AMMONIA PROCESS DESCRIPTIO: Desulphurization unit: The natural gas feed stock supplied to NFCL contains no HS, but it is anticipated that future supplies may contain sulphur compounds which have to be removed in order not to poison the reforming catalyst and the LT shift catalyst. NG from battery limit is heated to 385 °C reaction temperature. In the feed stock pre-heater and is passed through the hydrogenator a bed of Nickel-Molybdenum catalyst is provided to catalyze the hydrogenation of organic sulphur compounds to HS. There are two types of organic sulphur compounds that may be present in the feed stock. One is called “Normal sulphur” containing HyS, COS, CS; and mercaptans and the other is called “Less reactive sulphur"containing thiophenes, thioether etc. In case of normal sulphur, except marcaptans, hydrogen recycle is not is consumed where as for less reactive sulphur, recycle hydrogen is consumed as per the following hydrogenation reactions. RSH + H; > RH + H;S (Mercaptans) . R,SR + 2H; > RH + R\H + HS (Thioethers) R,SR + 3H; > RH + R,H+2H,S (Thiophenes) If sulphur is present, natural gas is mixed with recycle gas from synthesis is compressor in order to avoid carbon deposits on the catalyst due to catalytic cracking o' higher hydrocarbons. If any of these gas mixtures pass through the hydrogenator reactor and reacts to produce H2S. The above reaction is exothermic but insignificant. H-S produced in hydrogenator reactor and that already present in NG is then removed in HLS absorbers containing one bed of ZnO catalyst to absorb the sulphur. The absorber are operating in series with the second vessel acting as guard, where the ZnO in first vessel is getting exhausted a break through of H2S from the first vessel may be observed the operation will continue with the second vessel is in service, while the first vessel is being reloaded with fresh catalyst. The sulphur content at the exit of hydrogenator reactor ZnO bed takes places as follows. ZnO + HS > ZnS + H,0 ZnO + COS > ZnS + CO,Reforming section (General Steam reforming is a vital part of the front end in ammonia producing plants. Here CO, COs, and Hy are generating during the reaction between methane and higher hydrocarbons present in the NG with steam. The steam reforming takes place in two steps: 1, Primary reforming. 2. Secondary reforming. The operating equilibrium parameters are 769 °C and 30.5 kg/em"g and the maximum tube wall skin temperature allowable is 800 °C, The methane cone at the exit or primary reformer is 14.03% and from the secondary reformer is 0.6%. Primary reforming: The hot desulphurised NG and the recycle gas mixture from reformer outlet is combined with HS steam to give a steam to carbon mole ratio of 3.3:1.0. The combined steam-natural gas-recycle gas mixture is preheated to 520 °C in heat exchanger coil located in the waste heat recovery seston ofthe primary reformer utilizing the heat from flue gases, leaving the reformer radiant section. Following the preheat. The gases are distributed through hair pin tubes, into vertical reformer tubes filled with nickel catalyst. The primary reforming of the natural gas is done in a HaldorTopse design side fired furnace. When hydrocarbons under go steam reforming the following reactions take place producing a mixture of H>, CO, COs, CH, and excess H2O simultaneously over nickel catalyst, C,H, + 2,H,0 > nCO; + 2n + m/2) Hy— heat CH, +H,0 > 3H; + CO- heat CO, +H, > CO + H,0 ~ heat For higher hydrocarbons reactions start at 500 °C and for methane at 600 °C.Secondary reforming: The partially reformed gas from primary reformer contains 14.03% CH, (dry basis). The methane content is further reduced to 0.6 mole% at high temperature in the secondary step. Here, in the secondary reformer, the heat is supplied by combustion of part of the gas achieved by mixing air into the gas as compared to the indirect heat by firing in the primary reformer. This combustion provides heat for the rest of the reforming. The methane slip exit primary reformer is so adjusted that the process air supplying the reaction heat in the secondary reformer will give the Hy/No ratio of 3:1 in the synthesis gas. ‘The partially reformed gas from the primary is directed to the refractory lined secondary reformer at 769 °C and 31 kg/em’g. Process air supplied by process compressor at 33 kg/cm?g and 177 °C is preheated to 550 °C in heat exchanger coils located in convection section of passes to secondary reformer. The reaction takes place between the part of partially reformed gas with in the upper empty space of reformer resulting in short rise of temperature to above 1200 °C. From the empty space, the gas passes down the nickel catalyst based where the reforming reaction is completed with simultaneously cooling of the gas. The outlet temperature is 943 °C and the methane concentration