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United States Patent (19 3,876,754 Pursley I45 Apr United States Patent (19 3,876,754 Pursley i45 Apr. 8, 1975 54 PREPARATION OF CHORINE PENTAFUORDE EXEMPLARY CAM (75 Inventor: John A. Pursley, Northridge, Calif. 1. A process for producing chlorine pentafluoride (73) Assignee: North American Rockwell comprising the steps of continuously passing fluorinc Corporation as one reactant and at least one member of the group consisting of chlorine, chlorine monofluoride and 22 Filed: June 9, 1964 chlorine trifluoride as another reactant into a reaction 21 Appl. No.: 374,886 chamber adjacent the lower end of the chamber, maintaining the temperature and pressure in the reac tion chamber sufficiently high to effect reaction be 52 U.S. Ct...................................... 423/466; 1491 tween sail reactants to form gaseous chlorine penta 5 l l int. Cl........................... C01b 7/24: CO 1 h 9) 8 fluoride in a mixture with gaseous fluorine; continu 58 Field of Search........................ 23/2()5; 423f466 ously passing said mixture from the reaction cham her at a place adjacent the upper end of the chamber into 56. References Cited a condensing chamber at a place adjacent the upper UNITED STATES PATENIS end of the condensing chamber; maintaining the tem 2,982,62() 51196 Beattie et al.......................... 23/205 perature in said condensing chamber sufficiently low 3.34.638 5/1964 Lawton et al..................... 23/205 X to effect condensation of chlorine pentafluoride from OTHER PUBLICATIONS said mixture; withdrawing condensed chlorine penta Stacey et al., Advances in Fluorine Chemistry, Vol. 4, fluoride from said condensing chamber, and continu Butterworths Inc., Washington, D.C., 1965, pp. 240 to (usly recirculating the uncondensed gils from the con 242. densing chamber at a place remote from the upper cnd of the condensing chamber to said reaction cham Smith, Science, Vol. 141, pp. 1039 to 1040 (Sept. 1 1, ber at a placc adjacent the lower end of the reaction 1963). chamber. Primary Eva miner-Leland A. Sebastian S Claims, 1 Drawing Figure Attorney, Agent, or Firin-Rohert M. Sperry PATENTED APR 81975 2 4. 5 42 2O (G 58 57, 5 50 53 as a cd co 49 2 8 68 SS Y sa) y 2 is a N-56 gal all 67 l INVENTOR. JOHN A. PURSLEY BY Meulue ATTORNEY 3,876,754 2 PREPARATION OF CHLORINE PENTAFLUORDE this invention by maintaining the temperature in the condensing chamber low enough to condense the fluo This invention relates to process and apparatus of in rides and by maintaining the temperature in the reac dustrial plant size for production of chlorine pentafluo tion chamber high enough to effect reaction. ride (ClF) by reaction of fluorine with at least one 5 The chemical reactions involved in this invention are member of the group consisting of chlorine, chlorine represented by the following equations: monofluoride (ClF) and chlorine trifluoride (CIF). This invention is an improvement on the invention Cl, +5F, - 2CIF ( . ) which is disclosed in patent application. Ser. No. CIF + 2 F. - CIF {2} 3 3,410, filed Sept. 30, 1963 now U.S. Pat. No. () 3,756,780, by Donald Pilipovich et al., for the synthesis of chlorine pentafluoride. As mentioned in that patent CIF -- F -s CIF (3) application, chlorine pentafluoride is an extremely high As is explained in the aforementioned patent applica energy oxidizer of greater oxidizing potential than chlo tion, Ser. No. 313,410, an increase in pressure will rine trifluoride which finds utility as an oxidizer for 15 cause an increase in yield of chlorine pentafluoride for rocket propellant fuels. The boiling point of chlorine each of the above equations, whereby pressures of pentafluoride is about -14°C. 20,000 psi, for example, would result in a more facile The fluorine and the chlorine-fluorides for the chem production of chlorine pentafluoride than 1,000 psi, for ical reactions of this invention are highly reactive with all organic compounds and with many inorganic com example. From an economical standpoint, it is desir pounds including glass and water with which they are able to employ conventional equipment rather than violently reactive. Stainless steel is resistant to reaction special heavy duty equipment. Balancing the factor of with the fluorine and chlorine-fluoride chemicals in cost of equipment for a small plant against increase in volved in the process of this invention; however, items yield due to increase in pressures, equipment designed of plant equipment having moving parts and employing to handle reactions occurring up to about 2,000 psi lubricants and elastomer seals are objectionable. provides satisfactory results. A practical minimum for It is a general object of this invention to provide pro plant production is a pressure of about 500 psi. cess and apparatus for continuous type production of As is set forth in the aforesaid patent application, chlorine pentafluoride, operable at high pressures with complete fluorination of chlorine and (or) chlorine out mechanical compression. fluorides to form chlorine