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1 F. HABER & R. LE ROSSIGNOl. PRODUCTION OF AMMONA. APPCATION FLED AUG, 13, Patented 0ct, 31, SN s: St. SEAL t -> Ei. Aa 44 / A. g; Ag/fader 2 t/ 2 weams suicidity itains

2 UNITED STATES PATENT OFFICE. FRIZABER, AND RoBERT LE ROSSIGNOL, OF KARLSRUHE, GERMANY, ASSIGNORSTO BADISCHE ANILIN & SODA FABRIK, OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY., A CORPORATION OF BADEN. PRODUCTION OF ANYONIA.. Specification of Letters Patent. Patented Oct. 31, Application filed August 13, Serial No. 12,680. o all whom it may concern: Be it known that we, FRITZ HABER, Ph. change of heat takes place much more rap D., professor of chemistry, and ROBERT LE idly... ordinary than when the gases are maintained at RossIGNOL, bachelor of science, subjects, re Should this transfer spectively, of the King of Prussia and the ence of heat from the hotter gases to the King of England, residing at Karlsruhe, cooler gases be insufficient to reduce the tem Germany, have invented new and useful Im perature of the hotter gases to the degree 60 provements in the Production of Ammonia, necessary to enable the ammonia to be con of which the following is a specification. veniently extracted therefrom, additional 10 Although it is known that on passing means of cooling should be employed. The mixture of nitrogen and hydrogen over a. removal of the ammonia from the gases as catalyst at a raised temperature a small frac aforesaid can be effected either by cooling 6 tion of the gases is converted into ammonia, the mixture of gases containing ammonia no method for carrying out this process so until the ammonia separates out in a liquid as to produce ammonia on a technical scale state, or the ammonia can be absorbed by has hitherto been discovered (see Zeitschrift means of any suitable absorbing agent, or fir Elektrochemie, 1907, p. 24). Attempts these two methods can be combined in such 70 have been made to increase the quantity of a manner that the first, more easily conden ammonia formed, by withdrawing the am sable portion of ammonia is removed by con 20 monia from the gases after they leave the densation and the remainder is then extract catalyst and then passing the gases thus ed by means of an absorbing agent. In freed from ammonia again over the catalylst either case, the removal of the ammonia 7 (Zeitschrift fir Anorganische Chemie, vol. takes place without the pressure to which 44, p. 376), but the results obtained have not the gases are subjected being released. We have further discovered that if the condi led to any technical process being discovered. We have now discovered that ammonia can tions under which the process is being be obtained from its elements in a manner Worked are such that a comparatively high 80 concentration of ammonia is obtained in the which is capable of commercial existence by passing a mixture of nitrogen and hydrogen, gases leaving the catalyst (for instance by or gases containing them (the proportion using a very effective catalyst, such for in - being preferably one volume of nitrogen to stance as osmium, or by working at a very high pressure), the advantages obtained 8 each three volumes of hydrogen), over a catalytic agent at a high temperature and from a heat regeneration, such as hereinbe removing at a lower temperature the am fore described, are of relatively less impor 3 monia contained in the gases leaving the tance, so that the process can be carried out catalyst. The gases from which ammonia by working under continuous pressure and has been removed are then passed over the separating the ammonia from the gases leav 90 catalyst again and this may be done by re ing the catalyst in the manner hereinbefore turning the gases to the part of the appara described, without causing heat to pass from tus containing the catalyst over which they the gases leaving the catalyst to those from have already passed and so treating them re which ammonia has been removed and which peatedly with the same quantity of catalyst. are about to pass over the catalyst. 9 One method of carrying out the process Further, the process must be carried out con tinuously under pressure and the quantity 'according to our invention may be as fol 4 of ammonia removed from the gases may be lows: The catalyst is introduced into a me replaced by an equivalent quantity of nitro tallic tube to the end of which a heat regen gen and hydrogen and at the same time the erator is attached. The heat regenerator 100 hot gases leaving the catalyst can be used can be of any suitable form, for instance it to preheat the gases from which ammonia. may consist of a worm tube with a number 0 has been removed and which are about to of narrow, coils, or it may consist of a sys be passed over the catalyst. In order to tem of such tubes, or it may merely be a effect this regeneration of heat, a small pre number of straight parallel tubes. The gas- 10 eous mixture containing nitrogen and hy heater is sufficient, since when the gases be ing treated are subjected to pressure the ex drogen in suitable proportions enters the other end of the metallic tube, passes over -.

