4 DEVELOPMENT OF A PROCESS THE MANUFACTURE © A CASE STUDY UREA The primary purpose an concluding this book with a case sludy is tn show students how the chemistry they have learned is used in the solution of & veal industrial problem, We have tried to do this by considering the stages in the development of w process and showing how an understanding of chemical principles is involved at each stage and, indeed, is necessary 10. -caery ont the peojcet to a successful conclusion. This case study deals with viable and important process of the modern chemical industry. In order in maintain some continuity in the case study, we have adopted the concept of following the history of the product from the stage at which @ chemical reaction is fest conceived as a reasonable possibility, through the stages by which it becomes viable as & process, (o its final fruition asa full-scule operation. The development of a process progresses by a series of question-and answer steps, Initially the questions ace simple: “Ts thers a de particular produet?” “Can it be made frorr phe startin, small number of reaction stages?" “Is it required in ore-ton or housand-ton “quantities?” The questions increase rapidly in number and complexity the Investigation pracesds, but it is generally possible to recognize three key questions that are of prime importance and can be answered only in terms of basic chemical concepts. 1. Areuetion ( make # desired product from available starting materials is proposed will such a 1 occur te an appreciable extent? 2. Ifrreaction does occur, is the rate of reaction adequate? 3ed evelopment of a Process 3. Since the desired product will be mixed with unchanged reactants and by-products, how ean it be isolated in the required purity” These basic questions are considered in turn im the wren ease study that Follows, M1 INTRODUCTION In 1773 Re Wed a while crystalline substance from the urine ef an animal; he ter urine. Some vears later the chemical formula was found to be NH,CONH,. But it was in 1828 that urea really caught the attention of chemists, for it was in that year Wohler prepared urea [rom ammonium cyanate, an inorganic compound. nH.cNO HEM NHCONH, cereal Urea The exeitement came from the fact that this was the first time anyone had ever made an organic compound in the laboratory. The symthesis of urea is considered to be the beginning of synthetic organte chemistry. Before 1828 many chemists believed that only the living processes could produce organtc compounds such as urea But ures was not to remain merely a laboratory curiosity marking the ‘beginning of a new chemical cra, [n 1862 Basarov earned how te make wica from ammonia and carbon dioxide which, because of the simple raw ma- terials, broughl it into consideration as a product that might be made economically on at large scale. The reaction is illustrated by the following equation 2NH,+CO, === NH,COONH, = NH.CONH, + H.0 Une Although the eeaction dates back to LNO8, it did not attain commercial importance unl 1920, when the 1 G. Farbenindusirie developed 2 com- mercial urea probes. The first major prouction of xinea im the United Staios was pioneered hy BuPent in the carly 1930s at Bolle, West Virginia Alter Workd War It the use af urea in the United States expanded rapidly Production facilities for the manufacture of urea now number approximate 50 inthe United States alone. Ueea production in the United States during 1972 was 3.200.000 metric tons, This production figure serves to point ont ‘the importance of urea as a product in the modern chemical market.Introduction Ms The phenomenal rate of expansion of urea production is due to the in- creasing use of ure as a nitrogenous fertilizer. as x cattle feed supplement, and as a raw material in the manufacture of plastics, The most impartant use of urea is as a nitrogenous fectilizer. In fact, it is rapidly becoming the leading solid nitrogenous fertilizer, ‘Urea is the most concentrated solid nitrogenous fertiliz lable, having 4 nitrogen content of about 46°. which is 30%, higher than that of ammenium nitrate and more than 100", higher than ammenium sulfate. In addition, under some field conditions, urea nitrogen is not so easily leached from the soil as the nitrogen in ammonium nitrate. Consequently, it is the recommended fertilizer in regions with abundant rainfall ur for irrigated lands. Urea can be applied in a solid form, as a concentred solmion with ammonia, or mixed with phosphorus and potassium salts, It ean also be applied by spraying plamis with a solution containing 5 to 6.0", urea together with otker agricultural chemicals such as pesticides, fungicides, sana) micronutrients, On acid soil thal are nat treated with lime, the eMMcicacy ‘of urea nitrogsa is higher than that of nitrogen from ammonium nitrate. Because of the higher nitragen concentration, the transportation and ap- plication costs are 1d) to 20%, Jess for urea than for ammonium nitrate, ‘The use of ureu in vineyards, tobaceo fields, hop fields, root plant cultures, and so on, results not only ina crop inerease but also ensures an improvement in their quality. When used in hardy fruit growing and market gardening, it speeds up ripening by about two or three weeks. Tn reeent years, in addition to its application us a mineral fertilizer, urew is used in stock feeding as a substitute for albuminoid fodder for beef cattle because the nitrogen in 1 kg of urea is equivalent to between 2.6 and 28 kg of protein, ta 60 kg of oil-bearing seeds, ar to between 22 and 25 ky of oats, In addition, 1 kg of urea preduces am increase between 1.0 and 1.2 kg of meat or 6 kg of milk, The forégotng discussion has served to answer the first question that must bedealt with in developing a new chemical process—" Is there ademand for the particular product?” In the ease of ures, the answer was not dificult jo obtain, for it had long been recognized that urea could function as at excellent solid nitrogenous fertilizer. Thus, a tremendous markel ¢xssted for urea, if process could be found for producing urea at a prive that would ke it competitive with other solid nitrogenous fertilizers, Before we discuss the development of the various steps in (he manufaclure of urea and the factors affecting each step, it would be beneficial to consider a simplified flow sheet, In so doing, the purpose behind each stage in the development of the process can be put inta perspective more cusily.ani Developennit ofa Process ‘nccreue oR. ‘BY-PRODWCT SALT _ C0} rte Figure 141 Sompliied flow soe! for wees manufacture 142 THE PROCESS The process far synthesis of urea from carbon dioxide and ammonia is illustrated in Fig. 141 Ammonia and carbon dioxide are compressed and fext continuously into reactor that is maintained at a sufficiently high temperature and pressure to form a melt of ammonia, carbon dioxide, ammaniun carbamute, urea, ana] water. A continuous stream of the melt flows from the reactor, theoweh A pressure let-down valve, to the carbamate stripper where the melt is separated into liquid phase of urea and water (and perhaps varying amounts of ammoniven carbonate and ammenia) and ¢ geseous phase af ammor carbon diuxide, and small quai cof water. This gas is reeyeled 10 the process or used in the production of by-product salts such as ammonium nitrate or ammonium phosphate. The liguid product of the carbamate sicipper can be used in the preparation of ured-ammonia solutions or it can he processed further in an eveporater to produce & salid urea ‘We can now stidy the cfleer af several process variables and the problems associated with the development of each of the Four steps in the manufacture of ure, 14.3 THEORETICAL BASIS FOR UREA SYNTH SIS In order to develop a commercial process for manufueturing urea tram CO, and NH, a sumber of questions must be answered. The first question that‘Thuuretical Basis fur Urea Syatbesis at we must answer is, “Will the resection of CO, and NH, to form urea occur to an appreciable extent?” Second, we must determine if the rate of reaction is adequate, and since the desired product will be mixed with unchanged reactants and by-products, how can it be recovered in the required purity? Since the first step in the synthesis of urea is the reaction of CO, and NH to form ammoninin carbamate, the first order of business in our process development program will be (0 study this reaction 143.1 The Formation of Ammonium Carbamate @ is formed on simple contact of anhydrous CO, und NH, When these two compounds are dry, carbamute ulone is formed fegardless of the rélabve