMINIUM: 1400'C IRON : 1837'C SODIUM : 700'C CALCIUM: 25-447'C MOLYBDENUM : 2692'C CHROMIUM : 1980'C SELENIUM : 45.5'C From the above, it is imaginable that to lower the melting temperature of titanium carbide below 2000'C, the obvious choice are ; Calcium and Selenium. Calcium would be the first choice as regards cost and accessibility and i cannot at this stage comment on the selenium case on the basis of cost BUT IT SHOULD BE STATED THAT HAVING A M. P OF 45. 5'C IT THEORETICALLY STANDS THE BETTER CHANCE OF ACHIEVING THIS PURPOSE assuming of

course, this is favourable cost-effectively. Sodium might also suceed in reducing the melting temperature below or just above 2000'C. ) k TA-f'a/E ! > 'e$ < z- sztfcy-h c & d--r Tj' W-Itkbt4l--T Choice of electrodes is another consideration to be made.

Another embodiment of this work relates to the reaction of metal carbide and metal hydride to produce the metal and methane. It should be noted that the thermal reaction of any two of the listed"essentially and/or moderately ionic" compounds referred to earlier would also summount or better still, result in metal extraction.

For the example listed above, it is ; expected that the following would take place : TiC + 2TiHS" TTi + CH4.

It must be stated that while titanium hydride is written as divalent here and throughout this work, it is of uttermost importance to stress that the tetravalent hydride would also do the reduction quite well and that the sole difference is just a matter of stoichiometry.

Again, these two reagents are very stable and it is hoped that the relatively inexpensive, seperate or singular step preparation of these two, by processes similar to those already described as part of this work i. e carbon reduction of titanium oxide at an appropriate temperature to yield titanium carbide until half the titanium has been oxidised, and then hydrogen reduction of a acquired titanium metal at an appropriate temperature of around 400'C to yield titanium hydride and subsequent reaction at suitable temperature to produce the gas-methane assuming the reaction does indeed proceed. The singular step referred to above is one involving the reaction between say titanium oxide with titanium, hydrogen and carbon and making use of the fact that hydrogen reduction of the oxide does not occur and the only possible route is that involving titanium and in a similar manner, the available carbon will reduce the oxide and it may also be predicted that a small reduction of the metal will also occur noting fierce competition with hydrogen and it is hoped that at some point enough of the carbide and the hydride of the metal will be formed for this wanted reaction to occur.

Producing titanium on a large scale even on a slight expensive budjet is justified. This is because the metal has unique properties. It is a good conductor of heat and electricity. It is however, quite light in comparison to other metals of similar mechanical and thermal properties and unusually resistant to certain kinds of corrosion ; therefore, it has come to demand for special application in turbine engines and industrial chemical, aircraft, and marine equipment.

Other suitable category employable for use with compounds of interstitial peculiarity of carbides, borides, nitrides, hydrides and silicates and whose electrodiffusing properties and ionicity is ideally paired for are METALLIC SULPHIDES.

The half way reduction of metallic oxide is well recorded.

IMPRP.EMENTIN.THE PRgCE:55qF..LUWINIUM EXTRACTION THE PROCESS rUMInM EXTRACTION : This is carried out from a molten salt called cryolite (N < =\Z. A1F6) ; in the molten state at about 1250K it dissociates into Na+ and ALF6 about 2 to 8 per cent by mass of alumina, AL203, is added.

A typical electrolysis cell is shown schematically in later.

Mhen the alumina is added to the melt, comple : ; ions such as ALOF2- are found due to the reaction AlF6 3- + A1203 =) 3AIOF2 -.

This complu : ion breaks down and is in equilibrium with P) 13+, F-, and 02-. At the interface, Al3+ discharges to form aluminium metal. The reaction is simply : A 17.'---3 e ; =' > A I The anode reactions are much more complicated. During electrolysis, the anodic process consists of the deposition of oxygen, probably from oxygen-donating anions such as AlOF2-. The positive electrode is carbon and the deposited oxygen reacts chemically with the carbon to form carbon monoxide and then further to carbon dioxide. Thus, the overall anodic reaction may be represented as ; 3 0 + 3/2 C = > 3/2002.

The overall cell reaction is : A1203 +3/2 C = > 2Al + 3/2 Coq2.

