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This document discusses the history and commercial processes for producing urea. It describes three main commercial processes: the Snamprogetti process, Stamicarbon process, and Toyo Engineering-ACES process. The Snamprogetti process reacts ammonia and carbon dioxide at high pressure and temperature to form ammonium carbamate, which is then decomposed to produce urea. The Stamicarbon process uses two reactors in series and purification stages to remove impurities from the urea solution. The Toyo Engineering-ACES process feeds ammonia and carbon dioxide directly into the reactor and strips the product at reactor pressure before purification.
This document discusses the history and commercial processes for producing urea. It describes three main commercial processes: the Snamprogetti process, Stamicarbon process, and Toyo Engineering-ACES process. The Snamprogetti process reacts ammonia and carbon dioxide at high pressure and temperature to form ammonium carbamate, which is then decomposed to produce urea. The Stamicarbon process uses two reactors in series and purification stages to remove impurities from the urea solution. The Toyo Engineering-ACES process feeds ammonia and carbon dioxide directly into the reactor and strips the product at reactor pressure before purification.
This document discusses the history and commercial processes for producing urea. It describes three main commercial processes: the Snamprogetti process, Stamicarbon process, and Toyo Engineering-ACES process. The Snamprogetti process reacts ammonia and carbon dioxide at high pressure and temperature to form ammonium carbamate, which is then decomposed to produce urea. The Stamicarbon process uses two reactors in series and purification stages to remove impurities from the urea solution. The Toyo Engineering-ACES process feeds ammonia and carbon dioxide directly into the reactor and strips the product at reactor pressure before purification.
In 1828, WOHLER discovered that urea can be produced
from ammonia and cyanic acid in aqueous solution. Since then, research on the preparation of urea has continuously progressed.
In 1907, urea was produced on a limited industrial scale by dehydration of Cyanamid, which was obtained from calcium Cyanamid:
CaCN2 + H2O + CO2 CaCO3 + CNNH2
CNNH2 + H2O CO (NH2) 2
THEORY OF REACTION In all commercial processes, urea is produced first by reacting ammonia and carbon dioxide, in gaseous phase, at high temperature (165 170C), and high pressure (132 148 bar) in presence of ammonia- carbamate saturated solution in which the carbamate, in liquid phase is formed. The reaction is fast and exothermic:
2NH3 + CO2 NH2COONH4 (1)
H = - 117 k j/mol
In the second reaction, which is slow and endothermic, the ammonium carbamate dehydrates to produce urea and water.
NH2COONH4 NH2CONH2 + H2O (2)
H = + 15.5 k j/mol Urea Synthesis
UREA PROCESSES
1- The Snamprogetti (SNAM) process In this process NH3 and CO2 are converted to urea via ammonium carbamate at a pressure of 150 to 160 bar and a temperature of 180C to 190C. An molar ratio of NH3 to CO2 3.5 is used in the reactor to give a CO2 conversion of 65%. The reactor effluent enters a falling-film stripper where a large part of the unconverted carbamate is decomposed by the stripping action of the excess NH3 . Because of the high stripping temperatures (200-210C), bimetallic tubes (made of zirconium and 25-22- 2 stainless steel) are needed to avoid corrosion in the tubes and erosion near the bottom of the stripper. Residual carbamate and CO2 are recovered downstream of the stripper in two successive stages. The first stage operates at 17 bar, and the second stage operates at 3.5 bar. Ammonia and CO2 vapors from the stripper top are mixed with the recovered carbamate solution from the High Pressure (HP) / Low Pressure (LP) sections, condensed in the HP carbamate condenser and fed to the reactor. The urea solution that leaves the LP decomposition stage is concentrated in the evaporation section to make a urea melt.