propertians af the two constituents. CO, () + 2NH (a) = NHsCONH, (5) (ay The reaction is an equilibrium reaction, and the system is divariant. That is, the pressure depends upon the temperature und the compnsition af the gas phase, When the initial product is carbumune, this composition is fined and the dissociation pressure depends only upon the temperature. We would expect Eq. 14.1 to occur in the forward direction ta an ap- preciable extent only at such temperutures that the pressure is below the dissociation pressure of ammonium carbamate, or comversely, the pressure on the reaction sysiem must be maintained ubove the wupor pressure of ammonium carbamate at any given aperating temperature. The Dissociation Pressure of Ammonium Carbamate. The disseciarion pressure of ammonium carbamate at various temperatures was measured in the laboratory,’ and the data are given in Table 14.1. The vapor from solid ammonium carbamate, as determined by analysis, is practically all NH, and CO;, since ammonium carbamate vapor dissociates very rapidly. Therefore, the “vapor pressure” of ammonium carbamate is also the dissoviation pressure, The vapor pressures enclosed in brackets at 180°C and 200°C are extrapolited values obtained from the plot of lag P versus 1/7’ shown in Fig, 142. The reason for the extrapolsted values being higher than the experimental values is that the pressure measured at high temperatures is complicated by the simultaneous decomposition of ammonium eurbamate into urea and subsequent decomposition of urea into biuret and amntonia ‘The plot of log # versus 1/7 as shown in Fig. 142, strictly speaking, is not a straight fine. It is a curve with a slope of inereasing steepness as thexs Development of 3 Process Table 14 Ammoaium Coetamate Diss. Pressure, ee ath, 40 o.31 a Loe 80 5 109 a5, 120 a 140 26 16a 38 180 150, (190) 200 200, (380) temperature rises, But, if we de make the approximation that the experi- mental points fall on a straight line, we can derive Eq. 14.2 _ 714g r where P is in atmospheres and T in degrees Kelvin. This equation ean be tised to calculate the disseciation pressure for any given temperature. Since the melting point of ammonium carbamate is 145°C, pweasures calculated 5 Log P 14) ‘Se wr 2 esse ‘a 31 wo 2s 28 BF ae es eee 4x aot ca Figere 142. Dissoelacion pressure of ummoniem carlanesic, Sore: Reference |Ticietical Basi for Urea Syathesis 8 below this temperature will be for the dissociati ‘of The solid and for tem peratures above 145°C for liquid ammonium carbamate, The dissociation pressure data for ammonium carbamate can be used to calculate the eguilibrivrt coustant fer its dissociation, These calculations are show in the next section, Equilibrium Constant for Ammontin Carbamate Dissociation. The equilib. rum constant for the dissaciation of carbamate to form ammonia and carbon dioxide Gin he derived in the following way NH,CO;NHL (3) = INH, (8+ CO.) (143) Kp = Poo, Phi (44) Pro, ad Pay, are the partial pressures of CO, and NH. respectively. In the case of synthesis from the stoichiometric ratio of carhou dioxide and ammo: the case of healing ammonium carbamate in vacuum, Kp may be calculated from the total pressure P, 2s shown in the following equations: (as) (14.6) (14.7) ‘The calvulated equilibrium eenstants from var measurements are listed in Table 14.2 us dissociation pressure Fable 14.2. Equilibrinen Constants for Aminiomiuen ‘Carbanate Dissociution0 Development uta Peueess This phase of the: study shows thal since ammonium carbarwate has a high dissociation pressure, it is formed most readily under high pressure, From these considerations, therefare, it will be advantageous in plant operation touse # high pressure to obtain a high yield of ammonium carbamate, whieh in turn will produce @ high yield of urea, Furthermore, in a continuous Now manufacturing process, the applied pressure in the reaetor must be substantsally higher than the equilibrium dissociation pressure of ammonium carbamile correspunding lo the uper ing lempersture in the reactor. Otherwise the reaction WH,CO,NH, = 2NH, + CO, will more or less caneel the reaction in which ammonium carbamate is formed, thus decreasing the ammonium carbamate concentration and hence decreasing the yield of urea. On the other hand, ammonium carbamate can be removed from the system by decomposing it to NH, and CO; under a low applied pressure and high temperature. This property will form the basis for developi method for separating ammonium carbamate from urea, The heat of formation of ammonium carbamate at constant volume can also be calculated from the dissociation pressure of ammenium carbamate by use of the vant Hofl equation: dink, -aE Tee oo (4s dt RT i Calevlations using the slope of the plot given in Fig. 14.2 yield a value of 378 keal of heut evolved for every mole of ammonium carbamate formed at constant volume. ‘The following equation cun be used te convert the value al constant volume into the value at ennstant pressure, AH = AE —AnRT (149) AH isthe heat of reaction at constant pressure, AK is the heat of reaction al constant volume, £m is the change in the number of moles of gas involved in the reuction per mole of ammonium carbamate formed. Using 3 for the value of Aw Jt temperature of 28°C, By. 149 gives a value of — 396 keal/mole for the heat of formation of solid ammonium carbamate.* Using a vulue of 3.6 keal/molz for the heat of fusion of ammoniuin carba- the heat of formation of molten ammonium carbamute can be cal- culated as follows: 2H (a) + COs (e) ——+ NH.CO,NH, (8); AA = —39.6 keall (14.10) NH.CO.NH, (5) + NHCO;NH4 (0: AM = 3.6 keal cg.)adding Eqs. 14.10 and 14.11 gives 2NH, (y) + CO, (@) ——s NHACO NH, (); AN = — 360 keul When liquid] ammonia is the reactant instead of gaseous ammoni of reaction is given by Eq, 14.14, 2NH, fg) + CO; (ey) ——+ NH,CO.NH, (i); AM = -360kcal (14.12), 2NH; — 2NH;¢ AH ~ 95 keal (14.13) INH. (N+ CO, Igy + NH.COLNH, (i): AA = —26.5 kcal 4.4) Thus, when ammonia and carbon dioxide react to form ammonium carba- mate, a great deal of heat is evolved. This heat must be removed in the process of manufacture to prevent the reaction temperature from reaching that level at which the carbamate dissociation pressure becomes equal to the pressure being maintained in the reactor The next step in our investigation is 10 study the rage of the formation of ammonium carbamate The Rate of Formation of Ammonium Carbamate. Lahoratory studies show that the rate of formation of ammonium earhamate from pascous NH. and CO, is very much influenced by the pressure. All other condlitions being eonstant, the rate ineteases about propartisnately to the square raot of pressure, The rate of formation of ammonium carbamate likewise increases with the temperature, The curves in Fig, 14.3summarize this behavior, At constant FORMED PER HOUR WEIGHT OF SOLO Wit Hiy a “J Figure 14.3. Rate of farmatioa of ammonium TempcRATURE,C scarbumatean Drovolapmment ofa Pree pressure the amount of ammonium carbamate Formed per unit time at first increases slowly, passes through & maximum, then decreases very rapidly and becomes zero al temperalune T, which corresponds to that fur whieh the dissociation pressure is equal to the reastion pressure, In industrial production, therefore, it is advisable to operate at the highest peessure possible and at the highest temperature compatible with this pres- sure, The reaction of CO, with NH. which is rather slow at ordinary pressure and temperature, becomes almost inslantunoous at pressures of the order of 100 lo 15G-aim and al temperatures of about 150°C, Under these reaction conditions, equilibrium data from the previous section in dicate that the formation reaetion for ammonium carbamate goes almost se completion. The next step in the reaction ta produce urea is the dehydration of am- moninm carbamate: to form urea and water acoarding ta bq. 14.15. NH,CO,NH, == NH,CONH, + 1,0 (415) 14.3.2. The Comversion of Ammonium Carbamate into Urea IFammonium carbamate is heated ina closed vessel. a part of it dissociates; and if the degree of filling of the apparatus is sufficiently high, the pressure produced by dissociation prevents the decompesition of the remaining aanmonium carbamate, which dehydrates spontaneausly tn yield urea.! This dehydration occurs solely in the Solid or liquid phase and not in the gas phase. The dehydration reaction is an endothermic process with AH js ¢ = 85 kcal. AS with most organic ammonical salts, the deliystration with the forma- ban of the amide is never complete, but rather isan equilibrium