PROCESS FOR THE PRODUCTION OF AMMONIA

Abstract: Ammonia is prepared by passing a feedstock containing hydrogen and nitrogen over a catalyst comprising a Group VIII metal catalyst and an alkali or alkaline earth metal promoter supported on graphite-containing carbon of speci­ fied surface area characteristics. At least 75% of the hyd­ rogen initially present in the feed is converted to ammonia without recycle.

Description: PROCESS FOR THE PRODUCTION OF AMMONIA This invention relates to a process for the production of ammonia. With increased pressure on the worlds food resources the demand for nitrogen containing fertilisers based on ammonia has grown rapidly in recent years. Current Haber processes using nitrogen and hydrogen as feedstock generally use a potassium promoted iron catalyst, usually with other promoters such as alumina. The reaction EMI1.1 is highly exothermic and thus the equilibrium shifts to the right at lower temperatures. However, present day commercial catalysts are not sufficiently active at lower temperatures to enable the reaction to reach equilibrium within the short time the reactants are in contact with the catalyst. Activity increases with temperature and therefore a compromise has to be reached. Furthermore, these catalysts require the presence of relatively high concentrations of hydrogen in order to retain their activity. Thus previous processes have been limited to producing a reaction product containing ammonia and considerable quantities of unreacted hydrogen and nitrogen. In the case of commercial processes this has necessitated the provision of recycle facilities which are expensive both in terms of initial capital costs and subsequent operating costs. Our GB 1565074 discloses a process for the production of ammonia from nitrogen and hydrogen utilising a catalyst comprising (i) as support a graphite-containing carbon having (a) a basal plane surface area of at least 100 m2/g, (b) a ratio of BET surface area to basal plane surface area of not more than 8:1, preferably not more than 5:1 and (c) a ratio of basal plane surface area to edge surface area of at least 2:1 and preferably at least 5: :1, and (ii) as active component (a) 0.1 to 50%, preferably 1 to 30%, most preferably 5 to 10X by weight of a transition metal of the 4th, 5th and 6th horizontal Periods of Groups V, VI, VII and VIII of the Periodic Table expressed as % by weight of total catalyst and (b) 0.1 to 4 times by weight of (a) of a promoter selected from Groups IA or lIA of the Periodic Table or the lathanides or actinides. The Periodic Table referred-to in the present specification is the Periodic Table published on page 9 of the Classification Key for Patent Specifications, Division C2, Organic Chemistry, published by the Patent Office, London 1977. We have now discovered that the Group VIII metal catalyst disclosed in GB 1565074 is sufficiently active to achieve significant conversion even when the hydrogen is present only in low concentration and thus to produce a reaction product containing ammonia, unreacted nitrogen and little unreacted hydrogen. After product removal, the remaining material can be used as fuel gas or recovered cryogenically if necessary. Expensive recycle facilities are not required. Thus according to the present invention there is provided a continous process for the production of ammonia which process comprises passing a feedstock containing hydrogen and nitrogen over a catalyst comprising (i) as support a graphite-containing carbon having (a) a basal plane surface area of at least 100 m2/g, (b) a ratio of BET surface area to basal plane surface area of not more than 8:1, preferably not more than 5:1, and (c) a ratio of basal plane surface area to edge surface area of at least 2:1 and preferably at least 5: :1, and (ii) as active component (a) 0.1 to 50%, preferably 1 to 30X, most preferably 