is 0.6%. In the combustion zone of secondary reformer, the following reaction takes place between process gas and air and oxygen gets completely consumed. Combustion Reaction: 2H, + 0; > 2H,0 CH, + 20; > CO; +2H20 Reforming reaction: In the catalyst bed methane reforming reaction takes place as follows: CH, +H,0 €9 3H: +CO CO+H,0 €> CO; +H; CO- Conversion: Carbon monoxide present in the reformed gas is converted to carbon dioxide in two shift converters, The following reaction takes place in the shift converters. CH,+H;0 > CO; + HzThe above mentioned shift reaction taking place in the shift converters. The converters will only proceed in contact with a catalyst. The equilibrium is favoured by low temperature and higher steam to gas ratio, while the reaction will be higher at higher temperatures, As the reaction results in temperature increases, the outlet gas will be at an unfavorable equilibrium if heat is not removed before the conversion is completed. Hence the conversion is completed in two steps. The shift reaction increases the amount of H, in the process gas. High Temperature Shift Conversion: ‘The HT Shift converter contains copper promoted iron oxide catalyst. At the main start of the plant, the catalyst must be activated, which is mainly a reduction of FeO) to Fe,0,. The reduction will take place at a temperature above 250 °C. But the temperature should not be allowed to exceed 400 °C during the reduction in order not to decrease the activity of the catalyst. When new, the catalyst can operate at q gas inlet temperature of 350 'C, Afterwards, the optimum inlet temperature will be higher but as long as the outlet temperature has reached 470 °C, the activity will only decrease slowly. The cold catalyst can be heated by steam alone, both when oxidized and reduced drops of liquid water on the hot catalyst may be introduced with the steam. The fresh catalyst contains however 0.3% sulphate which will be given off as HS during the first week of the operation. Normally the catalyst is not oxidized by steam alone, but should be oxidized by adding a small amount of air to the steam before it is accessible. As it is pyrophoric, it is in reduced state ow Temperature Shift Conversion: LT Shift convertor contains CuO, ZnO and AIO. As the catalyst is extremely sensitive to ‘S’ which may be liberated not only from the preceeding HT Shift catalyst but also from secondary reformer refractory material. The LT shift convertor is bypassed during the initial stage until the gas is practically ‘S’ free. The chloride may be present in the process steam and quench water, due to maloperation of the water treatment system and in very small amounts. Besides chlorides, sluphur and gaseous silicon compounds are also catalyst poisoning. When the catalyst is in a reduced state, temperature above 250 °C normally is avoided. A short exposure to 300 °C will have no adverse effect on the catalyst. The normal operating temperature is between 200-220 °C. The actual temperature of the inlet gas to be selected is dependent on the activity of the catalyst. The CO; content is reduced to 0.22 % (dry basis) in the LT Shift Converter.co2 oval section (G- 5 ‘This unit provides process gas free of CO, (limit 1000 ppm) for the production of ammonia and necessary CO, for urea production. In this unit, CO> in the process gas is absorbed by the GV solution in an Absorber. Stripping of the absorbed CO, is done in two tegenerators and CO; stripped is supplied to urea plant. CO; removal section known how is by Giammarco-Vetrocoke of Italy. The Vetrocoke solution consists of K,COs, Vanadium Pentoxide, Glycine and DEA where V:Os is the corrosion inhibitor and glycine/ DEA are activators. The chemistry involved in the removal of CO; is chemisorption and is as follows: CO+H,0 €9 HCO; +H =“) K,CO; + HCOs+ H” €> 2KHCOs K,CO, + CO, * H,0 €> 2KHCOy The reaction rate of (3) depends on the reaction rates of (1) and (2). Reaction rate of (1) is slow and the activator activates this reaction by quickly introdycing the gaseous CO, in the liquid phase. The activator glycine reacts with CO. and forms glycine carbonate according to the reaction NH,CH,COO’ + CO, €> COO" NHCH,COO + H™ COO" NHCH,COO'+ H20 €> NH;CH,COO'+ HCO; Solution regeneration is carried out at two pressure levels, one at 1.04 kg/em* and the other at 0.1 kg/cm? for better utilization of stripping steam compared to the usual technique in which great part of the stripping steam exits the regenerator as unused excess. In regeneration reaction (3) is reversed by the application of heat and pressure reduction and the lean and semi-lean K CO; solution is recirculated for further absorption of CO, The unconverted CO and the unabsorbed CO, remaining in the process gas are reduced to a limit of less than 10 ppm by methanation reaction. This reaction is important