Jan. 15, 1952 C. D., WLDER 2,582,941 PROCESSES OF PRODUCING URANIUM CHLORIDES Filed Oct. 2, 1944

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INVENTOR. 6ozEMAW Z. WZZZOER

ATTORNEY . Patented Jan. 15, 1952 2,582,941

UNITED STATES PATENT OFFICE 2,582,941 PROCESSES OF PRODUCING URANUM CHELORDES - Coleman D. Wilder, Oak Ridge, Tenn., assignor to the United States. of America, as represented bysion the United States Atomic Energy Commis Application October 12, 1944, Serial No. 558,452 8 Claims. (C1. 23-145) 2. - This invention relates to the manufacture of a pating carbon tetrachloride vapor in a speedy uranium chloride product, and more particularly stream of dry air, passing the resultant mixture re of uranium pentachloride over an uranium compound heated to the neigh - - - - - a ...... g a substantial proportion of borhood of 550° C. whereby uranium pentachlo uranium hexachloride, by a process for chlorinat: ride is formed and vaporized into the current, ing various, compositions comprising uranium moving the resulting vaporous mixture into a compounds, with carbon tetrachloride vapor car collecting receptacle so that most of the uranium ried by a Swift current of air. chloride will condense and settle out, and send This invention has for an object the rapid pro ing the gas stream through a dust separator to duction of a uranium chloride product compris strip it of the residual uranium-containing par ing a large proportion of uranium pentachloride ticles. and various proportions of uranium hexachlo The apparatus employed comprises a device ride. for supplying carbon tetrachloride, a device for A further object of the invention is to provide supplying dry air, a flash boiler in which the a high-yield, low-loss process for the production 5 carbon tetrachloride is vaporized and mixed with of uranium pentachloride which is economical the air, a reaction chamber in which the ai and suitable for large scale production of said carbon tetrachloride admixture is reacted with chloride. m the uranium-containing raw material, a heater A further object of the invention is to provide about the reaction chamber, a delivery duct for - a process for the production of uranium penta 2 conducting the vaporous reaction product from chloride and more or less uranium hexachloride the reaction chamber to collecting means, a re by means of a continuous reaction wherein vari ceiver for collecting the bulk of the principal ous compounds of uranium are reacted with product (uranium pentachloride, with or without vaporous, carbon tetrachloride which is carried uranium hexachloride) and an electrostatic sep by a rapid current of air. 2. 5 arator for removing the remainder of the reac A further object of the invention is to pro tion product that, in dust-like form, has been vide a process for the production of uranium carried through the receiver by the air stream. pentachloride and more or less uranium hexa Referring now to the drawing, there is shown chloride wherein a large effective reaction sur near the center a reaction vessel which comprises face and maximum heat transfer is obtained 30 a horizontal heat resistant cylindrical tube if, through employment of a high velocity of the constructed of Pyrex glass or the like, about 4. chlorinating mixture of carbon tetrachloride and inches in diameter and about 4 feet long. Lo 2. cated in the tube is an open-ended boat or A process has now been discovered and ap tray 3 containing a charge 3 of uranium com paratus designed for treating uranium com pound. For raw material such as uranium tri pounds, especially oxides and lower chlorides, Ox uranium tetrachloride, a charge of 10. with carbon tetrachloride in a swift current of 'o 15 kg. is commonly used. A heater compris air, whereby uranium pentachloride is formed, ing a refractory, shell is and a wound electrical vaporized, rapidly swept out of the reaction zone, resistance heating element 5 having two leads 6. and quickly cooled. 