PATENT SPECIFICATION Application Date: Feb, 27, 1930, Ne, 6631 |: 30. Complete Left : Deo, 26, 1980. Complete Accepted : April 23, 1981. PROVISIONAL SPECIFICATION, Improvements in the Manufacture and Production of Metals from Metal Halides. 1, Janes Yar Joussox, a British Sub- ject, of 47, Tancoln's Lan Wilds, in tho County of “London, Gentleman, do hereby declare the nature of this faven- 5 tion (whieh lag been communicated to mo from ‘abroad. by. T. G._ Farbenindastrie ltenzeatha, of Fraaknrtonifain, Germany. a Joint ‘Stock Company organ ined under the Lins of Germany) ‘0 be 10 as follows Y faving regard to the hydrogen, halide axising in the reduction of metal halides with hydrogen it has" been customary Hitherto to constructor coat the apparatus 45 for the said reduction of or with ceramic anaterial My foreign correspondents have now fousd that the reduction aay he carried ou in a much more convenient manner ju a metalic, Zor example in an ordinary iron ‘or stool apparatus, provided that Ghose parts of the apparatie which come into contact with the. hydrogen. halide formed are kapt hot, ‘The employment of metalic apparatus he great arate age that the heat necessiry for carry ot the said reduction can bo directly supplied through the walls to the reagents ina convenient manner. ‘The tempera ‘80 tures at which the metallic parts of the apparatus are to be kept depend on the Specific metal employed and_the concen- {ration of the hydrogen hatide formed in the gus mixture, which may be higher the Ligier the temperature of the metallic parts,” has, for example in the case of fron the hydrogen chloride concentration sabe ab ih 260, per vent of the hvdrogen present when the iron parts are Kept at 700° Centigrade, srhereas the con- centration of hydrogen chloride may rise to about B0 per cent. at 000° Centigrade. Tron parts eoming into. contact with hydrogen halide should, however, never bp cooler than about 400° "Centigrade. Generally speaking, it ip advisable fo'uso for the construction of the apparatus the same metal as is to be produced therein, When employing a nobler metal than that to be proluceds for example copper for Apparatus in which fron is. fo be: pro. diveed, these “metallic parts. through ‘which’ the “heat “fs_not "supplied may i 45 50 he kept at lower temperatures than would be neceseary in the case of loss joble metal theconomtraton, of iydrogen halide may be higher, ‘The tiuploymont of melal for the construction of tie heat conveying parts is of particu. Jer advantage, sinco the production of retals from tho corresponding halides, for Sample the production of on fom iron fords by means of hydrogen, is in most tases strongly endothermic and therefore diffeatties atise when employing ceramic taterial for the construction of the appa- Totus a5 was usual hitherto, These dif callie are obviated. according’ to the Present invention by heating the reaction Chamber hy means of heating devices con- structed of metal. Any ris of the metal being corroded by an attack of hydrogen is much lessened by employing metals as Dare as possible, as for example iron free from caivon. ‘ihe following metals may, for example, be employed for the con: struction of the apparatus, copper, in, nickel, cobalt, “ehromium, end’ their halides may be reduced.” As. further Iietal halides which may be reduced by means of hydrogen. in apparatus con structed in accordance. with the present Enventjon inay be mentioned zine clorde, molybdenum’ chloride and tungsten chloride, The following Examples will further ‘Mluatrate the nature of this invention, but the invention is not resrcted to. these Examples. Exporter 1 6 kilograms of pure “sublimed iron chloride are charged into a wrought. iron tube, 1600 millimetres im length and 150 millimetres in internal diameter. In the tubo, which may be heated externally by meats of electrical resistance heating, js arranged a second iron tube 70. milli- sotres in internal diameter in which like- ‘wise an electrical resistance heating ele- ment is embedded. By leading for about 20 hours a current of 200 litres of hydro- gen per hour through the outer tube and Simultaneously heating the outer take to fan internal wall temperature of 600° Centigrade and the inner tube to an external wall temperature of 700° Centi- 346,921 90 105346,921 ‘grade, the outer tube becomes coated with 8 homogeneous, finely-orystalline layer of pure iron, while the greater part of the Hon sopaates in 9 more coherent form, 5 parily in exystals soveral, contimotres in See, on the inner heating