5 to 10% by weight of a metal of the 4th, 5th and 6th horizontal Periods of Group VIII of the Periodic Table, expressed as % by weight of total catalyst, and (b) 0.1 to 4 times by weight of (a) of a promoter selected from Groups IA or IIA of the Periodic Table, wherein at least 75Z of the hydrogen initially present in the feed is converted to ammonia without recycle. Preferably a plurality of consecutive reaction zones is employed and at least some product ammonia is removed from the line between each reaction zone and its successor and the resulting mixture, depleted in ammonia, is supplied to the succeeding reaction zone for further conversion to take place. This results in improved conversion yields. The product ammonia in the line between each reaction zone and its successor is preferably liquefied before recovery. Preferably liquefaction is achieved by heat exchange with the feedstock to that particular reaction zone with additional cooling. The system preferably comprises from 2 to 5 reaction zones. The preferred Group VIII metals are ruthenium and osmium, particularly the former. Preferred promoters are the alkali metals and barium, particularly rubidium and potassium. The graphite-containing carbon support may be prepared by the method disclosed in GB 1468441 comprising the steps of (1) an initial heat treatment in an inert atmosphere at a temperature between 900"C and 3330"C, (2) an oxidation stage at a temperture between 300"C and 12000C, and (3) a further heat treatment in an inert atmosphere at a temperature between 1000C and 30000C, preferably between 1400"C and 2100"C. The Group VIII metal component and the promoter may be added by conventional impregnation techniques as disclosed in GB 1565074. Prior to the introduction of the feed to be processed, the catalyst should be activated by heating in a reducing atmosphere, normally the hydrogen/nitrogen process stream. Broad and preferred ranges of process conditions are as follows: Broad Range Preferred Range Temperature OC 200-600 250-500 Pressure bars 30-300 60-200 Space velocity v/v/hr 100-30,000 500-10,000 Preferably the feedstock molar ratio of hydrogen to nitrogen is in the range 2:1 to 0.25:1, most preferably about 1:1. Because of the requirement of previous commercial catalysts for hydrogen and nitrogen in stoichiometric amounts, it was only possible to use steam reforming or partial oxidation processes with a cryogenic unit to supply pure oxygen and nitrogen. A gas containing a mixture of hydrogen and nitrogen in a ratio in the range 1:1 to 1.4:1 can readily be synthesised by the partial oxidation with air of a wide range of hydrocarbon materials ranging from natural gas to fuel oil and coal, and purified by conventional techniques. This provides a relatively cheap feedstock which could not be used by prior art processes utilising conventional catalysts since the hydrogen and nitrogen are present in the wrong proportions. The use of the single pass system also permits a larger concentration of inert components such as methane in the feedstock than previously. These must be minimised in conventional-systems since they build up rapidly to a high level in the recycle stream. Furthermore, the feedstock can be obtained from the partial oxidation unit at a pressure which is suitable for ammonia synthesis. The only compression required will then be for the air and feed supplies to the partial oxidation unit. Residual product can be recovered by washing with a weak aqueous solution of ammonia in the manner described in our GB 2034293-A. The invention is illustrated with reference to the accompanying drawing which is a simplified process flow diagram. Feedstock derived from synthesis gas containing nitrogen and hydrogen is fed by line 1 through a heat exchanger 2 to a first bed reactor 3 containing a catalyst. In the reactor 3 the feedstock is