phenomendn, ‘The phase diagram for the ©20,-NH, reaction mixmee is given in Fig, 14.4. gh +65 vagaco, [mig HCO 1069 9.0 mh, 20 | ae op | 9p oo ano aay/ TemrenaTunt ate, 3 ‘Mea anon wwsourian 2 i somes ii soutien Figure Had Phisse guile moxie ef thesysiem NIH, CO, HO. Senne: Reference“Thcuretical Blass Far Urea 5) shove an ‘The diagram shows that smmonium earamute reuets with the water of dehydration to form ammonium carbonate Up to 60°C five components exist in the system. They are NHJHCO,, (NH,),CO, -H,0,(NH.HCO,), ° (NH,),COs, NHJHCQ, “NH; CO;NH,, and NHCO,NH.. Ammonium carhonate is relatively ineffective in urea synthesis, However, the tendency for ammonium carbonate to fort is very much reduced when both the Teinperature aie pressure are raised to a high level, or when there isan excess of Ny in the system. Abuve 60°C the solute is predominantly ammonium earbamute, which begins to eltange (0 ure as the temperature is increased — particularly when itis raised above 130°C under supcraimospheric pressure ‘Thus al synthesis temperatures of 150 to 190°C the dehydration of am- monium carbamate is an equilibrium reaction in which a complex homo- geneous mixture is obtained, consisting of water urea, unchanged ammonium cacbamule, and ammoninm carbonate produced by Ihe reaction of waler with ammonium carbamate. Effect of Temperature on the Conversion Vield of Ammonium Carbamate to Urea, fn order to-define the relationship between conversion yield and tem: perature, solid sen ale was loaded inte sealed glass tubes to loading density of | gloc, The pressure in the tubes was not theasured exept thal the Lube wasal atmospheric presstite andl room temperature when it was closed and before the temperature was raised, After equilibrium had been achieved at the test (emperature, the tubes were broken open and analyzed for the urea content. The data from these experiments ate shown in Table 143 and are plotted in Fig, 14.5." Itcan be seen that the conversion af ammonium ‘Table 14,3 Experimental Vields of (Uren from the Debydration of Ammonium Carharnate ‘at Various Temperatures el Yield, ¥ 4 a 4 4 4 4m4 Development nf a Process 5 — a Fy 4 “ UREA MELO, § “ "a Ce a a } ‘TEMPERATURE, "C Figure 145 Effect of temperature on Ibe conversion of ations carbamate fo urea Sinuree: Rosen 7 carbamate te urea gradually inc until it reached approsimately $ decreased with increasing temperanure Thedeerease in the degree of conversion of ammonium carbamate to urea ubowe IXFC may be explained by the fuet that the degree af decomposition of ammonium carbamate into its initial components, CO, and NH. also increases with rising temperature. Therefore, although the yield of the conversion reaction to form urea is improved hy increasing temperatures, thre Pressure must also be increased to prevent the reagents from becoming gaseous. Consequently, the working pressure in the reactor must be higher than the dissoctation pressure of ammonium carbamate at the reaction femperslure to avoid poor conversion yiekds, ised us the reaction temiperacure increased % al 90°C. The conversion then suddenly Effect of Pressure on the Comersinn Vield of Arimonisa Carlvaaiate tor Urea. The effect of pressure on the conversion of ammonium carbamate to urea is shown in Table 14.4. As can be seen, the yield of urea increases significantly when the pressure inceeases.® [Pthe process were to operate at 160°C, then the pressure in the reaetor must be greater than 189 lm to obtain a yrcld efeater thin 46%. As higher teiperciiures are used, the pressire in the reavinr must also be increased, For example, the maximum yield at 180°C is obtained ata pressure of 210 atm. jar in our studies of ng with steichio- Effect of Excess Components on the Viel af Urea, ‘Thu: those factors that affect the yield of urea, we have boen weHoretical Basis for Uren Sythesis us ‘Table 1.4 Effect of Pressure ua the Conversion of Ammonium Carhumate to Krew at 14h Pressure, ate Urea Yield, % 6 36.2 76.5 42.2 a 44.2 107.5 45.3 136.5 46.2 metric amounts of reaetantsand products. That is, aecording to the equation 2NH, + CO, = NH,CO,NH, = MH,CONH, + H,0 (14.16) the molar ratio of NH3¢CO, is 2:1. Now according to the law of mass action, an excess of ammonia must increase the degree of conversion of CO, to ures, and an excess of CO, must increase the degree af conversion of NH, to urea, Data on the conversion of ammonium carbamate in the presence of excess ammonia iato urea are given in Table 14.5." The data were obtained by Table 14.5 The Effest of Excess Ammunia nn tbe Comersinn of Ammosium Carbannate int Urea fonee ieee starting carbanate ant Materials Urea, % carbamate ° tres 1 iyo 3 Terbomacd + Il, 23.0 tres + to «3 2.0 Cactonael + 5 oo Oren 1 10 + 3s 43 Carbamacg + Nig 76.5 rea = H0 = Mls rs Carbenace + Mi, 23 Urea + Ilz0 + sil; 219.016 Dovdopmend uf a Preece ry ie rd amet ato ACESS AMMONIA, x Figere 146) Pllcr of excess ammonia am ammonium cirhanmalesuren equilibrium at 1S5°C. Sinarces Relerence % approaching equilibrium fram both dicections. As can be seen, the percent of conversion is independent of the direction from which equilibrium is established. The data in Table 14.5 are plotted in Fig. 146. Part of the favorable effet that excess ammonia has on the conversion ef ammonium carbamate io urea may be accounted for by its dehydrating activity, which reduces the water content of the molten reaction mixture, thus preventing its reaction with urea and thereby shifting the equilibrium toward the urea side. Increasing the amount of excess ammonia in a manufacturing plant in order to increase the conversion yield of urea is economical only to a certain limit, Beyond this, any further excess becomes unpcofitable because of rising uiilities, electrical energy snd steam requirements necessary for removing the excess ammonia from the product urea. In addition, an inezease in the NH: CO, ratio resubs is an increase in the specific volume of the molten mass in Ute reactor. This results in # corresponding reduction in rate of urea proxiuction, The most favorable exoess of ammoma is that which allows the minimum constimption of utilities and the highest production af urea Jor the given synthesis and pkint gas separation equipment, This value is estimated from pilot plant data in & latce section. AAs the data in Table 146 show, excess CO, has ne appreciable cflect om the conversion of ammotium carbamate to urea A plausible reason why an excess of carbon dioxide dues not have a large effect on the degree of conversion is because cxeess carbon dioxide remains in the gaseous phase in the reactor, while the formation reaction of urea praceeds in the liquid phaseeoretival Mass toe Urea Symmes ery Table 14.6 Effect of Excess Carbon Dioxide om the Conversion of Ammonium Carhamate intw Urea Conversion of Starting Exess — Carbanate ito Materials Cy, § Urea, 4 eee 81.0 4a Urea + Hg0 + Cb 1ne!0 4410 Carbonate + co. flat ts oe ne : When ammonium carbamate is converted inte urea, one mole of water is produced along with each mole of urea, According to the law of mass action, extra Water eniering with the reactants would have an adverse eflect on the yield of urea, The data shown in Fig. 14.7 confirms this relution- ship." Tn addition to reducing the conversion of ammonium carbamate to urea, extra water would take up room in the reactor and thereby reduce the productive capacity. Extra water also dilutes the urea solution from the Teactor, thereby increasing the load on the evaporators, and a resulting increase in energy consumption. New that we have studied all of the variables that affect the conversion of ammonium carbamute into urea, the question may be asked, “How can we calculate the yicld of urea for any given sct of operating condition: ‘The next section deals with answering this question ‘YHELD OF UREA, WTS, I prea Maca wareR ADDED, wT, Figure 14.7 Etfecr of water ce pield of ures at 130°C, Sewer; Referenoss | unlDevelopment af a Process Calcutating the Urea Vield, Our stushes harve established that the quantity of urea produced from the reaction af aitmenia and carbon dioxide involves he equilitium of a system comprising five components: NH, CO;, i nod urea, these along with temperittine aad cael of which has an effect upoa the others. seven varia piessure, a To calculste the equilibrium yield of utes from such system involves number of as-yet-unknown quantities, such as the uctivities of the com- ponents under high temperature and high pressure, conditions. To get around this dithewlty we use in approximation calculation based upon