2- Stamicarbon (STAC) process: 3-The Toyo Engineering-ACES (Advanced Process for Cost and Energy Saving) process :
In this process the synthesis section operates at 175 bar with an NH3 to CO2 molar ratio of 4.0 and a temperature of 185 to 190C. Liquid ammonia is fed directly into the reactor while gaseous CO2 is sent from the centrifugal CO2 compressor at the bottom of the stripper. The reactor effluent is stripped at essentially reactor pressure using CO2 as the stripping agent. The overhead gas mixture from the stripper is fed to two carbamate condensers in parallel. Here the gases are condensed and recycled under gravity to the reactor along with absorbent solutions from the HP scrubber and absorber. The heat generated in the first carbamate condenser is used to generate 5.0 bar steam, and the heat from the second condenser is used to heat the solution leaving the stripper bottom after pressure reduction. The ACES stripper uses a ferrite-austenite stainless steel as do the carbamate condensers. The reactor and scrubber are constructed with 316L urea-grade stainless steel. The inerts in the synthesis section are purged to the scrubber from the reactor top for recovery and recycle of NH3 and CO2 Unreacted NH3 and CO2 from several sources are eventually recycled to the reactor via HP and LP absorbers. The urea solution that leaves the stripper bottom is further purified in HP (17.5 bar) and LP (2.5 bar) decomposers. The urea solution is first concentrated to 88.7% in a vacuum concentrator and then to the required concentration for prilling or granulating. 4- The Heat Recycle Urea Process (HRUP): In this process ammonia, recycled carbamate and about 60% of the make-up CO2 feed are charged to the top of an open- ended reactor coil at 3200 psig (220 bar). Ammonium carbamate is formed within the coil, exits the coil at the bottom and flows up and around it. The exothermic heat of carbamate formation in the coil drives the endothermic dehydration of carbamate to urea on the outside of the coil. This isothermal reactor design allows the conversion rate to reach 77%. The reactor has a uniform temperature profile that eliminates corrosion in the bottom of the reactor. The decomposers produce a 68 to 70 wt% urea solution that is concentrated under low vacuum in the Urea Concentrator to an 88 wt%. An atmospheric, airswept, falling-film evaporator then evaporates the 88 wt% urea product to make a 99.7 wt% urea melt product that is ready for prilling or granulation. 2- Stamicarbon (STAC) process:
Step 1 - Synthesis A mixture of compressed CO2 and ammonia at 240 barg is reacted to form ammonium carbamate. This is an exothermic reaction, and heat is recovered by a boiler which produces steam. The first reactor acheives 78% conversion of the carbon dioxide to urea and the liquid is then purified. The second reactor recieves the gas from the first reactor and recycle solution from the decomposition and concentration sections. Conversion of carbon dioxide to urea is approximately 60% at a pressure of 50 barg. The solution is then purified in the same process as was used for the liquid from the first reactor. Step 2 - Purification The major impurities in the mixture at this stage are water from the urea production reaction and unconsumed reactants (ammonia, carbon dioxide and ammonium carbamate). The unconsumed reactants are removed in three stages3. Firstly, the pressure is reduced from 240 to 17 barg and the solution is heated, which causes the ammonium carbamate to decompose to ammonia and carbon dioxide: NH2COONH4 ________ 2NH3 + CO2 At the same time, some of the ammonia and carbon dioxide flash off. The pressure is then reduced to 2.0 barg and finally to -0.35 barg, with more ammonia and carbon dioxide being lost at each stage. By the time the mixture is at -0.35 barg a solution of urea dissolved in water and free of other impurities remains. At each stage the unconsumed reactants are absorbed into a water solution which is recycled to the secondary reactor. The excess ammonia is purified and used as feedstock to the primary reactor. Step 3 Concentration 75% of the urea solution is heated under vacuum, which evaporates off some of the water, increasing the urea concentration from 68% w/w to 80% w/w. At this stage some urea crystals also form. The solution is then heated from 80 to 110oC to redissolve these crystals prior to evaporation. In the evaporation stage molten urea (99% w/w) is produced at 140oC. The remaining 25% of the 68% w/w urea solution is processed under vacuum at 135oC in a two series evaporator-separator arrangement. Step 4 - Granulation Stamicarbon developed a fluid bed system in 1976. The basic principle of the process involves the spraying of the melt onto recycled seed particles or prills circulating in the granulator. These seed particles gradually increase in size as the process continues. The heat of solidification is removed by cooling air. Since the contact time between liquid urea and air is much lower than in prilling, the dust formed in granulation processes is much coarser, and it is easier to remove. All granulation processes require the addition of formaldehyde to the urea before it is sprayed on the crystal seed surface. Formaldehyde serves as and anti-caking agent during the granulation process and slows the release function so that the fertilizer efficiency is higher The Theory Concept of Granulation Process The granulation process is basically depends on increasing in the size of the seed particle, and that can be done one of the following methods: - a) Agglomeration Binding of the particle together by the melt or solution, and that led to non-homogeneity in the formation, and low mechanical properties for the formed granule. b) Stratification The size of seed particle is increased simulteancy with accumulation of the layers around the kernel and this method is celled abo onion formation. c) Accretion The size of the seed particle is increased by the continuous evaporation of the solution and the crystallization of very small particles on the kernel. All Hydro Agri fluidized bed granulation; depend on the second method for the formation of urea granules. Their granules are homogenous and have very high mechanical properties and low moisture content.
Theory of Condensation The condensation reaction is the first reaction that takes place in urea plant. The reaction may achieve in two common types of condensers: I- The falling film condenser or vertical type II- The pool condenser or horizontal type The condensation capacity of the two types of condenser is determined by the heat transfer coefficient, the surface area of the tube bundle and the temperature difference between the process side and cooling side.