40 and a surrounds the tube . A tube 21 extends How the foregoing objects and related ends through a plug 22 of some heatresistant material, are accomplished will be apparent from the fol such as asbestos, into, the interior of the tube. lowing exposition, in which are disclosed the it at its a dit end, to provide ingress for the principle, the organization and divers embodi gases utilized in the treatment of the source mas ments of the invention, including the best mode terial. An iron-constantan, thermocouple (not contemplated for carrying out the same. Parts shown), inserted between the heater and the tube are given by weight throughout the written de it, is used to measureas: the furnace temperature. scription, which is amplified by the accompany The plug 22 is sealed to the tubes and 24 in a ing drawing of the apparatus in which the gastight manner by means of water glass or single figure is a diagrammatic side elevation view, 50 the like. partly in section, with some parts shown in con The gases passed into the reaction chambei. ventionalized form and some parts over-scale for through the tube. 2 include carbon tetrachloride. clarity. . . has beea thoroughly mixed with air In its broad aspect, the procedure compre a flash boiler 23, of whichwhi the tube 2 is an hended by the present invention comprises dissi extension. The lash boiler is preferably heated 2,582,941 3 - 4. by means of an electrically operated hot plate 92 in a gastight manner by means of water glass 26 controlled by a switch 27. The air enters the or similar luting compound. To prevent clogging boiler through an extension tube 24 which is of the passage for the reaction gases and to free connected to a source of Supply at the joint 25. the central portion of the cross 9 and its arm Ordinarily, the air is taken from an air pres 5 95 from any material which might accumulate sure line conventionally represented at 3. The on their interior surfaces during operation of the air passes through a joint 32 and line 33 to a apparatus, a scraper 97 carried on a rod 98 is drying device. 34 comprising an open-ended cyl provided. This rod is slidably and rotatably inder filled with calcium chloride. The line : 33 mounted in a plug 99, made of rubber or the like, extends through a plug 35 which seals the adit it) which closes the arm 93 about the rod in a ga S end of the drying device. 34. The air leaves this tight manner. A hand wheel 00 fixed on the device through a line 36 extending through a plug rod 98 serves as a means for manipulating the 37 Sealed in the exit end of the device 34. The scraper. - A simple plug 0 of rubber or the like line 36 conducts the air into a second and similar closes the arm 94 in a gastight manner. drying device 38 comprising an open-ended cyl The arm 95 extends through a plug 102 in the inder filled with anhydrous magnesium perchlo mouth of a large receiver 3, to a point near its rate. The line 35 extends through a plug 39 center. --Suitably the receiver is constructed of sealed in the adit end of the drier 38. The air glass or other chlorine-resistant material, and leaves the exit end of this device through a line has a capacity of about five gallons. The reac 40 which extends through a plug 4 sealed in the 20 tion gases pass down arm 95 into the receiver 3 exit end of the drier .33. The line 40 is con where the bulk of the uranium pentachloride set nected by means of a joint 42, with a line 43, tles out... The gas from which this material is which in turn is connected with the extension 24 separated in the receiver, escapes through a vent at the joint 25. tube to 4 also extending through the plug G2. Extending into the boiler 23 through a gastight The escaping gas passes through a joint 95, a plug 5 is a carbon tetrachloride feeder tube 52, line fos, a joint 07, a line. O8, and a side arm having on its end inside the boiler a capillary ?o for delivery to a device for removing the last nozzle 53. The tube 52 constitutes a part of a dust-like traces of uranium compound therefrom. carbon tetrachloride supplying device comprising Access to the principal part of the line 108 for a reservoir 55 and a tube 54 joining these parts. 30 cleaning purposes is gained by removing a plug The capillary nozzle 53 is of such dimensions that f09, thereby avoiding dismantlement of the appa a considerable pressure is necessary to force the ratus. carbon tetrachloride therefrom in the desired Usually, some of the uranium pentachloride is announts. Air pressure is utilized for this pur carried out of the receiver 03 by the stream of pose. . It is Supplied from a source of air pressure gas passing therethrough. This transported shown conventionally at 6. The air from this material is in the form of a powder that does Source is Supplied through a joint 62 to the line not settle satisfactorily and is difficult to collect. 