the overall reacti 2NH, +O; NH,CONH, + H,G 417) Starting with 2 moles af NH, and 1 mole of CQ, and obtaining an equi- Tibsium yield ¥ of urea in moles nce there are # total nf 3} moles of weactanls the mole fraction of urew in the reactor is Nunes 14.18) likewise, the mole fractiom af wat ¥ ‘iGo y 0a a9) The mole fractions of unreacted NH, and CO, are (14.20) 4.21) (14.23) (423)Vhourvteal Bass far Ursa Spmahests mm ce we have already determined ¥ as a function of 7, 1 Fig. 14.5 establishes a series of values for ¥ ai fur the range 13 te IXPC, data given in tion of temperature in ¥ where T is in degrees Celsius. Equation 14.24 is vi ature range of 130.40 190°C, Therefore, F may be-caleulated from the temperature and then K from ¥. For a nonstoichometric mixture, the nonsterchrometric reaction cun be expressed as follows: aNH, + bH,0 + CO, =— XNH,CONH, + (a — 2X)NH, + (h = X00 (1425) 10-27 + 0198 (14.24) where is the extent of conversion of CQ, to urea expressed us a fraction ‘of the CO, in the total feed; @ is the molar ratio of NH CO, in the total feed: und b is the molar ratio of H,O/CO, in the total feed. The total feed is fresh feed plus any recyele feed to the reactor. The equilibrium expression for Eq. 14.25 ts as follows: (14.26) Equation 14.26 can be solver for X after the value for K has been obtained from Bg, 14.23 Now that we can calculate equilibrium conversion yields of urea, it is necessary to study the rite at which equilibrium is established 14.3.3 The Rate af Formation of Urea Sludies on the rate of formation of urea are important and essential to the: successful development of (he une synthesis process, For one thing, the design of the reactor ina continuous flow process for manufacturing area will be determined by the residence time required for the urea reaction mixture to reach equilirium. Studies presented in the first part of our development program indicated that under conditions that give a high yield uf urea, high temperature and pressure, the formation of ammonium carbamate from CO; and NH, is almost instantancous. Therefore, we necd only Lostudy the rate afdehyd ra of ammonium carhamate ta estabhsh the overall rate of formation of urea, The effect of time and temperature om the conversion of ammenium Tramale ter ures is given in Fig. 14.8.'* The datu show that the velocity of the dehydration of ammonium carbamate is strongly affected by tem- perature. By examining the shape of the reaction velocity curves in Fig. 14.8,YIELO OF UREA, % o 4 8 @ & 2 2 2 a 36 4D TIME OF HEATING HRS, Figere HB Rate of sunversion af ammoaium earbaonnle iole sen, Sowrce: Reference it can be seer that at temperatures below 145°C, the melting point of am- monium carbamate, the shape of the velocity curses is of curves for autocatalytic reactions, A reasonable expk that the reaction velocity is slower in the sob phase than in the liquid phase. It may also be considered that the water formed during the dehydration reaction depresses the melting point of the reaction product, thereby acting as u catalyst ‘The effect o’excess NH ,.on the rate of conversion of ammonium carbamate to ures is shown in Fig. 149. The data indicate that approximately the Same amount of tinte is requiced te reach oquilibrium as was required for the stoichoimetric minature, id from Bateh Reactor Dat 14.3.4 Sumnary of Process Variables Obi The laboratory data that we have gathered thus far in our development of a ured synthesis process have served to establish the following process gvide- lines: The first stage in the synthesis is the combination of ainmionis and carbon dioxige to preduce ammonium carbamate. 2NH; + CO, NH;CO,NHy This reacthon is followed by dehydration of ammonium carbamate 10 give urea and water NH,CONH, + H,0. stions are reversible and aocur simultancously in the reuetor, The n B cxothermic and gocs capilly 19 campletion under the proces ng conditions of high temperstures and pressure; the second is endothermicTheoretical Basis for (neu Sythe al 0 60 so ELD OF UREA, & 0 10 pos cece 50 Excam hy = = = = OE ee o T a 5 ee TIME OF HEATING, HRS, we t0 urea in che presence of excess NH and, depending on the process conditions adopted, gues to 401 to 80% completion, Reaction pressures are within the range 130 (0 260 aim, and temperatures within the range 160 to 200°C, AL these temperatures and pressures the urea, ammonium carbamate, and components in the reaction mixture sre in the liquid form. Pxcess NH, over the stoichiometric ratio af will increase the conversion yicld of urca, while on the other hand, excess water will decrease the yield A reaction time of approximately | he is required in order to approach the equilibrium yield of urea. The eflluent from the reactor consists of a gaseous mixture of unreacicd ammonia and carbon dioxide, water vapor, and an aqueous solution of urea, ammonia. snd ammonium carbamate The next stage in our urea synthesis project deals with the development Of a method for recovering urea in a pure usable form from the reactor effluent, In addition, the economies as well as environmental considerations of the process require Unit the unreacled ammonia be recovered. Therefore, a method will be developed for recycling the unconverted reactants buck to the reactor or divecting them to other uses, such as the manuiscture of -copraductsaR ovelagunead of a Precess 143.5 Processing of the Reactor Effluent We have already learned that ifarnmoniume carbamate is heated at a pressure that is lower than its decomposition pressure it will decompose into NH and CO,. At low pressures and with heating, these gases cun then be stripped from the liquid phase thereby leaving a solution of aqueous urea. A method for treating the reactor effluent based upon these principles is to allow the urea synthesis enelt to flow from the reactor, through a pressure let-dowa valve, to a carbamate stripper. You may recall that tite flow seheme for this type of separation was given in Fig. 14.1. The product streum will be cooled as a result of the flashing chat occurs, Consequently, he temperauure of the material entering the carbamate stripper will be a function of the op- erating pressure of that vessel Additional heat must be aelded to vaporize soluble ammonia and de- sompeseammonivmearbamatcin the carbsumale stripper in order to decrease the quantity of ammonium carbamate and soluble ammonia an the liquid product. However, if temperatures much above 120°C are used in the carbamate stripper it is observed that decomposition of same of the urea ta undesirable biuret will occur. We will need to Inok more elesely at this decompasition in our next phuse of studies. Theoretically, 1 mole of water is produced per mole of urea; and, there+ af all the ammonium carbamate were dossdciated in Ue stripper, its liquid product wauld be a urea-waizr solution having a urea concentration af approximately 75 w1', In order to fornta solid soluble product, the urea- ‘water solution can be spray dried, evaporated, and erystallized, or it ean be evaporated and prilled. Prilling is a process whereby molten urea is sprayed into @ tower, The drops of molten urea are cooled in a countercurrent stream of air introduced at the bottom of the tower by fans, whereupon they solidify in the form of spherical prills. During this processing, the length af time that the matertal is held at temperatures abowe 110°C must be kept ail a minimum in order te lessen the decomposition of urea to biuret ‘Gur earlier studies demonstrated thal the conversion of carbon diaxide to urea in the absence of excess ammonia is only about Si per pass, Therefure, exces ammonia will normally be used. This inereases the conversion of carbon diexide but decreases the conversion of ammonia. Consequently recovery of the off-guses, especially ammonia, from the carbamate decon- poser is mandatory from an economic standpoint, Accordingly. tte result ing NHj-CO, gaseous miatuce must either by recycled tu the rector ar else used for the synthesis ef same other produet (this is the se-called “once-through™ process)-—un alternative that may not always be econom- ical.th a Recycling ofthe afTygas, however, is nota simple operation, Initial attempts to recyele the all-gases from the decomposer by direct compression (withaut separation) were found to be impractical because of precipitation of solid ammonium carbamate in the compressor system. (Remember that high pressure favors the formation of ammonium carbamate.) Therefare, same ‘other method must be found for recycling the NH ,~CO, mixture. There are scveral feasible ways