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(12) United States Patent (10) Patent No.: US 7413,722 B2 Ikubo (45) Date of Patent: Aug

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(12) United States Patent (10) Patent No.: US 7413,722 B2 Ikubo (45) Date of Patent: Aug USOO7413722B2 (12) United States Patent (10) Patent No.: US 7413,722 B2 ikubo (45) Date of Patent: Aug. 19, 2008 (54) METHOD AND APPARATUS FOR 6,361,679 B1 3/2002 Kikkawa et al. MANUFACTURING NITROGEN 6,908,601 B2 * 6/2005 Satchell et al. .............. 423.406 TRFLUORIDE 6,984,366 B2 * 1/2006 Sylvret et al. ...... ... 423f406 6,986,874 B2 * 1/2006 Satchell et al. .... ... 423f406 (75)75 Inventor: Yuichi Iikubo, West Lafayette, IN (US) 7,074,3787,045,107 B2* 7/20065/2006 HartetDholakia al. et ......... al. .. ... 423f406 7,128,885 B2 * 10/2006 Satchell, Jr. .... ... 423/406 (73) Assignee: Foosung Co., Ltd., Seoul (KR) 2004/0096386 A1* 5/2004 Sylvret et al. ................ 423.406 (*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 U.S.C. 154(b) by 11 days. JP 62-104656 11, 1988 JP 63-014.725 1, 1989 (21) Appl. No.: 11/196,354 JP 62-277514 5, 1989 JP O1-0741.05 10, 1990 1-1. JP O1-0741.06 10, 1990 (22) Filed: Aug. 4, 2005 JP O1-334811 10, 1990 (65) Prior Publication Data (Continued) US 2007/OO31315A1 Feb. 8, 2007 Primary Examiner Wayne Langel (51) Int. Cl (74) Attorney, Agent, or Firm—Marshall, Gerstein & Borun COIB 2/083 (2006.01) LLP COIB 7/19 (2006.01) 57 ABSTRACT (52) U.S. Cl. ....................................... 423/406; 423/483 (57) (58) Field of Classification Search ................. 423/406, A method and apparatus for manufacture of NF by gas-liquid 423/483 phase reaction of fluorine and ammonia in molten3. ammonium See application file for complete search history. acid fluoride (AAF) in a static reactor in which the reactants (56) References Cited are conveyed primarily by thermal conduction or siphon. Optimally, the reactor contains one or more static mixing U.S. PATENT DOCUMENTS elements with little, if any, mechanical agitation. Reactant 3,043,662 A 7, 1962 Lipscomb et al. flow rate and reaction temperature are regulated by the rate of 3,055,817 A 9, 1962 Gordon et al. introduction of ammonia and cooling, as necessary The ratio 3,304.248 A 2f1967 Fullam et al. of hydrogen fluoride (generated by the reaction) to ammonia 4,001,380 A 1/1977 Gordon et al. in the reactor is significantly lower than taught in the prior art. 4,091,081. A * 5/1978 Woytek et al. .............. 423.406 This allows a lower reaction temperature. The present inven 4,543,242 A 9, 1985 Aramaki et al. tion is an improved synthetic method that offers enhanced 4,804,447 A 2f1989 Sartori selectivity and higher yields, improved control of reaction 4,975,259 A 12/1990 Hyakutake et al. kinetics, reduced operational and energy costs, and a greater 5,628,894 A 5, 1997 Tarancon 5,637,285 A 6, 1997 Coronell et al. margin of safety. 6,010,605 A 1/2000 Tarancon 6,183,713 B1 2/2001 Tokunaga et al. 23 Claims, 1 Drawing Sheet US 7413,722 B2 Page 2 FOREIGN PATENT DOCUMENTS JP 3O43251 T 1996 JP O9-357666 7, 1999 JP O1-0741.07 7, 1991 JP 10-137144 12/1999 JP O1-307242 7, 1991 JP 10- 141710 12/1999 JP O1-307243 7, 1991 JP 10-232049 2, 2000 JP O2-033457 10, 1991 JP 11-03.0333 2, 2000 JP O2-033458 10, 1991 JP 10-247239 3, 2000 JP O2-110167 2, 1992 JP 2000-029044 10, 2000 JP O2-164031 2, 1992 JP 10-278799 11, 2000 JP O3-215187 2, 1993 JP 11-237912 3, 2001 JP O3-21.5188 2, 1993 JP 3550.074 10, 2001 JP O3-211917 3, 1993 JP 2000-139846 11, 2001 JP 3O37463 3, 1993 JP 2001-376685 T 2002 JP O3-2742O6 4f1993 JP 2002-131823 11, 2002 JP 3O37464 6, 1993 JP 2003-029347 8, 2003 JP 3O43243 5, 1996 JP 2003-388952 6, 2004 JP 3.162588 5, 1996 * cited by examiner U.S. Patent Aug. 19, 2008 US 7413,722 B2 B US 7,413,722 B2 1. 2 METHOD AND APPARATUS FOR because the shear induced by mechanical agitation increases MANUFACTURING NITROGEN the Surface area of gaseous reactants resulting in an increase TRIFLUORIDE of un-reacted F. gas. Moreover, in contrast to the present invention, Method 2 BACKGROUND OF THE INVENTION 5 (electrolysis) is economically less efficient because it requires use of an electrolytic cell with nickel anodes. These The present invention is directed to a method and apparatus anodes Suffer Substantial corrosion and the process, therefore, for the manufacture of nitrogen trifluoride (NF) by reacting requires frequent maintenance not required by the present elemental fluorine (“F), gaseous ammonia (“NH) and a invention. Additionally, the energy costs for Method 2 are molten ammonium acid fluoride (AAF). In the preferred 10 higher than those of the present invention and the quality of embodiment, the method and apparatus concurrently pro the NH product is lower than that of the present invention duces co-product ammonium bifluoride (NHHF, ABF) because of metal ion contaminants. Finally, use of Method 2 that is salable after removal of excess hydrogen fluoride results in a Substantial expense for nickel anodes, an expense (“HF). that the present invention avoids. 