The urea stripping process ‘The technical manufacture of urea, with carbon dioxide used both as reactant and as stripping gas by P.J.C. Kaasensnoop ‘Stactsmijnen|DSM, Geleen, Netherlands ‘Summary —The economy ofthe technical production ‘of urea from emmonia and carbon dioxide is substan "tally improved if unconverted reactants ate reycled atthe synthesis pressure. Separation ofthese reactants from the reactor eluents can be effected by stripping with carbon dioxide gas. The high pressure of the ‘tripped vapours allows condensation at elevated temperature (150-170°C). Thanks to this high thermal level all of the condensation heat developed can be recovered as steam. 1, Introduction ‘The essence of the technical preparation of urea consists in reacting ammonia and carbon dioxide at elevated pressure and temperature. Initially a liquid pphase is formed in which the reactants are contained largely in the form of ionized ammonium carbamate. By debydration the carbamate is converted to urea. ‘The condensation is a heterogeneous, highly exo- thermic conversion: (!) * 2NHy(g)+C0,(@) = NH,COONH.() AFfeae, = ~28 kcal/mole (= 0atm, += 160°C) ‘The formation of urea is an endothermic equilibrium reaction proceeding in the liquid phase: NH,COONH,(1) s+ CO(NH,),(1)+H,0(1) Aly, = +7 kcal/mole (¢ = 160-180°C) ‘Therateofdchydration becomessohigh at 160°C that it can be utilized for the technical preparation of urea.(**) Owing to the volatility of the reactants, this temperature can be reached only if the synthesis is carried out under pressure. The practical condi tions therefore are: 160-200°C and 100-250 atm. The formation of urea takes place in an autoclave, in which slightly more than half of the ammonia and eatbon dioxide supplied are converted into urea and water. The reaction mixture consists of a liquid phase (the so-called urea synthesis solution), in which the liquid mixture of urea and water serves as a solvent for the volatile reactants—ammonia and carbon dioxide—present mainly in the form of NHJ and NH,COO™ ions. Because in a self-contained urea plant ammonia and carbon dioxide cannot be processed to recover by-products, they have to be converted completely into urea and water. Therefore it is necessary to separate the unconverted reactants from the urea synthesis solution prepared and to return them to the reactor. The way in which this separation is effected, largely determines the cost of the urea pre- paration. The strenuous efforts used in optimizing the technical preparation of urea have consequently been focussed on the development of the most economical recycling method. Until recently this was the so-called water recycling process, in which the synthesis solution is expanded in several stages. The gases released in these stages are dissolved in water on the counter-current principle, and the resulting concentrated ammonium carbamate solu- tion is pumped back to the synthesis unit. Although as regards mode of realization and energy consump tion this method was the most attractive, it has the disadvantage that the gases are released at a rela- tively low pressure, so that the dissolution also has to take place at low pressure, and, consequently, at a comparatively low temperature, As a result, the heat released in the condensation is lost: it has to be removed with the cooling water. In order to avoidP..C. KaaseNszoop this loss—which corresponds to an’ amount of heat equivalent to about one ton of steam per ton of urca—the reactants would have to be removed from the synthesis solution at high pressure, preferably at the synthesis pressure. The condensation can then ‘be effected at elevated temperature, and conse- quently steam can be produced, instead of the heat having to be removed with the cooling water. The Yolatilization of the reactants at the synthesis pres- sure cannot be realized simply by heating the syn- thesis solution. The temperature would then become s0 high that large amounts of decomposition prod- ‘ucts—e.g. biuret and cyanuric acid—were formed. It is possible, however, to expel the ammonia and the carbon dioxide from the synthesis solution at the synthesis pressure, viz. by contacting this solution with gaseous carbon dioxide flowing in counter current, while supplying heat. Gaseous carbon dioxide is only slightly soluble in a urea solution; under favourable conditions it will expel the major- ity of the reactants from the synthesis solution, without this having to be heated to an undesirably +high temperature. How this stripping is best realized depends mainly on the liquid-vapour equilibria.