as CO and CO, act as poison to the catalyst in the ammonia converter. In the methanator the reverse of reforming reaction takes place in the presence of nickel catalyst, thus forming CH, which is an inert in the synthesis of ammonia. The reactions occurring are as follows3H, + CO €> CH, + H,0 CO; + 4H, €> CH, +2H,0 ‘The reforming reaction is reversed because of the lower temperature favouring the formation of methane. The methanator contains catalyst and has approximately the same characteristics as of the reformer catalyst, being nickel catalyst on ceramic base. The operating temperature of the methanator would be from 300 °C to 315 "C, depending on the catalyst activity and the gas composition. The process gas leaving the methanator contains 10 ppm of CO+CO>. Ammoni: ithe: The ammonia synthesis tales place in the ammonia convertor as, per the following reaction. Ny+3H, €> 2NH; ‘The reaction is limited by the equilibrium of ammonia and only part of the Hy and N3 can be converted to ammonia per pass through the catalyst bed. High pressure and low temperature favour the equilibrium concentration of ammonia where as higher temperatures enhance the reaction rates. There is a compromise between thermodynamics and chemical kinetics. As a result there is an optimum level for the catalyst temperature at which the maximum production is obtained. The synthesis loop is designed for a maximum pressure of 155 kg/em’g and the normal operating pressure is in the range of 131-141 kg/cm’g. The reaction temperature in the catalyst bed is 360 °C to 520 “Cwhieh is close to the optimum level. The catalyst used is a promoted iron catalyst containing small amount of non-reducible oxides. A considerable amount of heat is produced by the reaction (AH = -750 Keal/kg of NH3 produced), and this is utilized for the production of KS steam and for preheating the boiler feed water. The conversion per pass is about 20% of Hs and Np present in the converter inlet and is therefore necessary to recycle the unconverted synthesis gas the converter. The Ammonia converter is a HaldorTopse series 200, Radial Type converter with the gas following through the catalyst beds in the radial direction. The advantage of the radial flow is that the pressure drop is less. The catalytic activity of small particles is very high and the special advantage of the radial converter is to allow the use of small catalyst particles without a prohibitive pressure drop. The converter contains two catalyst beds with inter bed cooling after first bed. There is also a provision of cold shot HaldorTopse KML/KMIR is used. The first bed has a volume of 28 m’ of KMIR catalyst and the second bed contains 68 m° of KMI type catalyst. TheKMIR catalyst is the pre-reduced and stabilized catalyst of KMI type. Sulphur compounds and compounds containing oxygen such as water, carbon monoxide, and carbon dioxide are all poisons to the catalyst and small amounts of catalyst poison will cause a considerable decreased in the catalyst activity. ‘The various parameters affecting the Ammonia synthesis reaction are as follows: Ammonia concentration in the feed. Inert gas concentration in the feed. H)/N; ratio in the feed... Reaction temperature. Circulation rate. Operating pressure. Catalyst activity. Refris yn and Ammonia Absorption: ‘The refrigeration section is used to liquefy gaseous ammonia and consists of a two compressor unit, a condenser, an accumulator and number of chillers. Ammonia produced in the ammonia synthesis. Due to high pressure and low temperature the loop gases are dissolved in liquid in ammonia to a certain extent depending ‘on their respective solubility. These gases are removed from liquid ammonia by flashing. as Recove init: In order to maintain the inert concentration in the synthesis loop at a constant value, a continuous purge is taken from the point where the concentration of inert is the maximum, If H, from this purge gas can be recovered and used for NH3 synthesis, increase in NH production to an extent of 5-7% is possible without proportionately increasing the feed. In PGR Hy is separated by cryogenic cooling in the cold box. The purge is sent to the ammonia absorber where ammonia is absorbed in the water. Ammonia is recovered from the water by performing separation in a distillation column. The purge ‘gas, which contains traces of NH and HO, is sent through the adsorption unit where the molecular sieves are used to adsorb the traces NH; and HO. The remaining dry gas contains Hz, CH,, No and Ar is sent to cold box where the gas is cooled to below -180 °C, where almost all the CH, and Ar and some N; are condensed. The uncondensed H, is recovered and sent to the ammonia synthesis section.PROCESS FLOW DIAGRAM AMMONIA PLANTS Steam Air C02 free Flue gase: CO, to. Carbon Dioxide ( CO2) Urea Plants Liquid Ammonia “— Product &