63, which has, as a side arm, a conventional Preferably, it is recovered by a fume remover mercury manometer 64 for indicating the air of the electrostatic type. These devices (com pressure. The line 63 is connected through a monly referred to as “Cottrell precipitators') are joint 65 to a line 66 which incorporates a pres well known in the art and need not be illustrated Sure regulating device for maintaining constant or described in great detail. As indicated in the ly and accurately a predetermined pressure on the drawing, the gas containing the fine particles body of carbon tetrachloride in the reservoir 55 passes from the arm into a dust collector at and appurtenant parts of the carbon tetrachloride a joint 2. The gas flows through a tube 22, feeder. This pressure regulating device com a cap 23, a tube f24 where it is freed from ura prises a closed bottom cylinder 67 containing nium chloride, and a tube f 25 to a flue (not a body 68 of sulfuric acid, into which a side shown) for disposal or further use. tube 69 from the line 66 extends. A plug 70 The cap 23 serves as an insulator and is nor through which the tube 69 extends, closes the 50 mally constructed of Sone plastic or cera?ilic Open top end of the cylinder 67 in a gastight man material, for example glass. The cap is cemented ner. Any air passing downwardly through the in a gastight manner to the tube 24. This tube, tube 69 bubbles up through the body 68 of the which is one of the electrodes of the separator, Sulfuric acid and out through a vent tube must be electrically conducting and is usually which extends through the plug TO into the free 55 made of brass, but . other metals, for example Space above the sulfuric acid in the cylinder 67. stainless steel, . may be employed if desired. The cylinder 6 is arranged for sliding movement Extending through a seal 26 in the cap 23 is along the tube 69 so that the head of sulfuric a central wire 27, preferably of Nichrome or acid, through which air can escape, can be con similar metal, which serves as the other electrode trolled. This pressure regulating device pro 60 of the separator. The lower end of the tube 24 vides a very Satisfactory arrangement for main is fitted with and sealed in a gastight manner taining a definite uniform preSSUre. On the car to a collar 28 bearing a flange 29. This collar bon tetrachloride supply. The line 66 is con piece is preferably made of metal, for example nected through a joint 72, a line 73 and a joint stainless Steel. T4 to a line 75 which extends into the interior 65 A. frame comprising a bottom plate 39, the of the reservoir 55. In order to equalize the flange. 29, and a suitable series of bolts such as pressure between the reservoir 55 and the tube 52, f3 together with their respective thumb nuts 2, side arm T6 of the line 75 is connected through 32, holds a jar 33 With its mouth against the a joint to a line 78 which extends through a underside of the flange 29 in a gastight manner. plug 19 into the interior of the tube 52. 70 In order to insure proper insulation and spacing At the exit end of the tube is a two-inch of the wire f2 within the tube 24, there is a glass cross 9 having arms 92,93, 94 and 95. The scentrally located well 34, of glass or the like. arm 92 extends into the tube through a plug cemented to the bottom of the jar 33. Located 96 of Some heat-resistant material such as asbes in this well and suspended by the wire 27 is a tos, and this plug is sealed to the tube and arm, 3 heavy weight 35, of lead or the like. This weight 2,5829. S is free to move vertically so that the same tension short time, the gray-black color of the main body of the Wire is maintained even though the wire of the naterial and the yellow color of the sur may expand Or contract for Soine reaSon Sutch as face layer disappeared with the formation of a tenperature change. jet-black material, thereupon brown fumes con Electrical connections for impressing voltages nenced to form. The reaction mass at this stage between the tube 2A and the wire 2 comprise seemed to be a mixture of a liquid and solid. a high-potentiai conductor 39 and a ground wire The brown fumes condensed in the receiver in ... The separator operates on 25,000 volts D. C., the form of a fine brown powder. The treatment Supplied as indicated in the wiring diagram by was continued until the reaction maSS had dis two 110-volt A. C. transformers 36 and 3 and : appeared from the reaction chamber. Most of a rectifying device 38. the reaction product was a brown powder which in moving downwardly in the precipitator, the collected in the receiver, but a small amount finely divided uranium chloride particles become of a black crystalline substance comprising Sub electirically charged in the field existing between stantially UCls deposited at that end