# US 10,870,153 B2 · Thermochemical processing of exothermic metallic system > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,870,153 B2 - Document ID: US10870153B2 - Status: Granted - Kind: B2 - Application number: 16/315,601 - Filed: 2017-07-06 - Published: 2019-07-04 - Granted: 2020-12-22 - Earliest claimed: 2016-07-06 - Assignees: Kinaltek Pty. Ltd. - Applicants: Kinaltek Pty. Ltd. - Inventors: Jawad Haidar - Web page: https://patentgrep.com/patent/US10870153B2 ## CPC - B22F 9/20: starting from solid metal compounds - C22B 5/04: by aluminium, other metals or silicon - C22B 5/18: Reducing step-by-step - C22B 34/20: Obtaining niobium, tantalum or vanadium - C22B 34/22: Obtaining vanadium - C22B 34/24: Obtaining niobium or tantalum - C22B 34/30: Obtaining chromium, molybdenum or tungsten - C22B 34/32: Obtaining chromium - C22B 34/34: Obtaining molybdenum {(treatment or purification of solutions by adsorption on solids C22B3/24, by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42; preparation of molybdenum involving liquid-liquid extraction, adsorption or ion-exchange C01G39/003)} - C22B 34/36: Obtaining tungsten - B22F 2301/052: Aluminium - B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER - C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS ## Abstract This invention relates to a method for controlling exothermic reactions between metal chlorides of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb Cu, Pt, W, Pd, and Mo, and Al and the use of the method for preparation of metallic alloys and compounds based on base metals Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb Cu, Pt, W, Pd, and Mo. The method provides for a mixture of precursor chemicals including at least one solid base metal chloride to be mixed and reacted exothermically with a control powder based on Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb Cu, Pt, W, Pd, and Mo and then reacting the resulting intermediates with an Al scavenger. Reduction is carried out in a controlled manner to regulate reaction rates and prevent excessive rise in the temperature of the reactants and the reaction products. ## Claims ### Claim 1 A method for controlled exothermic reduction of a metal chloride of one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, Mo, Pb, Sb, Bi, In, Cd, Ga, Rh, Ir, Ru, Os, and Re, with an Al reducing agent, the method comprising: contacting said one or more metal chlorides, a control powder and an Al reducing agent, all in a fine particulate form, at a reaction temperature between 25° C. and a maximum temperature Tmax to form a metal or metal alloy product in a powder form and a by-product including aluminium chloride; and separating the by-products from the metal or metal alloy powder product; wherein the control powder includes one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, and Mo, or an alloy or compound thereof, and acts to control exothermic heat release from the reduction and to thereby keep reaction temperatures to less than Tmax; wherein Tmax is between 400° C. and 1100° C., and below the melting temperature of the metal or metal alloy product; and wherein the reaction is controlled such that heat generated by the reduction does not increase the reaction temperature by more than 600° C. from a temperature of said contacting. ### Claim 2 (depends on 1) The method according to claim 1, wherein Tmax is higher than the sublimation/evaporation temperatures of all of the one or more metal chlorides. ### Claim 3 (depends on 1) The method according to claim 1, wherein in a first step said metal chlorides are metal chlorides which are mixed and reacted with the said control powder and then resultant intermediate products are reacted with an Al reducing agent powder. ### Claim 4 (depends on 1) The method as claimed in claim 1, wherein the control powder is included in an amount sufficient to absorb heat generated by the exothermic reactions and limit increases in reaction temperature to less than ΔT=600° C., and where the amount of control powder per 1 kg of metal chlorides is between Mc/100 and Mc; and M c = Max ⁡ [ 0 , Δ ⁢ ⁢ G - ∫ T min T r + Δ ⁢ ⁢ T ⁢ ( M b ⁢ C p - b + M AlCl ⁢ ⁢ 3 ⁢ C p - AlCl ⁢ ⁢ 3 ) ⁢ dT ∫ T r T r + Δ ⁢ ⁢ T ⁢ C p - b ⁢ dT ] wherein Tmin=Tr, and wherein the ratio of the one or more metal chlorides to control powder is between 0.03 to 1 and 100 to 1. ### Claim 5 (depends on 1) The method as claimed in claim 1, wherein the control powder further includes an aluminium chloride. ### Claim 6 (depends on 1) The method as claimed in claim 1, wherein the metal chloride is selected from a chloride of one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, and Mo. ### Claim 7 (depends on 1) The method according to claim 1, further comprising: preparing a first stream of materials including the one or more metal chlorides; preparing a second stream of materials including the Al reducing agent; and preparing a third stream of materials including the control powder; feeding said streams into a reaction zone and mixing and reacting the said streams at temperatures between 25° C. and Tmax; wherein: Tmax is below 1100° C.; the Al reducing agent comprises a pure element, an alloy or a compound based on Al; and the metal chloride is a chloride of one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, and Mo. ### Claim 8 (depends on 7) The method as claimed in claim 7, further comprising: continuously feeding and mixing materials from said streams at temperatures increasing from a temperature T0 to a temperature T1 for a first residence time and then at temperatures between T2 and Tmax for a second residence time; wherein T0 is between 160° C. and 