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    United States Patent 09 Pinto [54] AMMONIA PRODUCTION PROCESS Alwyn Pinto, Stockton-on-Tees, England Imperial Chemical Industries Limited, London, England [21] Appl. No: 939,916 [75] Inventor: [73] Assignee: [22] Filed: Sep. 5, 1978 [30] Foreign Application Priority Data Sep. 16, 1977 [GB] United Kingdom wun 38713/77 [51] Int, CL? co1c 1/04 [52] US... 423/359; 423/361; 422/148 [58] Field of Seareh se 423/359-363; 125/374 377; 55/15; 422/148 bs References Cited US, PATENT DOCUMENTS 3,441,393 4/1969. Finneran eta. 1 23/359 3,705,009 12/1972 Dougherty 23/361 FOREIGN PATENT DOCUMENTS 1156002. 6/1969 United Kingdom. so 423/389 1136939 4/1970 United Kingdom .... 423/359 a 4,213,954 (45) Tul, 22, 1980 OTHER PUBLICATIONS ‘Olsen et al, Unit Processes & Principles of Chem. Eng., 1982, pp. 1-3. Primary Examiner—O. R. Vertiz. ‘Assistant Examiner-—Thomas W. Roy ‘Attorney, Agent, or Firm—Cushman, Darby & Cushman 1571 ABSTRACT ‘An ammonia production process comprising synthesis ‘gas generation and ammonia synthesis with heat recov- ery in the generation section by steam raising and steam superheating and heat recovery in the synthesis section by steam raising or boiler feed water heating is made ‘more controllable by effecting part of the superheating in the synthesis section, so that a shut-down of the syn- thesis section results not only in a decrease in steam flow through the superheaters, but also in a decrease in ‘the temperature of the steam fed to them, Thus over- heating of the superheaters, a defect of some earlier processes, is avoided. The process is operated with a synthesis pressure under 150, preferably 40-80 bar abs. and preferably synthesis gas generation is based on primary hydrocarbon steam reforming at such a pres ‘ure that synthesis gas compression is by under 50%. 7 Claims, 1 Drawing Figure Jul. 22, 1980 4,213,954 U.S. Patent 4,213,954 1 AMMONIA PRODUCTION PROCESS PROCESS OF PRODUCING AMMONIA vention relates to a steam system and in partic- lar to a process of producing ammonia including the system. Processes for producing ammonia comprise the suc- cession of three main chemical reactions, namely reaction of carbon with steam and/or oxygen, for example: Ci4+10CO+3H CHOCO 10-400 te City .0-+0042 shift reaction ©0410-0024 and ammonia synthesis 2 1, SHy2NHs Each of these reactions produces a gas at over 400° C., from which useful heat can be recovered as steam or boiler feed water. In the last decade processes have become established in which steam has been generated at high pressure, usually in the range 60-200 bar abs., Supetheated, let down in turbines exhausting at the pressure just over that at which reaction Ta is carried but, partly used in reaction Ia and for the rest let down in condensing turbines or turbines exhausting at low pressure. Various ways of integrating the heat recover- tes from the hot gases have been proposed. Tn one sys- tem, described in U.S. Pat. No. 3,441,393, steam is raised in boilers heated by process 28s from reactions 1 and IE and by flue gas from the furnace in which reaction Ia is carried out, the steam is superheated by the flue gas before being let down in the turbines, and the heat evolved in reaction IIs taken up by heating feed water forthe boilers, There have been many proposals to raise steam in a boiler heated by reacted ammonia synthesis ts (reaction III), and such steam can be superheated by heat exchange with the flue gas derived from reaction I. ‘A process in which steam is superheated by heat ex- change with process gas is described in Chemiker- Zeitung 1974, 98(9), 438-445. ‘These prior systems are subject to a control defect, namely that a shut-down of the ammonia synthesis sec- tion (steps c and d below) of the ammonia production process while the synthesis gas generation section (steps and b below) continues in operation results in a de- rease in the supply of boiler fed water and/or steam from the synthesis section and thus to @ decrease in the flow of steam through the superheaters. Since itis im- practicable to shut down the generation section quickly, the superheaters become overheated and may suffer Gamage. ‘We have now realised that if the ammonia synthesis pressure is les than 150 bar abs., for example in the ange 40-80, especially under 60 bar abs., it becomes possible to avoid this control defect. This is because itis practicable to construct a heat exchanger having steam 0 35 45 35 65 2 at 60-150 bar abs., on its cold side and ammonia synthe- sis gas at less than 150 bar abs., on its hot side, and thus to superheat steam in the ammonia synthesis section. By contrast, in synthesis processes at higher pressure it was practicable only to have water on the cold side of such heat exchanger, in order to keep down its tempera- ture. Thus in our process, whereas a shut-down of am- ‘monia synthesis decreases the flow of steam in the su- pecheatets in the generation section, it also decreases ‘te total superheating capacity of the plant and leaves those superheaters adequately loaded. ‘According to the invention an ammonia production process comprises the steps of {@) reacting a carbonaceous feedstock with steam and- ‘Jor oxygen to give a gas containing carbon monox- ides (b) reacting the product of step (a) over a shift catalyst to convert carbon monoxide and steam to carbon dioxide and hydrogen and removing carbon oxides and steam from the resulting gas; (©) reacting the hydrogen with nitrogen over an ammo- nia synthesis catalyst, cooling the reacted synthesis, ‘gas and recovering ammonia from it; (@) heat exchanging hot gases produced in at least step (©) with water in a boiler producing steam at a pres- sure in the range 60-200 bar abs. and/or in a water heater feeding such a boiler; (©) superheating steam from such a boiler by heat ex- ‘change with hot gases produced in step (a) or step (b); and (0 letting dowa such steam in one or more expansion ‘engines and thereby recovering useful power; and is characterised by in step (€) @ reacting and cooling the synthesis gas at a ‘a pressure under 150 bar abs., and ‘cooling the reacted synthesis gas at least partly by superheating steam produced in step (4) and/or re-heat- ing steam within or from one or more of the engines of step (0). In the succeeding description the term “stage” will be ‘used to denote an operation forming part of the above defined steps. Step (a) can be any suitable gasification process, for ‘example non-catalytic partial oxidation of coal, residual hydrocarbon or vaporisable hydrocarbon, catalytic partial oxidation of vaporisable hydrocarbon or cata Iytic steam reforming. Catalytic steam reforming is conveniently carried out in two stages: primary reforming a hydrocarbon feedstock with steam to give a gas containing carbon oxides, hydrogen and methane. This stage is carried out with external heating with the aid of a furnace, the flue gas of which is one of the hot gases produced in step (a); and secondary reforming the gas from primary reforming. by introducing air and bringing the mixture to equilib- rium, whereby to produce a hot gas containing nitro- ‘gen, carbon oxides, hydrogen and a decreased quantity of methane. The hydrocarbon feedstock is preferably methane or other steam reformable hydrocarbon such as a normally lgaseous or liquid hydrocarbon boiling at up to about 220° C. Primary reforming can be in one stage over a ‘catalyst with external heating or, when the feedstock is of a higher molecular weight than methane and espe- cially when it is normally liquid, can be in two stages, in the first of which the feedstock is converted to a gas of hhigh methane content at an outlet temperature under 4,213,954 3 (650° C. and in the second of which that gas is reacted in the externally heated process. Various types of sup- ported nickel catalyst are available for these hydrocar- bon-steam reactions. The feedstock preferably should be substantially sulphur-free (under 0.5 ppm S) and may 5 hhave been subjected to a preliminary catalytic hy-

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