of the re the Wire 27 and the tube 28 and move out i. action chamber that joined the collector. The Wardly, separating from the fiuid stream and brown powder was very fine and gave an analysis depositing on the interior surface of the tube 2: of hexavalent uranium 27.1%, tetravalent ura in accordance with the well-known operation of nium. 29.5% and chlorine 4.1%. In this instance these devices. From this surface the particles the analysis was made very promptly and it is drop, upon jarring or Scaping if necessary, into possible that there may have been some con the jar 33, irgin which they are removed from densed carbon tetrachloride mixed with the time to time for suitable processing. brown powder. Considering now the mode of operation, a In this example and in subsequent examples, it charge of material is inserted in the tube , will be noted that the results of analysis are re preferably after being placed in a suitable tray, 2 ported in terms of percentages of hexavalent and and the flash boiler is then connected as shown tetravalent uranium. It will be understood that in the drawings. A current of air from the this method of reporting is used because the pro Source 3 is then passed through the driers 3. cedure of analysis for UCls involves splitting the and 38, the flash boiler 23, the reaction chainber uranium pentachloride product into a hexavalent in the tube , the arm 92, the cross 91, the re and tetravalent uranium compound and deter ceiver 3, the vent line comprising parts (4. mining the proportions of the two. From con f5, 8 and 0, the tube 22, the cap 23, the sideration of relative proportions, 27.1% hexa precipitating tube 24, the jar 33, and the ex Valent Uranium and 29.5% tetra Valent uranium tension 25. and 41% chlorine in Example I, it will be seen When the charge is at reaction temperature, 35 that the product has the empirical formula, pressure is applied from the Source 6 to the car UCl4.85 and comprises approximately 85% urani bon tetrachloride in the capillary nozzle 53, caus In pentachloride and 15% uranium tetrachlo ing it to drop into the boiler 23 where it is vapor ride, ized and intermingled with the previously de Ecample II scribed air stream, whereby it is passed over the s charge of uranium compound. The passage of The temperature of the reaction zone was the air-carbon tetrachloride mixture causes the raised to 550° C. and a charge of uranous-uranic formation of uranium chloride, which vaporized oxide (U3O8) placed therein. The starting ma into the gas stream and is carried along the pre terial had a purity of 99.8% and contained no viously described course thereby. Upon reach 5 chlorine. It had a hexavalent uranium to tetra ing the cooler portions of the apparatus, the valent uranium ratio of 2.01. The reaction uranium chloride condenses and the great bulk chamber was closed and a mixture of air and car of its settles in the receiver 03. Enough of the bon tetrachloride vapor passed swiftly there. material remains as a very fine suspension of through as described in Example I. The first particles in the gases to make further recovery noticeable color change, as the reaction pro worth While, and this material is removed from ceeded, was the formation of yellow needle-like the gas stream as it passes through the electro crystals on the surface of the reaction mass. static precipitator. These needles later disappeared, leaving a black, The invention will be further understood from molten maSS, similar to that formed when urani the consideration of the following specific ex um trioxide was the starting oxide. Some white amples. fumes formed early in the reaction. As the Eacample I yellow crystals disappeared, brown fumes Were given off and these were collected as a brown The temperature of the reaction zone was powder deposit in the receiver. Some of the raised to 550 C. and a charge of uranium tri- 6 brown material deposited immediately after leav oxide (UO3) placed therein. The material ing the reaction tube and the delivery tube had to charged had a purity of 99.2% and contained be tapped to eause it to fall into the receiver. neither tetraValent uranium nor chlorine. The For a short period after the brown fumes had reaction chamber was promptly closed and a begun to come off, the air and carbon tetrachlo mixture of air and carbon tetrachloride vapor ride were stopped and chlorine gas (alone) passed paSSed rapidly over the surface of the charge. through the reaction chamber. After about five The air was taken from a pressure line and dried minutes