pentafluoride is accom The apparatus of this invention includes a reaction plished by heating the fluorine and the chlorine chamber and a condensing chamber, the chambers containing reactant to a temperature of from about being inter-connected at their upper ends for flow of 100 to 400°C (preferably from 100° to 280°C) and by gas from the reaction chamber to the condensing compressing the reactants to at least about 100 psi, chamber with the pressures in the chambers being sub preferably to at least 330 psi. At temperatures signifi stantially the same. Fluorine as one reactant and chlo cantly above about 400°C severe corrosion of the reac rine and (or) chlorine fluoride as another reactant are tion vessels, (e.g., stainless steel, Monel metal) occurs continuously passed into the lower end of the reaction and the passive fluoride films on the reaction vessels chamber. The temperature and pressure in the reaction and flow lines either decompose or volatilize to present chamber are maintained sufficiently high to effect for 40 'fresh' metal for corrosion. mation of chlorine pentafluoride as a gas. The gaseous The yield of the pentafluoride, based on the chlorine mixture in the reaction chamber, which comprises fluo or chlorine-containing reactants is increased by using rine and chlorine pentafluoride, passes to the condens an excess of fluorine. When the reactants are fluorine ing chamber. The temperature in the condensing cham and chlorine, the mono, tri, and penta fluorides are ber is maintained sufficiently low to effect condensa formed; when the reactants are fluorine and the mono tion of the chlorine pentafluoride from the mixture. fluoride, the tri and the penta fluorides are formed, and The condensed chlorine pentafluoride settles to the when the reactants are fluorine and the trifluoride, the bottom of the condensing chamber from where it is pentafluoride is formed. The use of about twice the withdrawn. The uncondensed gas (primarily fluorine) stoichiometric quantity of fluorine for full fluorination is continuously recycled from the condensing chamber 50 to the pentafluoride provides improved yields; but if to the lower end of the reaction chamber. There is no the excess of fluorine be substantially increased then significant pressure drop from one chamber to the the reaction time decreases because of increased vol other. ume and consequent flow rate through the reactor, The motion of gases in the cyclical system of this in wherefore the yield decreases. vention, i.e., upward in the reaction chamber and 55 Inert gases, e.g., nitrogen and helium, do not affect downward in the condensing chamber, occurs through the qualitative aspects of the reactions of this inven convection as a result of the differences of density of tion; however, inasmuch as the process of this inven the gases in the respective chambers and the action of tion is cyclical and continuous, inert gases should be gravity. In the process of this invention, such convec avoided, otherwise they would accumulate in the sys tion is thermally produced. For the gases to ascend in tem and thereby substantially decrease the concentra the reaction chamber and descend in the condensing tions of the reactants. Purging of such noncondensible chamber, the static head of gas in the reaction chamber inerts may be effected through a vent at 80 in line 75. is less than that of the gas in the condensing chamber. Impurity traces of water or other oxygen containing In the case where the chambers are of the same height, compounds in the reactants cause formation of FCO, to induce convection it is needed only that the average 65 CIO, and FCIO as contaminants. Impurities of organic density in the reaction chamber exceed that in the con compounds result in fluorinated carbon compounds densing chamber. This is accomplished in the system of which would require periodic removal from the system. 3,876,754 3 4 The invention is hereinafter illustrated by description trifluoride. In a large scale plant the trifluoride is re with reference to the accompanying drawing, the single turned to the reaction chamber. FIGURE of which is a schematic representation of a The jacket 24 for the illustrated pilot plant is pro pilot plant for continuous cyclical flow operations in vided with a conventional refrigerative system permit volving chemical reactions of fluorine and chlorine to ting use of various temperatures. A tank 37 containing produce chlorine pentafluoride. a suitable heat-transfer fluid, e.g., trichloroethylene, is In the drawing, reference numerals 10 and 12 desig connected by flow lines 38 and 39 to the jacket 24, and nate a reaction chamber and a condensing chamber, a pump 40 recirculates the heat-transfer fluid through respectively, arranged sicle by side. The reaction cham the jacket 24 and the tank 37. For cooling the heat () transfer fluid, there is a cylinder 42 of liquid nitrogen ber 10 is defined by a tall cylinder 14 encircled by a connected by flow line 43 to a coiled tube 44 in the full-length jacket 15.
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