The theory of condensation is depending on the following items: 1- Pressure of condensation 2- Temperature of the reactants on the top tube sheet 3- Temperature of the cooling medium in the shell 4- NH3: CO2 molar ratio (1.8:1) 5- H2O: CO2 molar ratio 6- Gas: liquid molar ratio As seen from equation (1), three moles are reacted to yield only one mole. According to the decrease in volume in the direction of carbamate formation, the pressure will promote the reaction. In the most cases, applying pressure of 142 - 148 bar is optimum. The gas feed temperature must be enough to evaporate a considerable amount of ammonia dissolved in the (CO2 - NH3 - H2O) liquid feed. The temperature of the (CO2 - NH3 - H2O) liquid feed is 105 120 C. As seen also from equation (1), the condensation of CO2 and NH3 is an exothermic reaction. To promote this reaction, a cooling for the reactants must be built in the shell of the condenser. The cooling medium in the shell side of the high pressure condenser must be of a temperature of a value that adjusts the rate of condensation reaction. Below this value, the carbamate formed will crystalline. A cooling medium of a temperature of 145- 150 C being optimum to increase the condensation reaction, in the liquid phase, without crystalline formation of carbamate which usually takes place below 145 150 C, at pressure of 142 - 148 bar . Theory of Conversion In the next step of the formation of urea, 75% of the gases in the top of the carbamate condenser are condensed through the vertical tubes, while 25% of the gases are sending, associated with that condensed, to the reactor. The chemical interaction between NH3 and CO2 results in a strongly azeotropic behaviour of the binary system NH3 - CO2. An approach to the description of the phase equilibria if urea and H2O are added to the NH3 - CO2 system was given by KAASENBROOD and CHERMIN. They found that, the equilibrium in the NH3 - CO2 - H2O urea system under a pressure of 142 - 148 bar and NH3 : CO2 of 3 : 1 show the maximum CO2 conversion at high temperature. In the NH3 - CO2 - H2O system, the urea conversion according the equation (2) is a slow endothermic reaction. As a result, the conversion of CO2 into urea will be slowly independently of the chemical reaction rate. In this way, a significant residence time will be needed before all the vapours can be transported into the liquid phase, where the heat being realized and the global equilibrium can be reached. On this fact, it can be concluded that in the majority of the urea reactors the equilibrium is not reached, as there is strong evidence that gases of NH3 and CO2, in big amount, are still present at reactor outlet. The literatures on this conversion clarify that the conversion of carbamate into urea need at least 18 25 minutes at temperature profile of 176 183 C. Theory of Scrubbing In this step of reaction, the reactor gas effluent, the non reacted NH3 : CO2, are let to react at a lower temperature, compared with reactor, at the same high pressure also. As in the high pressure carbamate condenser, the condensation of the rest of the gases takes place in presence of a hypothetical mixture or initial mixture (CO2 - NH3 - H2O) liquid feed of a concentration lower than that fed to the high pressure carbamate condenser. The reaction is also takes place in a vertical set of tubes. The two phases are located in the bottom of the tubes set, in which the reaction started. The theory of the carbamate condenser is also applied, in which a cooling medium must be applied to promote the reaction. Increasing the ratio of H2O : CO2 molar ratio in the mixture results in a dramatic decrease in the reaction between the gases of NH3 and CO2, but of course increases the reaction between the gas of NH3 and the H2O in the liquid state. For this reason, the molar ratio of NH3 : CO2 in the gas mixture must be high enough to keep the ratio of gaseous NH3 : CO2 over 2: 1 after completing the reaction between the gas of NH3 and the H2O in the liquid state. In general cases, the H2O : CO2 ratio of the hypothetical mixture, fed to scrubber, from recirculation, is of 2 - 2.5 : 1, which indicates that: the NH3 : CO2 molar ratio in the gas mixture fed to scrubber must be, at least of 4.5 :1 The reaction in this stage usually proceeds as follow: 1. The gases are fed with the hypothetical mixture in the bottom of the scrubber 2. The gas liquid mixture goes up through pipes, in which the absorption for ammonia, in gas phase, into the liquid phase takes place to a certain limit The reaction of H2O and CO2, then, takes place in the ammonia rich liquid mixture and the heat of reactions are propagated to the cooling medium in the shell of the scrubber, which flows in countercurrent with the passage of reaction in tubes, to propagate the reaction Theory of Stripping From the late fifties until now, the energy requirements of urea plants have been reduced dramatically; steam consumption was in the order of 2 tons per ton of urea, excluding the energy to drive the carbon dioxide compressor. At present, this figure is 0.6 to 0.7 tons per ton, depending of course on steam quality. The steam pressure needed in these old urea plants was admittedly lower. Typically steam of approximately 12 bar was required while todays stripping plants need a steam pressure of at least about 20 bar. This large difference is mainly due to improvements made in the process itself rather than the increases in plant size that have since taken place. When the stripping process in the mid-sixties introduced, a saving of more than 40 per cent over the best existing conventional urea process was achieved.
References : 1- Synthetic Nitrogen Products Gary R. Maxwell DuPont Chemical Solutions Enterprise Memphis, Tennessee 2- Manual of Urea Plant Abu Qir Fertilizers Company