under these conditions, the reaction by passage through calcium chloride and anhy. stopped, no more brown powder being collected. dros ragnesium perchlorate in the order named, Thereafter the reaction was allowed to proceed as before being introduced into the reaction () previously described, with the change that small chamber. amount of chlorine was mixed with the air and The charge first changed to a gray-black color, carborn teachloride. This seened to cause a, resembling Somewhat uranous-Iranic oxide sheavier cloud of brown fumes to come from the (U3O8), and then a, at of yellow needle-like furnace and the material collected in the receiver Crystals formed over its whole surface. In a 5 was crystaine. - 2,582,941 7 8 The product collected gave an analysis of hex zone, at the rate of 6 cc. (liquid) per minute. a valent uranium. 29.2%, tetravalent uranium The reaction was continued for 38 hours. Urani 20.4% and chlorine 37.8%, i. e. the empirical um pentachloride was produced at the rate of formula was UCl5.11 indicating that the product 236 grams per hour. was 89% uranium penta chloride and 1.1% urani un hexachloride. The product analyzed was Eacample VII damp with carbon tetrachloride. The procedure of Example III was repeated Eacample III using a charge of 8 kilograms of a mixture of uranium pentachloride and uranium tetrachlo A charge of 4.5 kilograms of uranium trioxide 10 ride, as described in Example WI. Air contain was placed in the reaction- chamber at normal ing a small amount of chlorine was paSSed over room temperature and the temperature raised the charge at the rate of 225 liters per hour. to 550° C. A speedy current of air containing Carbon tetrachloride was mixed therewith at the carbon tetrachloride vapor was then passed over rate of 6 cc. (liquid) per minute as it entered the heated material. The air was dried by pas 5 sage through calcium chloride and anhydrous the reaction vessel. The reaction was contin magnesium perchlorate in Series, and passed into ued for 13 hours. Uranium pentachloride was the furnace at the rate of 100 liters per hour. produced at the rate of 369 grams per hour. The carbon tetrachloride vapor was admixed Eacample VIII with the air and passed into the furnace at the 20 rate of 5 cc. (liquid) per minute. The product The procedure of Example III was repeated was so fine a powder that great difficulty was using a charge of 8 kilograms of the Illixture of encountered in collecting it. uranium tetrachloride and uranium pentachlo At one time the air was shut off for a short ride described in Example VI. Air having carbon period. This caused the product to settle better, 25 tetrachloride mixed therewith at the rate of 6 but the rate of its formation appeared to be much cc. (liquid) per minute as it entered the reaction slower. The product collected was definitely vessel, was passed over the charge at the rate of wet with carbon tetrachloride, showing that an 300 liters per hour. The reaction was continued excess had been incorporated in the air stream. ioi 14 hours. Uranium pentachloride WaS pro Some uranium tetrachloride condensed in the . duced at the rate of 286 grams per hour. Appar cool portion of the reaction tube and caused eintly the higher rate of formation was due to the clogging difficulties. The material collected in faster flow of air. the main receiver gave an analysis of hexavalent Eacample IX uranium. 23.8%, tetra Valent uranium 33.9% and chlorine 41.6%, (UCl4.83). Additional material The procedure of Example III was repeated collected in the dust collector had an analysis of using a charge of 8 kilograms of uranium tetra hexavalent uranium 33.2%, tetra Valent uranium chloride including some uranium pentachloitide 26.1% and chlorine 37.1%, (UCl4.20). and having a slight amount of impurities, and having an analysis of hexavalent uraniuin 0.7%, Eacample IV tetravalent uranium 62.5% and chlorine 35.1%. The procedure of Example III was repeated 40 Air having carbon tetrachloride vapor mixed using a charge of uranium trioxide. Air was therewith at the rate of 6 cc. (liquid) per minute continuously forced through the apparatus at the as it entered the reaction tube, was passed ovel rate of 150 liters per hour, the air being admixed the charge at the rate of 373 liters per hour. The with the vapor of carbon tetrachloride intro reaction was continued for 7 hours. Uranium duced at the rate of 345 cc. (liquid) per hour. pentachloride was produced at the rate of 260 The temperature during the run was maintained grams per hour. No trouble