600° C., T1 is below 660° C., T2 is between 200° C. and 700° C., and Tmax is below 1100° C.; and wherein the first residence time is sufficient to reduce substantially all the starting base metal chlorides to a chlorine content less than 50% of the chlorine in the starting base metal chloride. ### Claim 9 (depends on 1) The method as claimed in claim 1, wherein the metal chloride comprises one or more of ZnCl2, VCl(2,3,4), CrCl(2,3), CoCl2, SnCl(2,4), AgCl, TaCl(4,5), NiCl2, FeCl(2,3), NbCl5, CuCl(1,2), PtCl(4,3,2), WCl(4,5,6), PdCl2 and MoCl5, and wherein reactions between the metal chlorides and the Al reducing agent are exothermic at temperatures below 500° C. and with energy release exceeding 10 kJ per mole of the said metal chloride. ### Claim 10 The method as claimed in 9, wherein gaseous by-products produced by the exothermic reactions induce additional mixing of the one or more metal chlorides, Al reducing agent and control powder. ### Claim 11 (depends on 1) The method as claimed in claim 1, wherein the control powder is a pre-processed partially reduced or fully reduced product from the contacting step or the separating step, and wherein base metal species in the control powder has a Cl content less than 50% of the one or more metal chlorides. ### Claim 12 (depends on 1) The method as claimed in claim 1, wherein the metal chloride reacts with the control powder by chlorine exchange reactions and/or single replacement reactions to produce an intermediate reducible species. ### Claim 13 (depends on 1) The method according to claim 1, for producing one of an alloy, compound or catalyst, comprising performing the method of claim 1 to produce a metal alloy product containing one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, and Mo, and containing more than 10 wt % Al; and a further second step of removing the Al by dissolving in an alkali metal hydroxide or in an acid. ### Claim 14 (depends on 1) The method as claimed in claim 1, wherein the metal chloride includes Ta Cls NbCl5, MoCl5, FeCl3, WCl(4, 5 or 6), VCl(3 or 4) or SnCl4 and the method comprises a primary step of reducing the metal chloride to produce an intermediate product, including TaCl(0, 2, 3 or 4), NbCl(0, 2, 3 or 4), MOCl(0, 2, 3 or 4), FeCl(0 or 2), WCl(0, 2, 3, 4 or 5), VCl(0, 2 or 3) or SnCl2. ### Claim 15 (depends on 1) The method as claimed in claim 1, wherein the metal chloride includes Ta Cls NbCl5, MoCl5, FeCl3, WCl(4, 5 or 6), VCl(3 or 4) or SnCl4 and the method includes the steps of: reacting the metal chloride with a control powder and the Al reducing agent in a reaction zone at temperatures below 600° C. to produce a mixture of metal or metal alloy, Al or Al alloy and metal subchlorides; and condensing metal chlorides evaporated from the reaction zone and return them to the said reaction zone; the condensed metal chlorides being in a solid powder or a liquid form; and processing the resulting mixture of metal or metal alloy, Al or Al alloy and metal subchlorides to produce a base metal alloy. ### Claim 16 (depends on 1) The method according to claim 1, further comprising: preparing a first stream of materials including the one or more metal chlorides and alloying additive precursors; preparing a second stream of materials including the Al reducing agent; and preparing a third stream of materials including the control powder; feeding said streams into a reaction zone and mixing and reacting the said streams at temperatures between 25° C. and Tmax; wherein: Tmax is below 1100° C.; the Al reducing agent comprises a pure element, an alloy or a compound based on Al; the metal chloride is a chloride of one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, and Mo, and the precursor materials for the alloying additive precursors include one or more of pure elements, chlorides, oxides, or nitrides of an alloying element. ### Claim 17 (depends on 1) The method according to claim 1, further comprising: preparing a first stream of materials including the one or more metal chlorides and alloying additive precursors; preparing a second stream of materials including the Al reducing agent; and preparing a third stream of materials including the control powder; feeding said streams into a reaction zone and mixing and reacting the said streams at temperatures between 25° C. and Tmax; wherein: Tmax is below 1000° C.; the Al reducing agent comprises a pure element, an alloy or a compound based on Al; the metal chloride is a chloride of one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, and Mo, and the precursor materials for the alloying additive precursors include one or more of pure elements, chlorides, oxides, or nitrides of an alloying element. ### Claim 18 (depends on 1) The method according to claim 1, further comprising: preparing a first stream of materials including the one or more metal chlorides; preparing a second stream of materials including the Al reducing agent; and preparing a third stream of materials including the control powder; feeding said streams into a reaction zone and mixing and reacting the said streams at temperatures between 25° C. and Tmax; wherein: Tmax is below 1000° C.; the Al reducing agent comprises a pure element, an alloy or a compound based on Al; and the metal chloride is a chloride of one or more of Zn, V, Cr, Co, Sn, Ag, Ta, Ni, Fe, Nb, Cu, Pt, W, Pd, and Mo. ### Claim 19 (depends on 1) The method as claimed in claim 1, wherein the control powder is a pre-processed partially reduced or fully reduced product from the contacting step or the separating step, and wherein base metal species in the control powder has a Cl content less than 80% of the one or more metal chlorides.