3 e. 20 SO the catalyst, then through the heat regener The coil c is connected by the pipe d with ator and then through the condenser, ab the coil d' in the cooling vessel D, the said sorber, or the like, to a circulating pump. coil d' terminating in a vessel E for the con From this pump the gases are returned densed ammonia, a pipe e passing up from along the outside of the aforesaid worm or this vessel and being connected to the inlet of other tubes of the heat regenerator, abstract a circulating pump F the outlet pipef from sing heat from the gases contained therein, which communicates with the end c of the and they then pass outside the tube con coil c. The pipeg having a tap g is for taining the catalyst and then into the other supplying to the system nitrogen and hydro end of this tube, over the catalyst again. A gen, or gases containing nitrogen and hy branch tube can be employed to admit of the supply of nitrogen and hydrogen to replace drogen. For the reason aforesaid, we pre the quantity removed in the form of am fer to supply pure hydrogen and nitrogen in combining proportions. The supply is, of monia. The parts of the apparatus to be course, effected at a pressure which will en kept heated are preferably covered with heat-insulating material and the whole ap able the gases to enter against the internal paratus is arranged so that the circulation can take place at a suitable If The tubes c, c' constitute the aforesaid heat regenerator which, together with the desired, the catalyst can be supplied with an amount of heat above that contained in or tubes or pipes, A and B, are inclosed in the tube H, the whole being strong enough to produced by the system, for instance, elec withstand the pressure employed, the small trical heating can be employed. The tem opening a at the end of the tube A being to perature, at which the catalyst is maintained prevent the tube A being burst by pressure varies according to the material used and inside it in excess of pressure outside it. enerally lies, say, between 00 and 1000 Packing of insulating material is filled in g But in employing the expression "high between the tube H and the tube B and coil temperature herein we do not mean to limit ourseives necessarily to a temperature as c, as shown at I. An electrical resistance wire J is shown wound around the tube B high as 00 C. The pressure can be varied for the purpose of heating the catalytic sub within wide limits, for instance the process stance or the gases as they pass to the cata can be carried out at a pressure of 10 at mospheres. If a higher pressure be em lytic substance. The liquid ammonia can be drawn off by the pipe e and tape. ployed the concentration of the ammonia When using the apparatus just described, increases and vice versa. If the liquid am monia which is obtained according to this the procedure may be as follows: Fill the example is not used as such, but is converted tube A with finely divided iron and then again into the gaseous form, it is advisable heat slowly by means of an electric current through the wire J while passing the gase to use the cold produced during its evapora tion for the purpose of cooling the gases ous mixture of nitrogen and hydrogen leaving the catalyst. through the apparatus. When the tempera When gases, other than simply nitrogen ture has reached about 60 C., increase the and hydrogen in combining proportions are pressure in the apparatus to about 10 at mospheres, by pressing the gases in through continuously introduced into the system and the valve g'. Then set the circulating pump the neutral gas or gases accumulate and F in action and apply a suitable cooling reach such a concentration that the reaction between the nitrogen and hydrogen is ad agent to the coil d' in the vessel D. Here upon the greater part of the ammonia is versely affected, the gases should be let out from the apparatus so that the apparatus liquefied and collects in E, while the un changed gases together with a fresh portion can be charged afresh with gases as at the commencement of the operation. We pre of the gas mixture which has passed into the apparatus through the valve G' are caused fer, therefore, always to work with nitrogen and hydrogen as pure as possible and in com to pass once more through the regenerator bining proportions so that the operation c, and the reaction tube A. We wish it to be understood that the need be interrupted as seldom as possible. The accompanying drawing represents in above is only one method of carrying out our vertical section an apparatus adapted for invention, and that the invention is not con carrying out the process of our invention. fined to this method, since it is readily ap A is a tube containing the catalytic sub parent that it can be varied in many ways stance and open at the end a, so as to com without departing from the nature of the invention. municate with the space b, between the tube Now what we claim is: and the tube B. The end a' of the tube A communicates with the coil c which is in 1. The process of producing ammonia by closed in an outer coil c' so as to leave a space between the two coils. The coil c. at constitutes a continuation of the tube D. a lower temperature ammonia contained in 70 SG 8 0 a 3u