was caused by the within the range 550° to 560° C. The run con Starting material being contaminated, aid the tinued for 70 hours. The cross at the end of the COritaminating Substances were not found in the reaction vessel was scraped every six hours. No final product. uranium tetrachloride was deposited within the 50 Eacample X reaction chamber. A yield of 1 gram of uranium pentachloride was obtained for each 4.31 grams The procedure of Example III was repeated of carbon tetrachloride used, using a temperature of 540° C. and a charge of about 10 kilograms of a 50:50 mixture of uranium Eacample V dioxide and uranium tetrachloride. Air, at the The procedure of Example III was repeated rate of 50 liters per hour, was passed through using a charge of 8 kilograms of uranous-uranic the reaction cylinder and allowed to escape at the oxide (U3O8) and a temperature of 540 to 560 delivery end thereof during the two hours re C. Air was passed over the charge at the rate of quired to bring the starting material up to the 130 liters per hour. Carbon tetrachloride was 60 Operating temperature. A vigorous stream of mixed with the air, before its introduction into carbon dioxide was passed through the collector the reaction zone, at the rate of 6 cc. (liquid) per System while the reactor was being raised to re minute. The reaction was continued for 63 action temperature, in order to remove any ai)- hours. Uranium pentachloride was produced at Sorbed moisture. The carbon dioxide passed the rate of 125 grams per hour. 65 through this part of the apparatus in a direction opposite to the course of the laden reaction gases, Eacample VI and was allowed to escape at the cross oi; the The procedure of Example III was repeated end of the reaction tube. Air was then iii: {d using a charge of 6 kilograms of a mixture of with carbon tetrachloride vapor at the rate of 8 uranium pentachloride and uranium tetrachlo 70 CC. (liquid) per minute, and passed over the ride having an analysis of hexavalent uranium charge at the rate of 100 liters per hou;. A co:- 6.6%, tetravalent uranium. 56.1% and chlorine position comprising about 40% uraniuin penta 31%. Air Was passed over the charge at the chloride WaS produced and separated froin the rate of 180 liters per hour. Carbon tetrachloride air current in the receiver at the rate of 256 grams was mixed therewith, before entry into the heated 5 per hour. 2,582,941 '9 10 Electingle XI stre. Assuming an optimum reaction tempera The procedure of Example X was repeated ture of about 550° C. and substantially atmos using a charge of 10 kilograms of a 50:50 mixture pheric preSSure conditions in the reaction Zone, of uranium dioxide and uranium tetracinioriie. these ranges for air and CC14 employed in the Air was passed-over the charge at the rate Qf 250 processimaybe...expressedimore generally, interms liters per hour. Carbon tetrachloride Was mixed of linear velocities of the gaseous inixture in the therewith, befo'e entering the reaction Zone, at reaction Zone (i. e., through an unobstructed the rate of 6 cc, Cliquid) per minute. A composi cross-section of the reaction Zone immediately tion comprising about 98% uranium pentaghlo following the ciiage), as equivalient to linear ve ride and 2% uranium hexachloride was produced O logities of about 1.7 to 5.i.cm. per Second for the at the rate of 225 grams per hour. &timixed gases, and wherein the air/CC14 ratio , the inixture Waries from about 1.3 to 3.2 by Wol Eacample XII time. Specific ratios of the gaseous components The procedure of Example X was repeated. &f the inixture and its linear Velocities for-other Air was passed over the charge at the rate of 490 15 reaction temperatures that lie Within the Scope liters per hour. Carbon tetrachloride WaSaixed of the invention may be readily calculated from with the air at the rate of 6.0 to 3.5 g.g. {liguit) tile data, given herein. per minute as it entered the reaction tube. A referabiy, the rate of addition of the carbon composition comprising about 68% uraniun tetrachloride is closely controlled. An excess does pentachloride and 32% uranium hexackaloiside 20 no harin as it is carriest through the apparatus was produced at the rate of.88 grams, per hour. and condenses With the Solid product, but an in Sufficiency Seems to hinder the conversion. For Eacample XIII charges in the neighborhood of 10 kilograms of The procedure of . Example X was repeated. uranium titioxide and an air fioW of 2U0 to 400 Air having Enixed therewith carbon tetrachloride 25 iiters per-hour, about 6 