The reversible potential of the aluminium production cell at 125, calculated from thermodynamic data corresponding to the overall cell reaction (i. e on the basis of the relation

zFV =-AG, is V. However, the potential needed to run the cell in practice is much greater than this, because of the overvoltage which is about 0. 6 V to 0. 7 V at a current density

of : WOO Am-2. The major oortion of this overootential is due to the anodic reaction. The cathodic reaction requires little overpotential. Then one has to add the'IR'potential drop through the molten salt itself which amounts-for a typical 85000 to 150 OOOA commercial aluminium production cell-to about 1. 6 to 2. 0 V, and also add that across the resistance between the molten aluminium cathode and the cathode bus bar system, which amounts to approximately 0. 5 V. Consequently, the total voltage needed neede to run the cell is approximately 4.7 V, about 3.5 V greater than the reversible thermodynamic potential of the cell. The electric charge that circulates where lkg of aluminium is liberated is constant, but the energy required is the product (quantity of electricity n p. d), so the cost of the energy needed to produce lkg of Al is proportional to the potential (here 4. 7V) which has to be applied to make the cell work at a desired current density.

From the above, it is evident that application of results on the overpotential of the anodic reaction and above all on the IR potential drop in the cell and the potential differences at the contacts could well lower the price of aluminium significantly. However the savings indicated by possible new methods or de sign changes would have to be sufficient to compensate for the cost of the new equipment as well as for the loss of capital due to the replacement o-f the old plant (before it has amortised itself). This kind of economic strait-jacket is not always allowed for by academic consultants to industry, who may think that new ideas are sufficiently justified if they are scientifically correct.

Bearing in mind all the above, the process described below intends to make amendments to rectify these inadequacies to provide an improvement in the extraction process thereby lowering the price of aluminium.

IMPROVEMENT PROCESS- In the commercial extraction of aluminium, it is a fact that alumina has to puri-fied by dissolvlng it in soda and the resuting hydrate heated to geh a purer alumina to which cryolite is then added.

This improved process requires that the alumina be converted to aluminium carbide by heating the alumina with carbon. By carbide classification, aluminium carbide is saltlike and exhibits chemical and physical properties similar to ionic compounds. It has been known-for a long time now that when water is added to such ionic carbides like calcium carbide and even aluminium carbide that ethyne and methane are produced in addition to their hydroxides respectively. The nature of the carbon specie diseminating from the carbide is usually referred to as C4- or@ methionine ion. This work relies on the

nature of this specie in a molten state," Tof/c-f-ex-e.'a. aluminium carbide has a melting point of 1400'C. The hitherto described process is evident economically at 970'C. It is therefore a visibly requirement to lower this temperature and it is thought that low melting carbide addition to aluminium carbide would make this realistic. Low melting carbides referred to are calcium carbide from which ethyne is made and which melts at between 25-445'C and/or selenium carbide of 2S'C melting point and/or sodium carbide of 700'C melting point temperature would do the trick.

Advantages of this process include : 1. The anodic graphite electrode does not need to replaced since a carbon or more or less, a carbon-like specie would be the migrating specie.

2. It is thought this would also reduce the overpotential of the anodic reaction which is the primary contributor to this overpotential 3. The process of extraction need not be stopped as it is usually the case to change the elecrodes. This would provide a continous process of aluminium extraction. Thermal reduction

of alumina with carbon can also be done on a continous basis.

With this process, no new equipment is necessary and coke is cheap. The only new process would be carbide production at relatively high temperature of between 1000-2000'C and this should be relatively cheap otJi--. zpe'oC.'Tir. cccn-M.

'fLf !. < , 'T' ! t C ( < b < 0'jc'\a, i.'J t r

Claims (13)