of handling this recycle problem. One method is to conduct the carbamate decomposition at two different pressure Jevels, Ifthe first level is at about 25 atm. the product sus will be mostly NH, and this can be recycled to the reactor without any difficulty. The reason for this is that at 23 a(m the ammonium carbamate will not decompose at the lemperature maintained Consequently, only the excess NH in the solution will be evulved and this will be free of CO, The product gas fram the second- slage decomposer (about 1 alm pressure} will be a msture of NH, and CO;, and can be used in x coproduct fertilizer plant. This is called the ~ partial-receele process." ‘Another method for recycling the gases is to remove the carbon dinxide from the off-gas stream of the carbamate decomposer before it is returned lo the reacior, This could be done by passing the NH-CO), mixture through 4 monosthanoloamine solution wherewpan the CO; would he selectively alsorbed nul the purified NH, could be condensed and pumped back inta the reactor. If the absorbing solution is a urea-nitrate mixture instead of ethanoloamine the ammonia gas will be selectively absorbed. Bath of these methods are referred to as “gas separation tolal-recycle" processes, since all of the ammonia is recuvered Another method for recycling the NH, -CO,, mixture is to absorb the gas mixture in water and roeycle the liquid solution back to the reacter. The additional water that will he introduced into the reactor will tend to reduce the urea yield; but if the amount of water ts carefully controled, che reduc sion will nol be too severe. This method for hundling the off-gases is referred ko as a “total solution recycle” process. Each of the methods that we have proposed for handling the MH,-CO. gas mixture is summarized in Fig. 14.10, We will dircet most of our attention to the development of the onve-through process. The ccason being that it is the simplest proeess and ean serve asa madel for developing the ather more complicated processes Before progressing into the pilet plant stage with our urea project. it is necessary that we look more closely at the problems associated with the thermal decomposition of urea. In attempting to concentrate the aqueous urea solution from the carbatnate decamposer. we have observed that some biuret is formed, We must fine some way of minimizing this biuret formation, ‘This phuise of the investigation is hanclled in the next sectinn.and evelopment of a Process sccm es i +005 + Hy mr win Ss AQUEDUS at — tie PMRTIAL RECYCLE PROCESS eicees Hy romesenene [ERAiERE ray |CARBAMATE STE | —eesan fares fees oe womeceeurrmers Sub = REACTOR UREA REACTOR ae AQUEDUS CARBAMATE RECYCLE Figure L410 Verious processes for hanaling SHC offs muistnre 143.6 Formation of Lindes! ke Impurities During Urea Processing ‘As has already been: noted), the urea rich product solution will be subjected to heat during the stripping, evaporation, prilling, and drying steps in the process of producing solid urea. It is important to deietmnine if this healing ‘will result in the decomposition uf the urea product with subsequent produc tion of undesirable impurities.Tseretical Basis for Urea Synthesis aS “ 2 . iw ‘BIURET roa OF UREA CHARGED 130 150 179 Figure 1 iempetature (per bor). Sourve, Redereene 13, Biuree formatson in soy wea vers Laboratory studies'? show that when dry urea is heated to temperatures hear, oF above, its melting point (132°C) it slowly decomposes irtn biuret NH,CONH, H,NCONHCONH; + NH, (14.27) Ursa Bioret Biuret has been found to be toxic and harmful to some crops. lis presence in most Fertilizer-grade urea should be kept below 1%. Therefore, it is necessary to determine and define the conditions where biuret formation is at a minimum. The eflect of temperature on the rate of formation of biuret in anhydrous molten urea was studied first, and the results shown in Fig. 1411. The data were obtained for an unstirred melt of pure urea, maintained at the indicated temperatures for 60 min? The data show that temperature is a very im portant factor in biuret formation, The dita plotted ia Fig. 1412 show the effect that water has on bivret formation in urea melts at 140°C, as can be seen, low percentages of water shave little effect on the initial rate of biiret formation: but after several hours, the Iwo curves Separute, and after 7 he, only two thinds as much biuret is Formed in the presence of water as is produced in thé control rur 4 comparison of the rate of biuret formation in urea melts ut 140°C in contact with air and in an ammonia atmosphere of | atm is shown in Fig, 14.13. The data show that biuret fermation is only about 60% as grewt in the presence of ammonia as compared to air,st Dretelupmes of a Proves IME, HOURS Figure HLI2 Bivret formaties a1 La0°C ta pare dey w ster st T4IFC), Seurne: Reference 13. pure urea aus §*, Tn summary we can say that biueet formation in the synthesis reactor ts minimal because of the presence of a large excess of ammonia in the reaction mixture, However, during the final concentration of the urea solution where excess ammonia is not present, significant amounts of biuret may form. Bincet formation at this stage in the process can be sninimized ithe selution is concentzated under a vacuum at the lowest possible temperature, Where pris ace preferred to crystals, the urea erystals should be melted and prilled in such @ way that the lime interval in which urea stays above 130°C is kept fo a minimum IURET FORMATION OF UREA CHARGED 1 2 3 ime, nouRs, Figure 14.1) East of atmanonin on biuret fo Presa fu Urca im air: pure anwBomia simrep hice Reference 1“Ae Pilot Mant Stage OT PLANT STAG! ‘Now that the beitch scale studies have been completed and a successful commercial process fur the praduction of ures appears possible, a decision has to be made about the next stage in the development project. This may be the construction of the full-scale plant if there is sufficient confidence in the “scale-up” off the process. If this is not the ease, it may be decided 10 build a “pilot plant” which is a model, say of one-twentieth ar one-tenth the capacity, of the propnsed full-scale plant, As the object is to study the problems likely to be encountered, the design has to be studied carefully so that the data obtained will be of maximum value. The scale of the pilot plant will vary according to the type of prablem to he investigated, Only a portion of 4 process may be studied if’ enough is known abeut the remaining sections. It shaulel be emphasized, however, that pilot plant experimentation should be considered carefully and, if deemed necessary, carried out on the sirallest seale that is feasible. At the pilot plant stage, the develapment costs of a process increase steeply. Because of their size, pilot plants are much more expensive thant Laboratory apparatus. Moreover, to be fully useful, they have to be heavily instrumented, including automatic control instruments, and 24-he uperation will often be necessary, requiring a team of plant operators. As a resull, the costs increase immediately by an order of magnitude over laboratory-scale operations, A further drawback of pilot plant work is the time-leg involved, for che plant has to be designed, the equipment brought together and erecied, and finally commissioned The teed for extensive pilot plant experimentation is not as great as it onor was. Improve! methods of chemical analysis, together with better mathematical techniques for correlating the resulls, have led ta a much betler understanding of the processes, Also, a3. result of the development of more reliable scale-up procedures, the chemical engineer cai have more confidence in the design of a plant item tens or hundreds of times larger than the laboratory equipment Nevertheless, information gained only fram laboratory work is often insufficient to permit reliable scale-up, and the construction af @ full-scale plant would involve uncertainties that might require much time and maney to rectify if difficultics arose during start-up. Pilot plant development would minimize this problern Yei, the importance of having some production from the plant us soon as possible may justify taking the visk that problems will arise when the plant is first put inte jwoxhuction. Under these conditions there-will be a corresponding saving in time and effort at the pracess develop- ment stage, and i may very well be that the seale-up from a pilot plant tothe full-scale unit wall not in itself be devoid of risk.a8 Development Fs Proesss The decision is never an easy one