cc. of liquid carbon-tetra at the rate of 7.5 -cc. (liguid) per minute, Was caloride per minute seems to give SOmeWhat Su passed over the charge at the rate of 250-liters perior operating and conversion conditions. per hour. Uranium gentachloride was groduced ihere seems to be no limit on the size of the at the rate of 155 grains per holl'. batch of raw material treated. Excellent results 30 have been obtained with charges as Srinall as 4 Eacample XIV to 5 grams and as large as 10 to 15 kilograms. The procedure of Example X Was repeated. The charge may be placed in a hot furnace al Air was passed over the charge at the rate of ready at running temperature, or the furnace 250 liters per hour. Carbon tetrachloride Was may be heated up after the charge is in place mixed with the air, immediately before it en 5 therein, -as desired. Some white fumes are gen tered the reaction vessel, :at the rate of 8.2 CC, erally given off at low temperatures and their dis (liquid) per minute. Uranium pentaghloride was posal intust be considered as a factor when the prosiuced at the rate of 145 grams per hour. cold furnace-cold charge procedure is employed. iwiany compounds or mixtures of compounds of it is preferred that the charge be at a tempera ui'anium inay be used as the source Qf uranium ture in-the-range 546 to 560'. C., for example 550 with satisfactory results. Compoungs Such as C., during the conversion, but it is possible to rainium dioxide, uranium trioxide, uranous produce uranium pentachloride using tempera uranic oxide, uranium tetraoxide and uranium tures as low as 425°. C. Runs at the specific ten tetrachloride, being especially Suitable for the peratures of about 4.75° and 500° C. were quite reaction and readily available, aregenerally used. Satisfactory. The oxychlorides, uranous oxychloride (UOCl2) It is to be particularly noted that the linear ve and uranyl chloride (UO2Cl2) are also converted locities of the reaction gases in the reaction zone, satisfactorily. The charge generally disappears relative to the particle size of the charge, are coil pietely when it is made up of the aforemen such as to rapidly Sweep the reaction product tioned imaterials. - . . 50 from the reaction Zoine Without at the same time Air from an ordinary compressed air line has sweeping any. Substantial quantity of the charge been found suitable. The air may be dried in any out of the reaction Zone and into the product, re suitable manner. The calcium chloride and ceiver. magnesium perchlorate, cylinders described have The term 'joint'is employed to cover a readily been used for convenience. Equivalent drying Separable gaStight connection unless otherwise means and arrangements will be obvious to those indicated by the context. skiied in the art, after-consideration of the fore Although many of the advantages of the pres going description. ent invention will be obvious to those skilled in The indications are that the faster the flow of the art, it is desired to , direct attention to the air, the better the yield of uranium pentachloride 60 'features of (i) being able to use many different obtained. The formation of yellow crystalline types of starting in atterial, because many avail material at the egress end of they reaction-chahn able uranium coilingolands.or. Inixtures of uranium ber indicates an upper limit for the air flow. compounds, appear to be suitable assource mate States of fioW of 250 to 400 liters per-hour are-pre rial; (2) using air to obtain the desired high ferred, but good results have been obtained with streaming effect; (3) employing carbon-tetrachlo rates as low as 100 or 150 liters per hour. Ac ride, a readily available, economical and easily cCrdingly it may be Stated in general terms that handled material; (4) utilizing a simple, inexpen preferred flow rates lie in the range of about 100 sive and easily regulated apparatus; (5) bringing to 400 liters of air per hour, based upon the 4-inch about a rapid and co::plete conversion or utiliza reaction tube that has been described herein for tion of the raw materiali; and (6) obtaining the purposes of illustration. The carbon tetrachlo final product as a poWaier, a form that can be ride ezriployed with this air may vary from about handled easily. 300 to 500 cc. (liquid) per hour. These rates of In résumé, a swift stream of dry air, having flow of air are given in terms of its volume at intermingled thereWith carbon tetrachloride Wa room temperature (20 C.) and atmospheric pres 73 por, is passed over a body of uranium compound 2,582,941.