tube, The thin coating layer on the outer tube isallowed to remain, the inner tube is withdrawn, the greater part of thé iron (about 2 kilo- grams) is removed therefrom, the appa- Fatus rouegumbld and fled with 9 fech charge. By working in this manner no comrosion whatever of the wrought iron paris of the apparatus takes place. ‘The 45 excess of hydrogen employed during the yeduction and which escapes with the hydrochloric acid formed is freed from the Iatier in the manner alveady known by washing with water, dried and retuned fo the process, Exar 2 10 kilograms of chromous chloride are heated at 950° Centigrade in a revolving ron, drum heated externally by means of heating gases while passing” hydro through the said drum at a rate of 2¢ 40 ubio metres per hour. 4050. grams of chromium in the form of fine needles are sbiaiued in 800 hours. ‘The chromium obiained is of great purity, in particular 1 fee fron cabo and therefore itis especially suitable for the production o chromium alloys, for example acid-proot steels and the Vike Exam: 3 Cuprous chloride is continuously passed at a rate of 10 kilograms per 2 hours throagh a revolving iron furnace heated externally by electric means, and heated at 450° Centigrade im a current of hydro- gen passed through the said furnace in the opposite direction ata rate of 5.5, cubic metres per hour. ‘The issuing gases are led away by means of tuhes of ceramic or similar acid-proot material. The copper is obtained am pulverulent amor- ‘phous form and in a state of great purity. Dated this 27th day of Bubruary, 1930, J. ¥, & GW. JOHNSON, 47, Lincoln's Tan Fils, London, W.C. 2, COMPLETE SPECIFICATION. Improvements in the Manufacture and Production of Metals from Metal Halides. I, Jaxms Yars Jorrson, a British Sub- ject, of 47, Tincoln’s Inn Fields, in the jounty of London, Gentleman, do hhereby declare the nature of this iaven- tion (Which has been communicated to me from abroad. by I. G, Farbenindustrie Alctiengesellechaft, of Frankfort-on-Main, Germany, a Joint’ Stock Company organ: ized under the Laws of Germany) and in what manner the same is to be performed, to he particularly described and ascer tained’ in and by the following state- ‘Having regard to the hydrogen halide arising in the reduction of metal bolides with hydrogen it has been customary hitherto to construct or coat the apparatus for the said reduction of or with ceramic matarial, My foreign correspondents have now found that the reduction may be carried out in a much more convenient manner in an apparatus constructed of ordinary iron suck as, for example steel, east iron or wrought iron, or iron alloys ‘consisting mainly of iron such as for example nickel or chrome steels, provided that those parts "75 of the apparnius whieh come into contact with the hydroren halide formed are kept hot. ‘The employment of iron apparatus ‘has the great advantage that the heat 50 5 60 0 necessary for carrying out the said redue~ Bee aa geared veg wally to tho reagents ina convenient Insnner, ‘The temperatures at which the iron parts of the apparatus are to be kept depend on the concentration of the hydro- fen halide formed. inthe. gas misture, ‘which may be higher, the higher the tem Deraiure of the iron parts, ‘Thus, for Gxamaplo the hytrogen chloride eoneentrac tion may be as hugh as 20 per cent. of the hydrogen present when te iron parts are kept at 100° Centigrade, ‘whereas the Concentration of hydrogen chloride ma Sino sbgut 6 pe cent a. 900 Cont je, Tron pars coming into contact Fith hydrogen halide. should, however, nares Cree an eeet Fens grade. The employment of iron for the onstruction of the heat, conveying” parts {S of particular advantage, since the pro- duction of metals from the cotresponding huaides, “for example, ‘the production of iton from iron eiloride ‘by means of hydrogen, isin most cases stronaly endothermic “and. therfore difleulies frit. when employing. eramie material for the consiruclion of the appt- rafus as wae usual hitherto, ‘These dite bullies aro obviated according to the present invention by heating the reaction 105346,921 3 chomber by means of heating devices con- structed of iron. Any risk of the iron being corroded by an attack of hydrogen is much lessened by employing iron oF 5 iron alloys as free as possible from sub- stituents which are removed by the action of hydrogen, as for example carbon, sul- phur and phosphorus. ‘The halides of the following metals may for example, be 40 reducolin the iron’ apparatus, copper, fron, nickel, cobalt, “chromium, snc, molybdenum