to make. It involves « careful analysis of the problems that may arise on sealing up each stage of the process. In the development of the urea pravess the next logical stage of develop mmeat is to gather some: pilot plamt data where the reastor is uperatedd under continuous-low conditions. The reason for going w the pilot plant stage 4s owing, 10 the uncertainties in scaling up a laboratory size barch unit to a full plant size condimous-flaw operation. The siart thing to de is tor study the process in a small-scale continuous-flow plant and then scale up from this unit The lahoratary batch process studies have generated encngh knowledge about the synthesis of urea so that a minimum amount of time nesd be spent in the pilot plunt stags. In a real situation, a considerable amount of scenomic analysis would be done at this point in order to justify he large pilot plant expenditures. A small continuous-flow unit capable of producing 250 Ib of urea/day ‘was constructed. A flow diagram for the unit is given in Fig. 14.14. Liquid CO, is used for convenience only, since in the full scale plant operation gascous CO; will be charged to the reactor, In the pilot plant the anhydrous yuids are introduced separately into the base of the keadslined reactor by means of single-acting hydraulic-type pumps activated by a common crank- shaft. Adjustment of the NH (CO, ratio is effected by changing the stroke length of the pumps. Both veactants enter the reactor where reaction and wonversion tg urea take plice, After Ieaving the reactor the charge, now consisting of a liquid mixture of urea, water, and ammonium carbamate, enters stillin which the dissociatian of ammonia carhamate isaccomplishest bby heat. The urea leaves the still as an aqueous solutinn. The smmonia and carbon dionide leave the still as gases where they enter an absorber in which ‘the ammonia is absorbed in a sulfuric acid solution. The carbon dioxide is Figure MEd Flow dingy for sures pile plantThee Pilot Plane Stage 9 ischarged to the utmosphere from the ubsorber, Thus, the unit is an example -of the simple “ance through” provess. he pilot plant reactor consists of a steel shell 14.9 em id. and 2m lang with a 3.2-cm thick wall. The anterior is lined with lead 1 cm thick, The carbon sieel heads of the reactor are held in place by means of nickel-steel studs and bolts. By using long-stem valves with the seats contained within the autoclave proper, all danger of freezing up the inlets with solid am- monium carbamate is ehiminated. The velume of the reastor is 35.8 liters. The dip stem in the exit port provides for a 2-iter vapar space. Therefare, the total volume of the liquid melt in the reactor is 33.8 liters. The type of data obtained during the pilot plant operation is indicated in Table 14.7. The operating conditions were adjusted to study the effect af lemperature, pressure, excess components, and feed rae on the yield of urea under continuaus-low conditions, The urea yields in the pilot plant opera- ion were in general found to be 5 to 10% lower than the yields calculated from Eg, 14.26, For example, the pilot phint yield of urea at a reactor tem- perature of 185°C, a pressure of 193 atm, and a NH3/CO3 ratio of 3.83 ix 65.1%; whereas the yield of urea as calculated hy Eq, 14.26 should be 72%, under theso conditions. Pilot plant studies on the effects of feed rate and excess ammonia on the conversion of carbon dioxide to urea and the urea production rate are sum- marized in Fig. 14.13. Data were obtained at 160°C and 193 atm. The curves show that increasing the total feed rate decreases the percent conversion ‘of carbon dioxide to urea but increased the urea yield per hour. They also show thal excess ammonia increases the percent conversion of carbon dioxide ta wrea, but that for any spacitic total feed rate, excess ammonia decreases the urea yield on an hourly basis. If'we were going to operate the urea pilot plant at 160°C and 193 atm of pressure with a NH,/CO; feed ratio af 4:1 so as te maximize conversion of CO, to urea, We would feed the reactants at a rate of & Ib total feed /he ‘On the other hand, if we wanted ta get the maximum amount of urea produce tion per hour, we would operate the plant with a total feed rate of 26 Ibyhr. ‘The pilot plint dais serws 19 detremsteite the dependence of conversion and yield on Lolal feed rate, The optimwin feed rate for the full-seake urea plant will be a function of operating and capital costs. When using the once- through process, the optimum [eed rate will also depend on the type and economic value of the by-product produced with the excess ammonia. For example if the by-product is of low economic value, then the ueca plant mould be operated to maximize the conversion of ammonia to urea. This ‘would call for lower feed rates, On the other hand if the by-produet had reasonably high cconomie value and it was desirable to maximize urea production, the plant would be operated at a high feed rateey rr st ct er aT Tare tests Vet err aK nz er oF ° 20 ptt cor 4 sit ve ser $51 est a6 set Set sel oer oer A} 1 Morompode| 94) 40g KEKE WHEE HH LPL OWEThe P af 12 eset sa i wo = Ea ag z 3 ge ud i. i pe das ee 2 TOTAL FEED, UBS/HR Figure 14.8 Pifects of foe WJ excess ummagaia on ures producto Inespective of the type and amount of pilot plant data that we gather, the final resolution of the optimum operating conditions for the full-seale urea plant can only be decided by actual operation, The pilot plant data can only serve as a 2uideline for designing the plant. Both the pilot phunt and laboratory batch studies have shown that the raze of urea production is increased by 1. Increased pressure. Incteased temperature (so long as the operating pressure is eub- stantially above the dissociation pressure of ammonium carbamate). 3. The nse af love excess ammonisa The question then nay be asked,” Why not operate the plant at the maximum pressure and temperature possible and with low excess armenia?” There are several reasons why this should aot be done. One reason is that increased presiure idereases the capital and operating costs of compression and reac tion equipment. Increased lemperatire in the absence of excess ammania aecelerates the decemposition of urea to biuret, But most important, all of the above conditions accelerate the corrosion race in the reaction system. ‘They do this to such a great extent, and so sevetely under certain conditions, that because af eormsion problems the reaction cannot be conducted under conditions that result in the maxintum production of urea A considerable amount of data has been gathered during pilot plant ‘operations on the corrosion rates of various materials under urea synthesis conditions. Some representative corrosion data are listed in Table 143,az Deredapaneat af Precese Table L188 Corrasion Rates wider Lleea Synthesis Coaditians ighest Corrosion Lowest Corrosion Rate Obtained Rate Obtained Material Tested Inches/tear Inches /Year 410 5.8. Total loss Oe 5.5. 5.4 p 0002 321 8.8. 8 2008 Nickel 3.0 Ffaudler glass a6 Tantalum 2008 001 Tefion Weight gain and blistered The highest and lowest cortosioa rates obtained are given ta indicate the iremcndous cfiect of operating conditions on the rate of corrosion. In general, it can be said that the corrusive conditions of (be urea synthesis reaction are very severe, Only a few materials exhibited «ny semblance of being re sistant, Tantalum showed good corrosion resistance for all tests to which it was exposead, but its high cust rules out its use—except perhaps, as a very thin liner. Most urea process equipment is now made of stainless steel where corrasien raies are minimized through passivation of the stainless stecl by incorporating oxygen in the range of 0. + 3% into the process stream. Even with ait injection, however, use of stainless steel still limits the reactor temperature to about 190°C and the operating pressure to about 208) atm. When all factors for a onee-through urew process are taken inte con- sideration [the factors to consider involve minimization of corrosion rites, minimization of capital investment, minimization of ammonia usage, and maximumization cf urea production), onr pilot plant and hatch studies sggest that the reactor should be opecated at a temperature of appraxi- tely 180°C under a pressure of approximately 200 atm. The feed rate and eaetor volume should be such that the eeactioa time (the residence for the reaction mixture in the reactor) be approsimately 1 Br. So as 10 maximize urea production, but yet minimize ammonia consumption, only a 10%, excess