1. CLAIMS: 1. An improvement in extractive metallurgy and process utilising the electrodiffusing properties of interstial compounds of carbides, hydrides, borides, nitrides, silicates and sulphides as a melt wherein the process utilises dimensions of a singularity of specie whereby there is metallic singularity and non metallic singularity of specie in a melt comprising both a low melting and high melting compounds primarily interstitial in nature and falling into categories as carbides, hydrides, borides, nitrides, silicates, and sulphides for metallurgical purposes.
2. 2. An improvement in extractive metallurgy and process as claimed in 1. as above wherein the electrodiffusing properties is further explored in a thermal capacity utilising the interstitial properties of compounds in carbides, nitrides, hydrides, borides, and silicates and sulphide in a batch and continous process in an electrodiffusion mannerism with the oxides of metals hereby referred to as metallic oxides and maintenance of a rule of specie singularity as in 1 and 2 above and as decribed as part of this publication.
3. 3. An improvement in extractive metallurgy and process as claimed in 1 and 2^ : above wherein, employment is made of hydrogen in a reaction utilising thermal means as a batch and continous process electrodiffusing in a manner as claimed in 1 and 2 as above wherein the electrodiffusing peculiar characteristic of carbides, nitrides and borides and slicates and sulphides is employed.
4. 4. An improvement in extractive metallurgy and process as claimed in 1, 2, 3, wherein, the employment of hydrogen is not only limited to a thermal process but either utilisation in an electric mini arc and or melt in conjunction with the interstitial compounds of carbides, silicates, nitrides, borides and hydrides.
5. 5. An improvement in extractive metallurgy and process as claimed in 1,2, 3,4 utilising the reduction with metallic sulphide in a melt or thermal process wherein pairing is with intersttial compounds of carbides, hydrides, borides, nitrides and silicates.
6. 6. An improvement in extractive metallurgy and process as claimed in 1, 2, 3,4, and 5 above wherein a well established phase diagram exists stipulating characteristics for all interstitial compounds of carbides, nitrides, borides, silicates, and sulphides and in particular, eutectoid hyper-eutectoid, and hypo-eutectoid temperatures giving peculiar nature of atmospheres and temperature for a peculiar morphological details and composition of metals to be extracted.
7. 7, An improvement in extractive metallurgy and process as claimed in 1,2, 3,4, 5,6, as above wherein the electrodiffusing properties of the interstitial compounds of carbides, borides, nitrides, silicates and hydrides is explored with the rule of singularity of specie wherein there is melt metallic correlation of the type as stipulated as part of this invention and equally as part of the above claims and equally non metallic singularity of specie equally emphasised as part of this work wherein a situation is not foreseen as in the following examples: Example 1: GB 512502 JOHNSON G W EXAMPLE 2 ON page 6 76 parts of chromium oxide are intimately mixed with 135 parts of a chromium metal containing 14.6 per cent of carbon in the form of carbide by grinding in a ball mill, The mixture is heated at 1200 degrees centigrade for 10 hours under a pressure of 30 millimetres (mercury guage) IN purified hydrogen at a speed of flow of 20 litres per hour per litre of reaction space. A wintered piece of metallic chromium of the same purity as the product of sample with less than 0. 01 per cent of carbon is obtained.

   Example 2: US 2516863 GARDNER D COLUMN + lines 1-23 and 41-52 The reaction starts at 675 degrees when calcium hydride begins to decompose yielding: Ta205 + 3CaH2 = 2 TaH + 3CaO + 2H20 + 137.5 Cal This reaction is adapted to be brought well under control if the process instead of being run in batch is to be run in a continous manner in a suitable electric furnace subjecting the TaH to yet higher temperatures as 1850 degrees +/ reduces the metal.

   Obviously the calcium hydride well mixed with alumium and tantalum pentoxide powdered can be used mounting in temperature so that the reaction takes place beyond the temperature of 1850 degrees when the hydrogen no longer forms tantalum hydride and no free hydrogen is retained by the metal.

   Ta205 + 2A1 + CaH2 = A1203 + CaO + H20 + 75.0 cal It is noteworthy that only bne fifth of the light metal is used in this case for the reduction as compared with the Bolton reaction.

   Please distinguish by singularity of specie in reaction and for particularity of purpose melt, thermal, batch or otherwise, .
8. 8. An improvement in extractive metallurgy and process as claimed in 1,2, 3,4, 5,6, and 7 as above wherein the electrodiffusing properties of the interstitial compounds of carbides, nitrides, borides, silicates and hydrides is explored with distinguishing features and rule of law of singularity of specie and purpose to differentiate from the below example with respect to TITANIUM EXTRACTION Example 1: Reference Titanium (1956) PAGE 7 lines 9-15 A modified form of the calcium reduction method of producing metallic titaniu m from titanium dioxide in which calcium is replaced by calcium hydride has been described by ALEXANDER et al. The reduction of the oxide is carried out at 600-700 degree centigrade under an atmosphere of hydrogen and the product after removal of calcium of calcium oxide, is a finely divided titanium metal metal containing a considerable quantity of hydrogen.