(*) 2. Stripping with carbon dioxide gas 21. The liquid-vapour equilibria of a normal binary system are represented in Figla. At constant pres- sure the boiling temperatures of the solutions become proportionally higher as the concentration of the higher-boiling component increases. If the constituents exert strong Van der Waals forces on each other, or if they are capable of chemical bond- ing, a maximum may occur in the liquid-vapour ‘Tie LIQUID-VAPOUR EQUILIBRIA Fiat. ‘Liguid-gas equilibria in binary systems at ‘constant pressure. Joop; in this maximum—called the azeotrope— liquid and vapour are of identical composition (Fig. 1b), For the ease that the two constituents are super critical, Fig. Ic gives the azeotropic liquid-gas equi- ibria, Ifa Tess volatile solvent is added to this sys- tem, a ternary system is formed (Fig. 2) in which the boiting points of the solutions give a special shape srtnriage ne ms (> >in eed Fic. 2. Liquid temperatures in ternary system with binary azeotrope, at constant pressure, (Supercritical ‘zeotropic components.) to the rx liquid plane, Sections of this plane, e.g, at constant solvent content, ate analogous to sections of the liquid plane for the binary system. The ternary liquid plane therefore appears as a ridge in the ¢-x space. If the peak points of this ridge are linked up, the topridge line a is obtained. The points on this Jine do not have the same E/F ratio as the points for the binary azeotrope. If, for instance, E dissolves more readily in S than does F, the ratio of E to F ir. the solution at the moment when the temperature reaches a maximum value is higher than the ratio in the binary azeotrope. The ratio becomes higher as the percentage of solvent increases, on account of which the topridge line is curved. As on this line also the temperature keeps rising, it may be defined as the line which starts in the binary azeotropic point and takes such a course along the ternary liquid plane that the di/dx on it is always maximum. Since the temperatures of solutions situated on either side of the topridge line fall off, the temper~ ature on the line RP—indicating 207, S—will decrease from f, (femperature on topridge line) to tgand 4, At 40% $ temperature series are obtained‘The urea stripping process which start from f, (temperature on topridge line) -and proceed to f2, fy and t,. Linking up the points of equal temperature gives the liquid isotherms. ‘These are the loci of the compositions of all solu- tions having the same vapour pressure at the given temperature. On each of these isotherms the temper- ature as well as the pressure is constant. There- fore, each of these lines is as much an isotherm in an isobaric figure as an isobar in an isothermic one. If the composition of a solution changes at constant Pressure and temperature, for instance owing to condensation of E and F with proportionate heat removal, or owing to evaporation of E and F with proportionate heat supply, this change in compo- ition cannot but proceed along the isotherm. The ‘Change is monovariant, a regularity, which, indeed, follows directly from the phase rule, It should be remembered that for a three-com- onent system the following relation holds: f= ¢~p+2; with c= 3and p = 2, the value of *F becomes: fa 3-242=3. Atconstant temperature and pressure f= 3~2 = 1. The behaviour described here is shown by the solution present in the urea synthesis equipment; the azeotrope there occurs in the binary system NH, ~ COz, the constituents of which are super- critical. However, the solvent generally is a urea solution (urea + water; equimolar solutions to be referred to henceforth 1s Ur. 1 H,0), so that the heterogeneous equilibria at constant pressure or FERRE would have to be represented in a wedron. Since no crystallization takes. place in the synthesis plant, and the water of the urea solution is only litte volatile in comparison with ammonia and carbon dioxide—so that, as a first approximation, the gas phase may be imagined to be free of water—the urea solution may be treated a6 if it were. single component and the system regarded as quasi-ternary. The representation in the tetrahedron is then simplified to a construction i composition triangle, as instanced in Fig. 2. If first approximation, the water is considered to be ‘non-volatile also in a practical treatment to which a solution is subjected, the change resulting from ‘Contacting a Liquid with gaseous carbon dioxide can be represented in a simple way. 2.2 ABSORPTION AND DESORPTION AT ‘CONSTANT PRESSURE Suppose a solution situated on the isotherm of Fig. 3 to be contained in a vessel placed in a thermo- stat. The top of the vessel is closed by a movable piston which is weighted so, that the last gas bubble over the solution is just condensed. Consequently, the liquid is at boiling point, without any vapour 9 Fic. 3. Solution in contact with carbon dioxide gas, being present, however. If carbon dioxide is passed into the solution, either of tne following reactions can occur, depending on the composition of the solution: (a) The vapour condenses. The composition of the liquid is now indicated by a point in that part of the isotherm which is over the topridge line. For, if into such a solution (L,) some carbon dioxide is introduced and totally absorbed, a solution will be formed which even has to be heated before regaining its original vapour pressure. (b) The vapour does not condense. The compo- sition of the liquid is then given by a point in that part of the isotherm which is under the topridge line. {f some carbon dioxide is supplied to a solution of this kind (L,), the temperature