of ammonia in the feed stream should be used. Under te! operating eenditions 4 46 19 S0°,, conversion of CO, 10 urea should be possible Ira rotal-recyele process is used, the synthesis reuetor should be operated ander a pressure ef 220 atm with the reactor temperstinre maintamed at approximately 190°C, The molar NH, ta CQ, rato in the feed should beMaterial umd Energy Balancy Fur the Synthesis Reactor tw a €nco- rmughe Process, wa about 4:1. Under these operating conditions, a 64 to 68% conversion of CO, to urea should be possible for cach cycle through the reactor, Under these operating conditions a material and heat balanee on the synthesis reactor ean be obtained, Both of these halances will depend en the particular type of process that is vsed (ie. whether the reaction is operated under onee-through, partialerecycle or tatal-recycle conditions), Sima: we are trying to develop the once-through process, we will restrict owr calcula tions to it 143 MATERIAL AND ENERGY BALANCE FOR THE SYNI REACTOR IN A ONCE-THROUGH PROCESS Calculations will be based on the following operating conditions: pressure in the reactor is 190 atm, temperature is 180°C, molar ratio of NH3 COs is 23.2:1 (w 10% excess), the degre of conversion of ammonium carbamate inte urea under these conditions is $0%,, The temperature of the reagents on entering the reactor is 25°C, and the temperature of the products leaving the reactor is 180°C, Ammonia is fed to the reactor as a liguid and a gas. Basis of calculation: The production of | metric ton (1000 kg) of urea Material Balance, The synthesis of urea from ammonia and carbon dimxide takes place by the fallowing equations 2NH, + CO, + NHCONH NH,CO,NH, ==! NH,CONH, + H,0 The theoretical consumption of ammonia and carbon dioxide per metric ton of urea is: INH, +CO, == (ONH, + H,0 De iT 44 ea 18 Ammonia required _ (247711000) NH, at anda Bovwlopment of x Precis The theoretical amounts of atimonia and carbon dioxide that have to be introduced into the reactor al a conversion of 50%, is: akg Ni toichiometric) — "80 1133 ke mas CO, teharged) = 7 Ke 66 ke Bula NH: CO, ratio of 22: 1 is used, therefore the amount of ammonia aciually charged is: ean NIL, toharaest) = agg = TBE ‘The amount of ammonium carbamate formed is 10 NH,CO,NH, = a) = 2598 ke where 78 denotes the molecular weight of ammonium carbamate, The amount of ammonia eansumed to form the earbamate is 1133 kg. therefore, the amount of unchanged ammonia is NHy = 1246-1133 = 113 ki “The amount of unchanged ammonia carbamate is NH,CO.NH, = (005)12598) = 1299 ke and the amount of water resulting from the conversion of ammonium carbamate inte un (1000 gi C18) EO 50 ke The material halance for the synthesis reactor for 1 ton of urea produced ib shown in Table 149. The ammonia shawn in Table 14. does not romain ‘Table 14,9 Materlal Balance for One Ton of Ure Production ‘Gutput Amount (Re) laput Ammen i2a6 Ure ine 368 Carbon dioxide 1456 Anwmanisim carbamate Las 9 Water 00 Mad Amntonia in excess 13 42 Total ma Total mmMate nt Every Balance for Me Spiihesis Reactor in a Once- Through Process a5 free because the water resulting from the renction dissolves the estos ammonia by forming ammonium hydroxide: NH,OH iF (35) = 292 ke where 35 represents the molecular weight of ammonium hydroxide and 17 the molecular Weight of NH. The amount of free water lft is 13 HO (fheo) = 300 — 7 (18) = 180 ke The energy balance for the synthesis reactor for the production of 1 metic Lon of urea is giver in the following. Energy Balance. Hut input plus heat liberated during reaction is 1. Heat contained in liquid ammonia: Oy = (1246 kg). 16 kealkeCH25°C) 2, Heat contained in carbon dioxide: Qs = (1466 kg44 (8.22 keal/kmole"CH25°C) = GREG keal 3. Heat evolved with the formation of liquid ammonium carbamate 134 keal NHAC) + COs (eb + NH;CO,NH(N AH = —265 keal JE KE 0365 ken at vkmok’ 2s = 55 jgiole 285 heal kamole) (10 mole/kmnoke) = £82,633 keal 4. Heat evolved with the formation of ammonium hycroxide from waicr and ammonia NH, + H,0() + NH,OH(ag)AH = —3.55 keal’mole 232KE sean cout . . Oe = Sy jeqras O50 Keabemole — 23,551 heal 5. Heal associated with the formation of urca—this means we need to calculate the heat for the reaetion (at 180°C) NH,CO.NH,() —— NH, CONH() + HOUAH The following equation may be utilized to ebtain the value of AM H,O(!) + NH,CONH,(s))- ——> NH,CO,NH6)4H se = ~6.8 keal (o}06 Developement of a Frncess ‘The chunge in the heat content of the reactant and the products in this reaction (hat accompanies the raising of the reaction temperature fram 28°C to 180°C can be represented by the following equations. Using an average specific heat of 1.0364 keal/mole"C for solid] and molten ammonium carbamate, we ebtain: NH,CO)NH.(s}ae¢ —— NHjCO,NHj(, 180°C}, AW — 45.64 keal (b) NHLCONILGs, 180°C) . NH,CO,NH,IKPCE = AH = +185 keal (ey Using an average value of 0.0192 keall°mole for solid and molten urea, we obtain NH,CONHsis, 180°C), ——+ NH,CONH fs, 25°C); AH = NH,CONH,(/. 10°C} ——+ NH,CONH,(s, 80°C}; AME = —36 kel Ce) Using an average specific heat of 1.0184 keal"mole for liquid water gives HOU, 18°C) ——+ H,0(,25°C), A= — 2.79 heal Of Adding Ey. a, 6, cd, and f gives NH,CO,NHg{l, 180°C) —— NH, CONH>(i, 180°) + H,O(l, [80°41 = — 7.98 keal Thus, while the decomposition of ammonium carbamate at 25°C is endothermic, it is éXethermic at 180°C. Therefore, the heal evolved in the formation of LOD kg of ures is: (1000 kg 7980 keal/kmaley (Gi kgimoley a The toral heat input is then @r=0, +024 01+ Os + Os = 36.138 + 6846 + 882,633 + 23531 + 134.061 = 1,083,205 keal‘Material and Fnergy alone forthe Synthesis Reactor in. Onee-Thewsgh Pros 7 ‘Heat Output |. Heat content of ures (1000 ky) 19.2 keal/kinol (60 ky 600 keal 2. Heat content of water (300 keh 18 + keub amo?) 180°C a 2g. = 55.21K0 keal 3. Heat eontent of unchanged ammonia 9, = (1S REID healamaleC 180°C) * 17 Kgikmole e = 28.476 eal 4. Heat content of unchanged ammonium carkamate (1299 kg) 364 keal male?CXIB0°C) es Te kgkmale = 109,116 keal then: ‘The (otal heat outpur @=G.+9.+05+ Os 7,600 + 55,200 = 28,476 = 109,116 = 250, 392 keal Since the iatal heat input was calculated 1 be Q, = 1,083,205 keal, the amount of excess heat = Q, — , = 1.083.205 — 250,292 32.813 keal This is the amount of excess heat produced when 1 ton of urea is produced at the given operating conditions. A sirmll part of this amount of heat is lost through the walls of the reactor, but the remainder must be removed from the system. In the once-through process, this heat is removed by a cooling jacket and/or a large excess of ammonia, In the partial-reeycle process, the excess heat is removed by recycling the excess ammuania, In the total-reeyele process, ihe excess heat is removed by recycting the ammonium carbamate solution.8 Dorclopmend of w Perce We now have reached the point in our development program where we can get some cstimate of the operuting und capital costs associated with a urea plant that utilizes one of the thre lypes of proposed processes. 146 CAPITAL AND OPERATING COSTS Thus farour studies have been aimed at gathering knowledge so that a plant can be designed 16 make sirea, But the rea plant has to make something che besides urea—it has 10 make money, Therefore, a urea plant will be built only afier it has beem established that the process is economical and that the plant is capable of making money. The capital cost for building a ures plant is a function of the size of the plant and the type of process used, that is, whether it is a once-through operation or a total recycle. The capital cost veesus capacity can be plotted arithmetically. By plotting the capital cost per daily ton of urea against plant size far a tolal-recycle process, the reduction in capital casts per ton as the size of the plant is increased becomes visually apparent as Fig, 14.16 shows, The fact that the capital element per ton of production decreases as the n = = [PLANT COST, CTHOUSKN® + FER BAILY TOW) 200 300 ro 508 cabacity, romsonr Figere 1.16 Capital cost per lon of urea pooxluced by toial-eeycle versus plant eapacilyCapital and Ope ing, Cuts me 410) Camparisoas of Capital Costs asc pon at Phin ‘with a Dally Production of 100 Tots of Urea Solution Porn Javestreat Cost per Process Instaited Daily Ton{1976} Snee-thnough $15,008 Partini rosyote 21,200 Complete recycle 31,000 plant grows bigger is ane of the most important driving forces in the chemieal industey today. It puts the producer with a larger pskant at & competitive ad- vaivtage because he can sell at a lower price than