   ALEXANDER P. P US 2038402 1936 ALEXANDER P. P US 2427338 1947
9. 9. An improvement in extractive metallurgy and process as claimed in 1,2, 3,4, 5,6, 7 and 8 above wherein theelectrodiffusing properties is explored of the interstitial compounds of carbides, silicates, borides

   hydrides and nitre. des is utilised in a manner to differentiate it from, as a batch and continous process, melt or thermal processess by the rule of singularity of specie and purpose so as to differentiate fromn the following; Example 1: REDUCTION IN PRESCENCE OF MOLTEN METAL OF No 6 tantalum and nioblum (1959) W. ROHN of the heraeus-vacuum-schmelze A. G claimed the production of nioblum and other metals by adding a mixture of carbide and oxide to the pure molten metal while evacuating the carbon monoxide. The reaction was reported to be vigorous. It is inconceivable that this procedure was actually adopted for niobium because of the difficulty in containing the reactive molten metal particularly as is claimed at a time (1934) when the melting of reactive metals had not been on a commercial basis.

   Undoubtedly, it is possible to produce niobium and tantalum by the reduction of their oxides with carbon or carbides but it is difficult to eliminate the carbon and oxygen to a very low le-v-el without the use of prolonged heat treatment at temperatures of the order of 200&commat;degrees in a high vacuum.
10. 10. An improvement in extractive metallurgy and process as claimed in 1,2, 3,4, 5,6, 7,8, and 9 above wherein the electrodiffusing properties and a peculiar characteristics as revealed in this invention and any before it, in a melt or thermal, batch or continous process is utilised by a process as described on page 8, is the suitability of DOWN'S PROCESS and in particular the application of chlorine to any of the process which forms part and parcal of this invention, be it batch or otherwise, a melt of two or more cabides, borides, nitrides, silicates, and hydrides or any blend of the of the above category. This is to differentiate it from any known work especially those as described below: EXAMPLE *1.

    CHLORINATION OF THE CARBIDE Metallurgy of the rarer metals-MILLER It is-most important that the pipe connecting the furnace and the condenser should be of ample size, short lenght and preferably heated in order to minimise the danger of the chloride being deposited at this point.

    The chlorinator is run continously and the zirconium carbonitride crushed to a suitable size is fed in at the top of the furnace which is maintained at about 500 degree centigrade.

    The zirconium chloride passes over into the condenser and is condensed as a loose fluffy powder which contains small amounts of impurity such as iron, chromium. silicon and zirconium oxide.
11. 11. An improvement in extractive metallurgy and process as claimed in 1,2, 3,4, 5,6, 7,8, 9 and 10 above wherein the electro-diffusing properties and peculiar characteristics of compounds of carbide, hydrides, borides, nitrides, and silicates is exploredwith the rule of singularity of specie of both cation and anion in a melt, batch or continous as a thermal process is explored for extractive purposes other than for any other purposes known and as cited any where else. Primary distinction is made to differentiate the example as cited below from any reference as part and parcel of this work in any publication or application before now.

    Example 1: ZIRCONIUM"2nd Ed, 1957 pages 73 line 9 to page 74 line 13.

    A Fundamental study of the iodide or hot wire process was made by R. B HOLDEN and B. KOPELMAN. They divided the process into four steps (a) SYNTHESIS OF ZIRCONIUM TETRAIODIDE AT ABOUT 300 degrees centigrade.

    (b) Transport to the hot filament of zirconium tetraiodide.

    (c) Thermal decomposition and (d) Transport of the liberated iodine back to the feed zirconium.

    Steps b and d. were combined and termed the gaseous transport step. The first part of the investigation was to measure the probability that a zirconium tetraiodide molecule will de compose upon striking a hot surface. Pure zirconium tetraiodide was introduced into an evacuated glass apparatus containing a molybdenum filament or target which was heated to various temperatures. The zirconium decomposed during the experiment and the amount was determined by analysis of the target for zirconium. The quality of zirconium tetraiodide impinging on the target was controlled by maintaining the iodidecrystals in a close-d chamber at a carefully controlled temperature which determined the pressure of the vapour.

    -The vapour passed through an effuser of the special design which permitted a calculation to be made to determine the fraction of tetraiodide which impunged on the target.

    The experiments show that the probability of a zirconium tetraiodide molecule decomposing when it impinges once upon the surface at 1300 to 1500 degrees centigrade in a vacuum is nearly unity.

    It was also shown by further experimenting that the step which determines the speed of the hot wire process is the step which the rate transport of the gaseous reactant. This applies when the fixed zirconium is not appreciably less reactive than the crystal bar used in the experiments. The result indicate that the speed of the iodide process coul d probably be accentua -ted by increasing the velocity of gases.