has to be lowered to effect complete condensation, However, if this liquid is intimately contacted with an amount of carbon dioxide gas at constant temperature, the gas phase G will be formed. This gas phase is situated ‘almost right on the NHy-CO, side. in addition thereP.1.C. Kaasewano09 is the liquid phase Lj, which is closer to the corner Ur. | HO than is the original liquid L,. For, the liquid phase Ls obtained after thorough mixing must lic on the isotherm and furthermore on the (straight) nodal line passing through the gross composition B ‘and connecting the gas and liquid compositions. Since the gas phase formed is situated virtually on the NH,-CO, side, Li must be closer to the comer Ur, | HO than L,. This shift occurs if both ammonia and carbon dioxide desorb from the solu- tion. It can result only from decomposition of ammonium carbamate, which must consequently be expelled from the solution. The boundary between absorption (L,+CO,) and desorption (L,+CO,) is observed in sotutions situated on the topridge line. If the carbon dioxide gas and Lz are contacted in a counter-current column, a rectifying effect will occur, on account of Which the composition of the issuing liquid may ‘come close to the comer Ur. 1 H,0. The ammonia at first present in the solution is for the greater part expelled as a result of the rectification; the amount ‘of dissolved carbon dioxide remaining in the solu- tion is likewise small, because carbon dioxide as such is litde soluble in urea solutions, even at elevated pressure. The carbon dioxide gas has stripped the dissolved NH, and CO, from the solution. Now that it is known in essence what kind of solutions can be stripped by means of CO,, it is important to find out how such solutions can be ‘obtained in the urea synthesis process. As already stated in the introduction, it would seem desirable to equalize the pressure in the synthesis equipment to the pressure in the condensing and stripping ‘sections. With this set-up the use of pumps is avoided, while it is possible to condense the stripping gases at ‘optimum temperature. The process takes place in a synthesis unit consisting of a condenser, « reactor, a stripper and an inert scrubber, which may be arranged as shown in figure 4. Gaseous carbon dioxide is passed through the stripper and is then fed to the carbamate condenser together with the gases desorbed from the urea synthesis solution, the freshly introduced liquid ammonia and recycled solution. In the condenser tubes the gas is pardly condensed, The temperature of the condensation is so high as to permit of generating steam. The liquid gas mixture leaving the condenser is introduced into the bottom of the reactor, where carbamate is 4 converted into urea and water and the major part of the gases is condensed, supplying heat for the adiabatic operation of the reactor. The urea synth- esis solution produced gravitates wo the stripping ccoluma, the inert gases are vented through the inert scrubber, Becyetecarn, Solution HP steam. [stuoper Condensate Ti bee Fio. 4. Urea synthesis apparates. 2.3 CHANGE OF THE COMPOSITION OF A SOLUTION OWING TO UREA FORMATION ‘The question as to what reaction conditions have to be chosen, can be answered only, when an insight has been gained into the change effected by the chemical reaction in the compositions and the tem- peratures of liquid and gas. The change of the com- position of a solution as a result of the formation of turea can be represented in diagrams of the type also used for heterogeneous equilibria (Fig. 5). MoltenThe urea stripping process ammonium carbamate here has the composition indicated by point 4. Upon conversion of the liquid phase into urea and water, the composition shifts along a straight line, the so-called reaction line, towards the point Ur. 1 HO, until chemical equi- librium has been reached; at the process temper- ature (t,) this is indicated by point 3. Fla. 5. Reaction lines Ifthe original composition is not stoichiometric, the reaction line is shifted, but remains parallel to AB. It may for instance be the line denoted by 4’C’, in which case the equilibrium composition is given by point 2". The curve BB’ is the chemical equi- librium isotherm at, - creme ent Fro. 6. (Chemical equilibrium Hines. ‘The liquids indicated by the points on these iso- therms do not all have the same pressure (5), The pressure will be minimum where the bond between NH, and CO, is strongest, ie. at the intersection ‘with the topridge line. The more the solutions deviate from the composition at this point, the higher their vapour pressure will be. Consequently, con the chemical equilibrium isotherm of 1, °C a pressure increase will occur starting from a mini- ‘mum pressure of p; atm#On the chemical equi- librium isotherm of f, °C a similar pressure rise will ‘occur, starting from p; atm (f, >t; pr>pa). If the points of equal pressure are linked up, the chemical equilibrium isobars are produced: lines indicating liquid compositions of equal vapour pressure and showing chemical equilibrium. How these solutions ‘can actually be made, appears from