partially converted to ammonia. From heat exchanger 2, the intermediate product passes to a cooler/condenser 32 and then to a separator 5 from which liquid ammonia is removed by line 6 and unconverted nitrogen, hydrogen and gaseous ammonia are passed by line 7 through heat exchanger 8 and thence to a second bed reactor 9 similar to the first. Product from reactor 9 is passed by line 10 through heat exchanger 8 to a cooler/condenser 33 and then to a separator 11 from which liquid ammonia is removed by line 12. Lines 6 and 12 unite to form a further line 13 which removes anhydrous liquid ammonia product. Further similar beds can be added with similar arrangements for feed and intermediate product offtake. Unreacted gases together with some gaseous ammonia are removed from the separator 11 by line 14, passed through a cooler/condenser 15 and fed to an ammonia recovery system comprising an absorber 16 and a stripper 17. In the absorber 16 the gases supplied by line 14 are contacted with the absorbent which is a dilute aqueous solution of ammonia supplied by line 18. Ammonia dissolves in the solution and the resulting concentrated solution of ammonia is removed by line 19, heated in heat exchanger 20 and passed to the stripper 17. The unreacted gases, containing more than 75% nitrogen and traces of other materials, are removed by line 21. The offtake gas may be used to fuel the turbines required for the compressors in the system (not shown, as a general purpose fuel gas component, or the hydrogen may be recovered cryogenically and re-used. In the stripper 17 the aqueous solution of ammonia is heated and the gaseous ammonia driven off is removed by line 22 and passed to a total condenser 23. The liquid product is collected in a drum 24 from which product is taken by line 25 and a reflux stream returned to the stripper by line 26. Stripped solvent, i.e. a dilute aqueous solution of ammonia, is withdrawn from the base of the stripper by line 27, passed through the heat exchanger 20 and a further cooler 28 to a surge drum 29 from which it is pumped to the top of the absorber 16 by line 18. Heat is applied to the stripper 17 by means of a reboiler stream 30 which passes through a steam heated exchanger 31. The invention is illustrated with reference to the following Example. Ammonia was prepared from synthesis gas in a plant similar to that disclosed with reference to the drawing with the difference that the plant contained four reactors and ancilliary equipment and not two as shown. Feedstock analysis, reaction conditions and product yields are given in the following Table. EMI6.1 STREAM <SEP> NO. <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6 <SEP> 7 <tb> TITLE <SEP> SYNTHESIS <SEP> REACTOR <SEP> NO.1 <SEP> NH3 <SEP> RECOVERY <SEP> REACTOR <SEP> NO.2 <SEP> REACTOR <SEP> NO.2 <SEP> NH3 <SEP> RECOVERY <SEP> REACTOR <SEP> NO.3 <tb> GAS <SEP> EFFLUENT <SEP> REFRIG. <SEP> FEED <SEP> EFFLUENT <SEP> REFRIG. <SEP> FEED <tb> TEMP <SEP> ( C) <SEP> 335 <SEP> 357 <SEP> -33 <SEP> 322 <SEP> 339 <SEP> -33 <SEP> 309 <tb> PRES <SEP> (bar) <SEP> 69.7 <SEP> 68.0 <SEP> 67.7 <SEP> 67.7 <SEP> 66.0 <SEP> 65.7 <SEP> 65.7 <tb> HYDROGEN <SEP> 4199 <SEP> 2431 <SEP> 0.32 <SEP> 2431 <SEP> 1371 <SEP> 0.18 <SEP> 1371 <tb> METHANE <SEP> 45.8 <SEP> 45.8 <SEP> 0.14 <SEP> 45.6 <SEP> 45.6 <SEP> 0.14 <SEP> 45.5 <tb> NITROGEN <SEP> 2999 <SEP> 2410 <SEP> 0.36 <SEP> 2409 <SEP> 0.27 <SEP> 2056 <tb> ARGON <SEP> 27.2 <SEP> 27.2 <SEP> 0.09 <SEP> 27.1 <SEP> 27.1 <SEP> 0.09 <SEP> 27.1 <tb> AMMONIA <SEP> - <SEP> 1179 <SEP> 1060 <SEP> 119 <SEP> 825 <SEP> 735 <SEP> 89.8 <tb> TOTAL <SEP> 7271 <SEP> 6093 <SEP> 1061 <SEP> 5032 <SEP> 4325 <SEP> 736 <SEP> 3598 <tb> STREAM <SEP> NO. <SEP> 8 <SEP> 9 <SEP> 10 <SEP> 11 <SEP> 12 <SEP> 13 <SEP> 14 <tb> TITLE <SEP> REACTOR <SEP> NO.3 <SEP> NH3 <SEP> RECOVERY <SEP> REACTOR <SEP> NO.4 <SEP> REACTOR <SEP> NO.4 <SEP> NH3 <SEP> RECOVERY <SEP> FUEL <SEP> GAS <SEP> TOTAL <SEP> NH3 <tb> EFFLUENT <SEP> REFRIG <SEP> FEED <SEP> EFFLUENT <SEP> WATER <SEP> WASH <SEP> RECOVERY <tb> TEMP <SEP> ( C) <SEP> 318 <SEP> -33 <SEP> 298 <SEP> 295 <SEP> 49 <SEP> 49 <SEP> PRES <SEP> (bar) <SEP> 64.0 <SEP> 63.7 <SEP> 63.7 <SEP> 62.1 <SEP> 19.6 <SEP> 15.1 <SEP> HYDROGEN <SEP> 703 <SEP> 0.09 <SEP> 703 <SEP> 391 <SEP> - <SEP> 391 <SEP> METHANE <SEP> 45.5 <SEP> 0.09 <SEP> 45.4 <SEP> 45.4 <SEP> - <SEP> 45.4 <SEP> NITROGEN <SEP> 1834 <SEP> 0.23 <SEP> 1833 <SEP> 1729 <SEP> - <SEP> 1729 <SEP> ARGON <SEP> 27.1 <SEP> 0.45 <SEP> 27.0 <SEP> 27.0 <SEP> - <SEP> 27.0 <SEP> AMMONIA <SEP> 535 <SEP> 464 <SEP> 71.1 <SEP> 280 <SEP> 279 <SEP> 0.55 <SEP> 2538 <tb> TOTAL <SEP> 3145 <SEP> 465 <SEP> 2680 <SEP> 2472 <SEP> 279 <SEP> 2193 <SEP> 2583 <tb> Note: All flowrates in kg mols/h. 1036 tonnes/day Ammonia. The average gas hourly space velocities of the gases through Reactors 1, 2, 3 and 4 were 3,000, 2,190, 1,490 and 2,030, respectively. The catalyst contained 7% by weight ruthenium and 14% by weight of potassium. It was prepared by impregnating a graphite-containing carbon support with.aqueous solutions of ruthenium chloride and potassium nitrate. The support was prepared by treating that carbon sold by Degussa A.G. under the trade name BKIV by the three stage treatment disclosed in GB 1468441 involving heating in an inert atmosphere, oxidation and heating again in an inert atmosphere. It was then acid washed as described in GB 2033776-A. After the final heat treatment the graphite-containing-carbon had the following surface area properties: Basal Plane Surface Area (bpsa) : 391 m2/g BET Surface Area (BETsa) : 769 m2/g Edge Surface Area (esa) : 1.8 m2/g Ratio of BETsa to bpsa : 1.97 Ratio of bpsa to esa : 217

Claims: Claims: 1. A continuous process for the production of ammonia which process comprises passing a feedstock containing hydrogen and nitrogen over a catalyst comprising (i) as support a graphite-containing carbon having (a) a basal plane surface area of at least 100 m2/g, (b) a ratio of BET surface area to basal plane surface area of not more than 8:1 and (c) a ratio of basal plane surface area to edge surface area of at least 2: :1, and (ii) as active component (a) 0.1 to 50t by weight of a transition metal of the 4th, 5th and 6th horizontal Periods of Groups V, VI, VII and VIII of the Periodic Table, expressed as % by weight of total catalyst, and (b) 0.1 to 4 times by weight of (a) a promoter selected from Groups IA or IIA of the Periodic Table characterised by the fact that at least 75 of the hydrogen initially present in the feed is converted to ammonia without recycle. 2. A process according to claim 1 characterised by the fact that a plurality of consecutive reaction zones is employed and at least some product ammonia is removed from the line between each reaction zone and its successor and the resulting mixture, depleted in ammonia, is supplied to the succeeding reaction zone for further conversion to take place. 3. A process according to claim 2 characterised by the fact that 2 to 5 consecutive reaction zones are employed. 4. A process according to any of the preceding claims wherein the transition metal is ruthenium. 5. A process according to any of the preceding claims wherein the promoter is rubidium or potassium. 6. A process according to any of the preceding claims wherein the temperature is in the range 2.00 to 6O00C, the pressure in the range 30 to 300 bar and the space velocity in the range 100 to 30,000 v/v/hr. 7. A process according to any of the preceding claims wherein the feedstock molar ratio of hydrogen to nitrogen is in the range 2:1 to 0.25:1.

Inventors: LOGAN, MARTIN RAYMOND, MCCARROLL, JOHN JAMES, TENNISON, STEPHEN ROBERT
Applicants: THE BRITISH PETROLEUM COMPANY P.L.C.
Application year: 1982
Main classification: C01C1
IPC codes: C01C1