the producer free a small plant and still meet all his charges ineluding the cost of servicing and re~ paying the capital A comparison of the capital costs for the these major weea processes is given in Table 14,10. The increase in cost of the recycle processes as compared ju the once-through process is due to the need for additional pumping equipment for recycling the ammonium carbamate or ammonia solution and larger reactors and decomposers to handle the larger velume of liquid that is fed to the reactor. In addition to the cost of building the plant, another important economic factor 1s the operating cost of the plant “The operating requirements for urea plants may be broken down into the normal subdivisions of feedstocks and ulilities to show the relative im- portance of cach iter. Estimates of these values as obtained from pilot plant data are shown in Table 14.11. This comparison of operating requirements shows significant diflerences in the consumption of ammonia and earhon dioxide, Since the ammania cunsumplivn per lor of urea greatly affects the production cost, it is always given careful consideration in designing a plant, In some plants one may think that the CO, is available free from an ammonia syntheses gas purifi- ation process. However, in most real economic situations, things arc free ‘until considered useful, and then accounting will fix a value on them that the prncoss developer must face. The value is often arbitrary or could be as high as market value if purchased outside. Thus while it looks free overall, it ie given a coat in caleulations About 65", of the electric power consumed in # urew plant is duc to CO compression. The remaining 35%, of the power is consumed by process pumps, conveyors, fans, and so on.- Derclopment ofa Prices Table 4.11 Comparisen of Feedsiock and Uiligy Requirements Far te Different Ure Proseeses (Based aa a 1 tomy plant) Unite/ton of prilled urea onco- Partial Total through Recyele Recycle Liguid Armonia Feed, tan 1.28 87 4 Consunption, ton a) “6 "64 In off-gas, fon [8 2 2 Garken Dioxide Feed, ton LAT er 183 Consumption, ton 73 83 283 In off-ss, ton a4 ret a Electric power, Ev-he 220 154 16 Stean (180 Tb/in), 1b . 2.0 2,380 Steam (30 lb/in), Uh aga Cooling water (11°C, rise) al 2.370 15,200 14,500 The steam and conling water are wsed in the decomposition of ammonium carbumate and subsequent condensing of the reervered ammonia gas. The feedstock and utility casts for the three processes can be calculated from the information provided in Tables 14.11 and 14.12, A comparison of these costs for the three processes is given in Table 14.13, It is quile clear thal the most importan! factor that controls the feedstock and utility costs is the amoust of ammenia used in producing a ton of urea, The total cost of producing a ton of urea in a 100 ton day plant is given in Table 14.14 Table 1412 Urility Costs (1976) cten Armonia ton 84,06 0, ten a Steam 1060 Tb 2.50 Cooling Mater 1000 gal 9.08 Electricity sen 08‘apital and. Operating Cass aa ‘Table 14.13 Comparison of Feedstack and Ui ity Costs per Tom of Pi Coat. Process Water Elec. Total Once-through $80.59 $2.20 $4.59 $6.60 Partial recycle 56.08 5.78 1.46 4.62 Total recycle 41,25 5.88 132 5.28 Urea in 1976 sid for an average prive of $135/ton. If only ures is sold, then the average profit before taxes per ton of urea produced is: Process Profit (S100 (hased on $135/ton urea)] ‘Onee-throngh 535.72 Pactinlsesyste 35.09 Totul-reeyeke 63.06 (One must realize that the actual profit will be considerably lower than these figures indicate, because we have net included in our calculations such costs as lahor overhead, sales cast, and sc on. The profit maegin foe the once-through and partial-reeycle processes can be increased by the manulacluré Of a byproduct with the excess ammonia Table 14.14 Urea Priduction Cost (Based amu 108) tonjduy plunt) far the Praductian of 1 Ton of Prilked Urea Once Partial Total Tren through Recycle Reeyele 1. Feodstock + uLitities 467.54 $84.73 2. Labor, per shige 4 S8¢he 1.92 198 3. capita charges 2105 @ year at 5H aaa 4. Taxes and Insurance 2 Wfyr oF plant 12a 1.78 2.54 5. Mainteauice # 5¥/yt ‘of plant investment 2.04 2.90 4.26 Total Production fest Tage Tear Tee ths an exanple ealewlation, Cake the case of the aueo-tkrough process Investnent 15 $15,000 per daily ton of urea. 10% v£ $15,000 is $1,500, Divide this Mgur by the curber of daily cont of urea in a year; $1.300/%65 - $4.11,that is available io these processes. For example, in the once-through process for every ton of urea produced, 0.63 ton of ammonia is available in the off-gas. This amount of ammonia cam be turned nto 3.2 tons of amrnnnina nitrate at a cost of 890/ton, The average value of a ton of ameneniam nitrate at 1976 prices is $96, Therefore, the profit obtained in converting the excess ammonia into ammonium sityate is $19.26. When this prolit is added to the profit from the sale of urea, we find that the total profit from operating a 100 tonjdlay ence-through urea plan is $5492/ton of prilled urea For the partial-recycle process where (1.22 ton af ammonia is in the off-ga, LO4 tons of ammonium nitrate cum be produced. This results in a profit uf about $6.24. When this is added t the profit (ram jhe sale of urea, the total profit per ton af urea produced in the partial-recyele plant is $61.33. At this point, a comparison of the various processes indicates that larger profils per ton of urca produced are achieved with the total-reeyele process. Aaother desirable feature: with this process is that there are no additional by-products swith which t J Aku, ovo integrited provesses are more difficult 1 operate than one. Although the capital investment jn a total= recycle plant is greater than for the other urea processes, i! is mot grewter— probably less—than the combined investments in the two integrated pro- esses that are necessary for the once-through urea plant, Tn deciding whether to build a urea plant or net, mast chemical companies would requite that the plant return at least 10° on capital before taxes However, before a company can choose one of the three processes as a basis for plunt design, « number of lictors as discussed in Chapter 2 must be considered, For example, the question ohow much cupital is available for investing in the ures plint must be considered, Market conditions fur the by-product should he analyzed, An evaluation should he male as in how the by-product fits imto the ovevall produet line of che company. Akko, the question of how much urea production ts required must be answered. Once I of these factors are .o consideration, then a proves can be chasen nil at plant slesignes. 147 THE DESIGN OF THE PLANT ‘Our developmental project has matured to the point where # plant ean now be designed for producing urew. For example, our studies have provided formation on the Followia 1. The general ow scheme nf the process difficulty is likely ta be experienced. 2 The likely effects of wurious impurities in the raw materials oa the yield and quality of product det Of points whereBetereneee ee 3. The type af reactor to be employed, and the conversion «ind yiclds that ean be expected 4. The quantities of heat to be transferted at various points. und whether these transfers arc likely to present problems. The problems of preduet purifiestion and other separations im the process and how they cam Ie dealt with 6 The materials of construction, 2. The probable oosts of the plant and of operating it It is now the responsibility of (he engineering group to luke our data and proceed Lo the detailed design of individual plant items, taking into can- sideration all the Ewtors involved te ensure that the completed plant will operate in courect und econemical way. M8) REFERENCE GD, Batis, fait Bas Chem, 3B, ABA AL, (ards) 00, 22 (195), 3. T Gambon, Chin, fu, (Piri) 74, 917 (1855), 4 KK, Chick and H.C. Hetheringion.. iy, Cibo $8. G.N, Lewis ane GH. Barrows, J. Am, Cihom, Soe. M4, 1818 (9124 SE Terres and HL Behrens. 2 Pips. Chom, (Lessa) A EI9, 685 (192% 7. KK, Clark, YL, Gada, amd ©. , ist, fd. Kc: Chow. 25, 10 & ® Soe 43, 190841922), 8. Kewusuanl, Bill Chem, Soe, Jap. 24, 148 (1951, H. J. Racuse ard V, L. Goldy, 4 as, Cheme. Sac. 52, 368 (19340, 10. S. Kuwasumni, Bail. Chor Sic, yp 25, 227 (1982) 11S. Kewasuni, dll Chom. Soe. Jug, 26, 213, 222 (0953), ane 27, 25001954), 12, “Proves Survey, U wr Chew. Bes asd) la iM. 1 CF Redemaws, F.C. Riewaleld, nod TS. LaVsola, fu Fay Chea, 90, 633 (1958), 48) 15. BLA. Bolovov, Ay N. Papa wav YK. Sokol Cer, dat SRY 18H (LIT