    "An interesting and unexpected funding was that the synthesis of the zirconium iodine and feed zirconium which proceed very slowly while the filament is unheated, increases rapidly as soon a-s the filament is heated, e̤c. smes. hotw ui to-'emi-t--light. It-was-assumed that the effect was a photochemical one due to the action of the light from the filament on the iodine PURITY OF THE IODIDE PROCESS ZIRCONiuM Commercial iodide zirconium contains approximately 2 to 3 per cent hafnium which is associated with zirconium in the mineral and which is NOT normally eliminated in the processing A recent analysis of iodide zirconium was published by the FOOTE MINERAL CO : as follows: Hf, 2. 4; Ti and Fe, 0.1 each, H2 0.02, Si, AI Ni, Ca, Cu. 02 and N2, 0.01 each; Mg 0. 003 per cent. The hafnium and titanium would be iodized and deposited as readily as the zirconium and must have been present in the crude metal. The relatively high iron value emphasises one of the draw backs in the iodide process Recent analysis of iodide zirconium indicates that material of a much higher purity than that quoted by the FOOTE mineral Co. is being produced.
12. 12, An improvement in extractive process and metallurgy wherein claims as cited in 1,2, 3,4, 5,6, 7,8, 9,10 andll above utilising the eletrodiffusing properties of the interstitial compounds of carbides, borides, nitrides, hydrides, and silicates as a melt and thermal batch or continous wherein provision is extended for steel production by any of the methods which forms part and parcel of this invention from Fe3C as ferrites, cementite, pearlite and austenite.
13. 13. An extraction process as claimed in 1, 2, 3, 4, 5, 6, 7, 8,9 10, 11, and 12 above and suitability in application for the transitional metals extraction from stable carbides, hydrides, borides, nitrides, silicates and sulphides.

    13. An improvement in extractive proc-ess. and metallurgy utilising the electrodiffusing properties of the interstitial compounds of carbides, nitrides, hydrides and silicates and borid - es in a melt and batch process, by mannerisms as described as part of this work and patent for the EXTRACTION OF NICKEL,

    which present an alternative to MOND'S process of nickel production which may require the formation of Nickel carbide from nickel carbonater other salts of interstitial nickel compoo.

    14. An improvement in extractive metallurgy and process whereby the electrodiffusing properties of the interstitial compounds of carbides, nitrides, hydrides, and borides and silicates is explored in a melt and batch and continous thermal process is explored for the extraction of TRANSITIONAL METALS forming stable carbides, nitrides, borides, hydrides and silicates by methodology and mannerism.'as form part and parcel of this invention and any before it, as part of this work Amendments to the claims have been filed as follows CLAIM (S): 1. An electrolytic extraction utilising within an electrochemical production cell, a mixture of carbides of high and low melting points in characteristics for the extraction of Aluminium, Titanium, Chromium and Vanadium. , wherein anodic electrode is graphite and/or carbon and the nature of methionine ion., C4-deposited unto the anodic electrode ensures greater half-live rather than dissolution.

    2. An electrolytic extraction process as claimed in 1. above, wherein range of metal extracted is seen to include gold from Au2C2, nickel from NiC and iron from Fe3C amidst a production cell mixture defined to sodium carbide, calcium carbide and selenium carbide in plurality.

    3. An electrolytic extraction as claimed in 1 and 2 above wherein an electrochemical production cell mixture is one seen to comprise a low and high melting point hydride for the electrochemical extraction of metals amongst which include Titanium.

    4. An electrolytic extraction process as claimed in 1,2 and 3 above wherein an electrochemical production cell mixture is one seen to comprise a low and high melting point borides for the electrochemical extraction of metals 5. An electrolytic extraction process as claimed in 1, 2 3 and 4 above in which within an electrochemical production cell, a mixture of low and high melting point nitrides is used for the extraction of metal 6. An electrolytic extraction process as claimed in 1, 2 3, 4 and 5 above in which within an electrochemical cell, M. e electrodiffusing properties of a low melting point silicate and a high melting point silicate in a mixture is used for the extraction of metals.

    7. An electrolytic extraction process as claimed in 1,2,

    3, 4 5 and 6 above wherein within an electrochemical product - on cell, the electrochemical extraction of metals has a basis to arise from a mixture comprising a low melting point sulphide and a high melting point sulphide. 8. An extraction process utilising the reduction of metallic oxide by metallic borides.

    9. An extraction process utilising the reduction of metallic oxides by metallic nitrides.

    10. An extraction process utilising the reduction of metallic oxides by metallic silicates.

    11. An extraction process utilising the reduction of metallic oxides by metallic sulphides.

    12. An extraction process utilising the reduction of metallic carbides by metallic hydrides especially titanium carbide and reaction with titanium hydride.