and tungsten. ‘The following Examples will further illustrate how the invention is carried out 15 in practice, but the invention is not re- stricted ta ‘these Examples. ‘Exacres I. 6 kilograms of pure’ ‘sublimed iron chloride are charged into a wrought iron tube 1500 millimetres im longth and 150 nillimetres in internal diameter. In the tube, which may be heated extemally by meats of electriea) resistance heating, is arranged a second iron tube 70_milli- aietres in internal diaineter in which like- ‘wise an eleotrical resistance heating ele- ment is embedded, By leading for about 20 hours a current of 200 litres of hydro- zen per hour throngh the outer tube and 30 simultaneously heating the cuter tube to an internal wall temperature of 600° Centigrade and the immer tube to an external wall temperature of 700° Centi- rade, the outer tube becomes coated with 35 a homogeneous, finely-crystalline layer of pure iron, while the greater part of the tron, separates in a more coherent form, partly in crystals several centimetres in size, on the inner heating tube. The thin coating layer on theouter tube isallowed to remain, the inner tube is withdrawn, the greater part of the iron, (about. 2 kilo- rams) is removed therefrom, the appa- ‘plus reeled au llag with froth charge. By working in this manner no corrosion whatever of the wrought ixon parts of the apparatus takes place... ‘The excess of hydrogen employed during the reduction and which escapes with the hydrochloric acid formed is freed from the latter in the manner already known by washing with water, dried and retuned to the process. ‘Bsanene 2 10 kilograms of chromous chloride are heated at 950° Centigrade in a revolving iron drum heated externally by means of Theating gases while passing hydrogen through the said drum sta vate of 20 60 cubic metres per hour. 4050 grams of chromium in he form of fine needles are obtarned in 300 hours. The ehromium obtained is of great purity. in particular it is free from carbon, and therefore it is 65 especially suitahie for the production of 50 85 chromium alloys, for example acid-proof stele onl the tke Exon 3 Cuprous chloride is continuously passed at a rate of 10 kilograms. per 2 hours through a revolving iron furnace heated externally by electric means, and heated at 450° Centigrade in a current of hydro- gen passed through the said furnace in the opposite direction at a vate of 5. cubie metres per hour. ‘The issuing gases are led away by means of tubes of ceramic or similar’ acid-proof material. The coprer is obtained in pulverulent_amor- phous form and an a state of great purity. 7 kilograms of pure ferrous chloride ave filed into an ison tube of 1500 millimetres Iength and 150° millimetres internal diameter, the inner wall of the said tube being provided with a thin layer of quarts, In the tube is arranged a second fron tube of 65. millimetres internal diameter which is heated at an external temperature of about 700° Centi- grade by burning a mixture of carbon monoside and osygen in the tube, On passing hydrogen preferably preheated by means of the issuing hot gases for 24 hours over ihe ferrous chloride at a rate 95 of 200 litres per hour the ferrous chloride fs reduced and the bulk of the iron formed, about 3 kilograms, is, deposited on the inner tube and may be discharged therefrom after withdrawing the inner tue. Hating may also be effected by a flame- loss surface combustion of heating: gases in the inner tube. 400 Having now particularly deseribed and ascertained the nature of my said inven- tion and in what manner Ue same is {o Be performed, T declare that what 1 1. Tn the manufacture and production of metals by reduction of their halides by means of hydrogen, carrying out the reduction in au apparaty: of which at least the heat conveying parts are made of iron, or iron alloys consisting mainly of iron kept at a temperatnre of at least 400° Centigrade, 2, Apparatus for the manufacture and production of metals by rednetion of their halides by means of hydrogen of which at 420 Teast the heat conveying parts axe made of fron, or iron alloys consisting mainly 3, The process for the manufacture and production of metals substantially as de- seribed in each of the foregoing Examples. ‘4. Metals when prepared in accordance with the preceding claiming clauses, 105 410 115 125346,921 J, ¥, & GW. JOHNSON, ‘Dated this 28rd day of December, 1930, 47, Lincoln's Inn Fields, London, W.C. 2, Agents, Ueedhill: Printed for Hie Majesty's Stationery OlBoe, by Tare & Maleomson, Ltd—1981