; : . * : : ; . . . : ; : 1. - 2 at a reaction temperature in the range 425 to range 540° to 560° C. to react therewith yielding 560° C., at a rate corresponding to approximately vapor of said higher chloride of uranium in ad 100 to 400 liters of air (measured at 20 Cand mixture with effluent gaseous reaction products atmospheric pressure) and approximately 300 to and recovering said higher uranium chloride. 500 cc. (liquid) carbon tetrachloride per hour from the effluent gaseous reaction products. through a reaction zone having a diameter of 5. A process for producing a chloride of ura four inches, to obtain a product comprisin nium having more than four atoms of chlorine,

uranium pentachloride with or without a sub-i to each atom of uranium therein comprising re stantial proportion of uranium hexachlorid acting a uranium compound containing uranium, The above ranges if molecularly combined with at least one element ride correspond4 to a rangeand of linear carbon velocities tetrachlo- for of the group consisting of chlorine -and oxygen in atomic proportions of less than five atoms to thecalculated gas mixture at a ofreaction about 1.7 temperature to 5.1 cm, per of secondabout each of uranium with a stream of carbon - tetra 550° C. and for a pressure in the reaction zone chloride vapor in admixture with air in which I of substantially atmospheric, and to a range of the volumetric ratio of air/CC14 is in the range . laratios (by volume) of about 1.3 to 3.2. 'I of about 1.3 to 3.2, which is flowing with a linear r, all the specific ranges of values for op-lii velocity of between about 1.7 to 5.1 cm. per second - conditions that are set forth herein are and at a temperature of between 425 to 560°, c. p ily for the purpose of better illustrating ielding the vapor of said chloride of uranium the invention, and one may depart from them 20 in the effluent mixture of gaseous reaction prod it considerably without sacrificing all the advan-i ucts, and recovering the chloride of uranium from tages of the invention, Said gaseous reaction products...... ; : ; ; ; ; : Probably many apparently widely different em. 6. ; The: ; ; ; ; process; ; ; ; ; ; ; ; ; as; ; ; ; defined; ; ; ; ; ; ; ; in; ; ; clai; ; ; wherein is is this invention may be made with Said uranium compound which is reacted with

arting from the principle, breadth and Said stream. . . . . of. . . carbon. . . tetrachloride vapor -inad spirit thereof, and it is to be understood that this "mixturefrom the with group air consisting comprises of auranous compound oxychloride, selected mentsinvention thereof is not except limited as to encompassedthe specific embodiin th uranyl chloride, uranium dioxide, uranium tri - claims. - - ; ; ; ; ; ; ; ; ; ; I oxide, uranous uranic oxide and uranium tetra What is claimed is: , chloride.7. In a , ,process , , for producing ai ; ;uranium ; ; ; ; ; chlo: ; ; ; ; ; : : 1. A process for producing the higher chlorides

of uranium comprising passing ride compound of the group consisting of ura h admixture with carbon tetracihloride vapor in rium pentachloride and uranium hexachloride ich the volumetric ratio of air/CC14 by the reaction of carbon tetrachloride vapor with diflowing at a linear veloci material selected from the group consisting | AA Arve in Aar-at-r- is a vir uranous oxychloride, uranyl chloride, uraniu dioxide, uranium trioxide, uranous uranic oxide and uranium tetrachlorid e improveme comprising; conducting the reaction by passing a stream of Said carbon tetrachloride vapor mixed eousnium reactionchlorides products, from Said and effiuent recovering gaseous said reac-ura- Witha air- inO a volumetric ratio in the range of tion productS. - about 1.3 to 3.2, air/CC14 and at a linear velocity 2. The process as defined in claim 1 wherein pf about 1.7 to 5.1 cm. per second over said ma said uranium oxide comprises uranium trioxide. terial. While maintained at a temperature in the 3. A process for producing a higher chloride of range of 425 to 560° C., whereby said uranium uranium comprising passing a stream of air in to chloride compound is more efficaciously produced. admixture With carbon tetrachloride vapor in 8. The process as defined in claim 5 wherein which the volumetric ratio of air/CC14 is about the temperature at which said uranium com 1.3 to 3.2 and flowing at a linear velocity of about pound is maintained during the reaction of said 1.7 to 5.1 cm. per second over uranium tetrachlo- admixture of air and carbon tetrachloride vapor ride maintained at a temperature of about 540° is in the range of about 540° to 560° C. , , to 560° C. to react therewith yielding vapor of COLEMAN D. WILDER. Said higher chloride of uranium in admixture with effluent gaseous reaction products, and recovering REFERENCES CITED Said higher uranium chloride from said effluent 55 The following references are of record in the gaseous reaction products. file of this patent: 4. A process for producing a higher chloride of N uranium comprising passing a stream of mixed UNITED STATES PATENTS air and carbon tetrachloride vapor in which the Number Name Date Yonetic ratio of air/CC is about 13 to 32 2,032,632 Renschler et al. ------Mar. 3, 1936 and which flows at a linear velocity of about 1.7 OTHER REFERENCES to 5.1 cm. per second over material selected from the group consisting of uranous oxychloride, Mellor: "Comprehensive Treatise on Inorganic uranyl chloride, uranium dioxide, uranium tri and Theoretical Chemistry,” volume 12, 1932, Oxide, uranous uranic oxide and uranium tetra pages 80, 83 and 84. chloride and maintained at a temperature in the 65 -