15 Method 3 is the subject of several Japanese patent applica The reaction is accomplished in a static reactor without tions, but in comparison to the present invention, is difficult to significant mechanical agitation that may contain static mix control except in a lab scale because the gas-phase fluorina ing elements and that may be configured in a closed loop. The tion of NH is highly exothermic and reaction kinetics are present invention increases reaction selectivity and yield of more difficult to control than with a gas-liquid phase reaction nitrogen trifluoride while minimizing creation of undesired Such as that of the present invention. Also, previous attempts and unstable by-products and, simultaneously, reducing to produce NF by the direct fluorination method, (3), and by operational costs and improving control over reaction kinet direct fluorination of NH in molten ABF resulted in yields 1CS substantially lower than those of the present invention. In the preferred embodiment, flow of reactants is accom plished without adding significant energy to the process (for 25 Competing Chemical Reactions mixing or pumping, for example) in excess of the energy The basic competing reactions are as follows: required to remove the heat of reaction. 3F+NH->NF+3HF Reaction 1 The rate of introduction of the reactants and the mainte nance of a proper temperature along the length of the reactor 3F+2NH->N+6HF Reaction 2 controls reaction temperature. NF is used in many industries, 30 for example, in semiconductor manufacturing; flat display 4F+2NH->NF+6HF Reaction 3 panel cleaning; as a fluorine source in the preparation of fluorocarbons; and as an oxidizing agent for high energy 4F+2NH+HO->NO+8HF Reaction 4 fuels. NF has advantages over elemental fluorine and com Reaction 1 is the desired reaction. Reaction 2 is most peting products in these and other applications because it is 35 favored thermodynamically, but produces only undesirable relatively inert at low temperatures, e.g., 300°F. or below, N and HF. Minimizing reaction 2 requires minimizing the and, therefore safer and more convenient to handle. Further, reaction temperature, since lower reaction temperatures favor NF, can safely be compressed to high pressures, e.g., 1,700 Reaction 1. Reaction 3 produces N. F., which is unstable and psig for shipment. a significant safety hazard, and large quantities of undesired In contrast to the present invention, known methods of 40 HF. Reaction 4 results from poor quality NH and F. producing NF demonstrate poorer yields and are less effi Currently, the most commonly used process for producing cient. The three principal known methods for manufacturing NF, is described in U.S. Pat. No. 5,637.285 (“the 285 NF are as follows: patent”). As described in the 285 patent, NF is produced by 1. reaction of a fluorine gas reactant, a gaseous ammonia the direct fluorination of ammonium ions by contacting gas reactant and an acidic AAF (NHFX HF where the ratio of 45 eous F with a liquid phase acidic ammonium acid fluoride NH to HF is approximately 1:2.55 or greater, preferably (NHFX HF where x is 2.55 or greater, and preferably greater 1:2.65 or greater or 1:2.85 or greater, in an agitated reactor than 2.65 or 2.85) while NH is separately contacted with the with a flat blade turbine operating at power levels of 5000 liquid-phase AAF to generate ammonium ions. In contrast to watts per cubic meter of reactor volume, preferably more than the present invention, this process typically gives NF yields 50 of 65% to 90%, but only at an elevated mixing rate in a stirred 35,000 watts per cubic meter of reactor volume: reactor at operating temperatures of 260°F. to 400°F. (126.7° 2. an electrolytic method such as (1) utilizing a molten flux C. to 204.4° C.), preferably 260° F-320° F (126.7°C. to 160° of NH, a metal fluoride, and HF, and circulating the molten C.), with lower temperatures favoring Reaction 1. The F is flux from an electrolyzer, to an ammonia Solubilizer, to an contacted with liquid phase AAF by using a specially NF reactor, to an HF solubilizer, and back to the electrolyzer; 55 designed sparger, having a plurality of Small holes, and the or (2) molten salt electrolysis using a metal electrode and contact is enhanced by mechanical agitation with a flat blade ammonium hydrogen fluoride as an electrolyte; and turbine.
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