the composition Figure 7, which was constructed by combining Figs. 2, 5 and 6. The location of the lines in this figure is based on experiments of 130 atm. ‘A liquid phase obtained by condensation of an NH-CO, gas mixture, passes along 2 reaction line traversing the composition triangle when urca is formed in it. As the chemical composition of the solution changes as a result of the reaction. this liquid phase may be raised in temperature up to the — reuse ne rim = oo © Fic. 7. Liguid phases inthe system (Ur. 1 Hg0-NHs-COsat 130 atm vapour pressure, points of intersection between the reaction line and the isotherms. If more heat is supplied than corre- sponds to this temperature increase, part of the liquid is evaporated at the prevailing pressure, and a(Fig.6)P.L.C. Kassenanoop the liquid phase no longer follows the same reaction line, The rate at which the formation of urea pro- ‘ceeds is determined not only by the temperature and the ammonia and carbon dioxide conceatrations, but also—of course—by the distance to the chemical equilibrium, 2.4 COUNTER-CURRENT LIQUID GAS [EXTRACTION ‘The question whether the maximum amount of pure carbon dioxide, that can be fed into the base of the stripper, forming part of a technical installation, is sufficient to strip the urea synthesis solution almost completely in a counter-current system, can be answered in the affirmative. As long as ammonia is contained in the sotution, expulsion will take place at the bottom of the stripper. At the stripper top the ‘gas phase is in contact with a solution the compo- sition of which can be represented by a point on the topridge line (see section 3.2). Under normal oper. ating conditions the gas phase that might be evolved from this solution has a molar NH,/CO, ratio of 2.7. In order that stripping may take place also in the top part of the tubes, the NH,/CO, ratio of the gas phase there present will consequently have to be lower than 2.7. For a representative case this ratio can be easily calculated. If at 130 atm about 95% of the route towards chemical equilibrium has been covered, the composition of the urea synthesis solution situated on the topridge line is: AE in the stripping process all of the ammonia and carbon dioxide is expelled from this solution, an amount of 1 mole of carbon dioxide per mole of urea leaving the equipment, will have to be supplied to a synthesis space in which the currents have become stationary. As follows from the liquid com- position, 20.8 moles of CO, gas will then have to be supplied per 100 moles of solution. Consequently, the gas phase at the top of the stripper tubes will contain: 10.7+208 = 31.5 moles of CO, and 47.7 motes of NH. ‘The NH,/CO, ratio of this gas phase is 47.7/ 31.5 = 1.51. As stated above, this gas is capable of expelling ammonia from the synthesis solution. ‘3. The technical realization of the stripping process This subject divides into a number of important points. 3.1 PROCESS CONTROL, Ifthe compositions of the solutions which are fed to the stripper and are obtained from the condenser are situated on the topridge line, the conversions in the synthesis equipment proceed under optimum conditions. (During the condensation the temperature will bbe maximum, since this condensation is azeo- topic; (b) During the reaction the solution passes through a seriesof compositions whosetemper- atures are always higher than those of other solutions containing the same percentages of urea and water; in consequence, the reaction rate will always have the highest value that can be reached at the given pressure of the system; (©) The synthesis solution discharged from u. ) reactor has the highest possible percentage of urea that can be reached in the reaction; con- sequently, the stripper receives a solution with the lowest possible content of ammonia + car- bon dioxide, which reduces the steam cost of stripping to a minimum, tis possible to obtain these optimum compositions by contacting the solutions with gases whose 'NH,/CO, ratio is somewhere near that of the azeo- ‘tropic composition. As appears from Fig. le and from the experimentally determined liquidvapour ‘compositions of Fig. 8, the composition of the gas phase in the binary system may be rather far from the azeotrope, without the liquid in contact with this“The urea stripping process ‘gas phase changing measurably. Since this holds also for the quasi-temary system containing the urea solution, itis possible to feed into the bottom part of the reactor a gas which (partly) condenses and thus compensates for the endothermic urea for- ‘mation, and at the same time prevents the liquids ve ‘ 6 t ete : ett || +6 ‘4 E 189 14857 20 40, 60 80, 100 Coe x ny Fic. 8. Ligid and vapour compositions inthe binary system NHg-COp at 130 atm (weight percentages) present throughout the reactor and the condenser from deviating perceptibly from the azeotropic or the topridge compositions. This regulating effect of gases is realized by so controlling the ammonia to the reactor, that the molar NH,/CO, ratio of, the vent gases leaving the condenser is between 25 and 3.5. 