4 O the gases leaving the catalyst, and then again been removed over a catalyst at a high tem perature while carrying out the process con tinuously under pressure and replacing the quantity of ammonia removed from the gases by a fresh quantity of free nitrogen-and hy drogen. 2. The process of producing ammonia by again passing the gases from which ammo nia has been removed over the catalyst by returning them to the part of the apparatus containing the catalyst already used, while carrying out the process continuously under pressure and replacing the quantity of am quantity of free nitrogen and hydrogen, 3. The process of producing ammonia by again passing the gases from which ammonia has been removed over the catalyst by re turning them to the part of the apparatus containing the catalyst already used, while carrying out the process continuously under 4. The process of producing ammonia by ammonia at a lower temperature from the gases leaving the catalyst and then again passing the gases over a suitable catalyst while carrying out the process continuously under pressure and maintaining substantial uniformity of pressure during the whole of the operations, -. The process of producing ammonia by leaving the catalyst while carrying out the process continuously under 6. The process of producing ammonia by leaving the catalyst, and repeating the oper ation on the uncombined gases while carrying out the process continuously under 7. The process of producing ammonia by leaving the catalyst and repeating the opera tion on the uncombined gases while carrying out the process continuously under, pressure and maintaining substantial uniformity of pressure during all the operations. 8. The process of producing ammonia by agent, removing ammonia as a base from the gases leaving the catalyst, and repeating the operation, while protecting the catalyst from the introduction of detrimental substances, and while carrying out the process continu ously under pressure and maintaining sub stantial uniformity of pressure during all the Operations. 9. The process of producing ammonia by ing out the process continuously under pres sure and replacing the quantity of ammonia removed from the gases by a fresh quantity of free nitrogen and hydrogen and at the same time causing the hot gases leaving the catalyst to preheat the cooler gases from which ammonia has been removed and which are about to be passed over the catalyst, 10. The process of producing ammonia by ing out the process continuously at a pres sure exceeding that of one hundred atmos pheres and replacing the quantity of tam quantity of free nitrogen and hydrogen. 11. The process of producing ammonia by ing out the process continuously at a pres sure exceeding that of one hundred atmos pheres and replacing the quantity of am quantity of free nitrogen and hydrogen, and at the same time causing the hot gases leav ing the catalyst to preheat the cooler gases from which ammonia has been removed and which are about to be passed over the cata vst. y; The process of producing ammonia by in a liquid state and at a lower temperature B OO 10 O 1

5 10 14 ammonia contained in the gases leaving the catalyst, then passing the gases from which ammonia has been removed over the catalyst, while carrying out the process under con tinuous pressure, and replacing the quantity of ammonia removed from the gases by a fresh quantity of free nitrogen and hydro Cel The process of producing ammonia by passing the gaseous mixtures of nitrogen and hydrogen around a catalyst at a high temperature and into a suitable condenser at a lower temperature and removing ammonia, therefrom and then adding to the gaseous mixture from which ammonia has been ex tracted a new supply of nitrogen and hydro gen, the whole of the operations being con ducted continuously under 14. The process of obtaining ammonia by gen and hydrogen, under pressure continu ously around and over a catalyst at a high temperature and then cooling said, mixture and extracting ammonia therefrom and add ing to the gases which remain after the ex traction of ammonia new nitrogen and hy drogen to an amount equivalent to the am monia removed, the whole of the operations being conducted continuously without re lease of the. 1. The process of producing ammonia by gen and hydrogen in desired proportions continuously under pressure over and around a catalytic substance and forcing new nitrogen and hydrogen under pressure into the mixture in a quantity equivalent to the diminution caused by the drawing off of the ammonia. In testimonv whereof we have hereunto set our hands in the presence of two sub scribing witnesses. FRITZ HABER. ROBERT LE ROSSIGNOL, Witnesses: J. ALEC, LLOYD, A. RENSLINGER. 3