3.2 REACTOR, CONDENSER AND STRIPPER ‘The urea reactor is a gas bubble contactor working on the uniflow or on the counter-current principle. It is designed as a cascade of bubble washers housed in a vertical cylindrical autoclave which has been divided into a number of compart- ments by means of screen plates. The reactants are usually fed in atthe bottom, partly as gases, parly as liquids. Hence, the currents are not distributed over the compartments by control elements operated externally, The condensation of the gases yields the necessary sensible heat and the heat required for the endothermic urea-forming reaction. Owing to the condensation, the compositions, amounts and densi- ties ofthe gas and liquid phases vary throughout the hheight of the reactor. In the stepwise numerical calculation of the reactor volume the compositions of the liquids may be taken to move along the top- ridge line. Also, ifthe openings in the screen plates have the correct dimensions, mixing between the compartments is negligible, on account of which the cascade of bubble washers may be calculated as a cascade of continuous stirred-tank reactors, At an overall pressure of 130 atm the temperatures in the reactor rise from 165 to 185°C. A daily output of 500 metric tons of urea requires about 50m? of reactor volume, In the condenser by far the greater part of the reaction gases is liquefied. All of the heat released in this process is used for the production of low-pres- sure steam. With temperature differences of 15-20°C, it is possible to produce 4 atm steam. In the con- denser pipes the gases fed in, form a two-phase current in which the liquid/gas ratio increases ‘gradually. As in this condensation the composition of the vapour is identical with that of the Tiquid {azcotropic composition), the condensation rate depends exclusively on the heat transfer. If inert gases are present, the heat transfer rate will drop sharply, especially towards the end of the conden- sation. Not only the heat transfer, but also the pressure drop caused by the two-phase current is of import- ance. This pressure drop is one of the factors deter- ining the height of the condensor over the reactor, if transport depends exclusively on gravity. ‘The stripper is composed of a series of parallel vertical tubes in which the solution to be stripped flows down along the wall, in counter-current to the carbon dioxide gas fed in at the bottom. The tubes are externally heated by means of steam. To achieve ‘8 satisfactory operation it is necessary that the liquid current and the carbon dioxide current be evenly distributed over the various tubes. To ensure this, each tube has been equipped with flow resistors for gas and liquid, which have such capacities that variations in gas density and differences in flow esistance between gas and liquid in the tubes cannot disturb the distribution. It is further seen to that thePLLC. Kaasewanoo liquid is fed in along the full circumference of the tubes. Owing to the short stay of the liquid on the ‘ube wall, only little urea will hydrolyze during the stripping process and more than 90% of the carba- mate can be expelled, while the biuret content of the solution rises by less than 0.1% by weight. The load of the tubes is limited to a maximum, determined by the force exerted on the liquid film by the gas flow. 3.3 Srammrry As is known from the study of evaporator- condenser systems, pulsations may arise in stream- ing fluids when vapour and liquid flows are coupled. Unstable srobie Butte Saigon Fro. 9. Stability of reacter-stripper system. ‘costo “ As the stripper may be viewed as an evaporator, stability fluctuations are essentially possible, With the arrangement of Fig. 4they actually appear under certain circumstances. The study devoted to this Phenomenon showed them to be due to an inter- action between the flow of expelled gas from the stripper to the reactor and the flow of liquid from the reactor to the stripper. In the reactor these flows are coupled, in that the gas bubbles displace the liquid and make it flow over; inthe strippe: coupling ‘occurs in that the amount of liquid stripped deter- mines the amount of gas expelled. Instability arises when deviations from the flow pattern tend to become greater. The fluctuations of temperature and pressure then resulting can be damped by buffering the liquid by means of throttled overfiows (Gee Fig. 9). Acknowledgments ‘The author is very much indebted to all those who studied the detail problems that had to be solved, before large-scale production units could be built. The list includes: Dr. J. Buiten—rectficati Ir. L. van Dierendonck—reactor design; Mr. P. Hendriks and Ir. C. van Koppen—stability; Ir. J. Logemann—pilot plant; Ir. J. Theron Mulder —fiuid flow; and Ir. D. Venderbos—conden- sation, References 1. Orsuxa, E. Kogyo Kagaku Zassht, €3, 494 (1980). 2. BARANSKI, A. Chim. Ind, 93, 408 (1965). 3. Frdsacques, M. Chim. et Ind, 60, 22 (1953). 4. Stamtcannon. Dutch Patent 101.446, April th, 1960. 5. Kawasunt, S. Bull. Chem. Soc. Japan, 24, 148 (1951)s, 25, 227 (1952); 26, 218 (1953): 27, 284 (1984), }