PROCESS FOR THE DISPLACEMENT FROM THE LIQUID TO THE GASEOUS PHASE OF THE EXCESS OF NH3 CONTAINED IN AQUEOUS SOLUTIONS OF UREA

Abstract: A process for the displacement, at 80 to 250 kg/cm², of the NH₃ excess contained in urea solutions having a tem­ perature of 150 to 230 °C and coming from a former stripping (isobaric with the synthesis of urea), performed in the presence of NH₃, wherein said solutions contain also CO₂, in amounts lower than 25% b.w. with respect to urea, and wherein said displacement is performed in countercurrent with CO₂, within a falling-film heat-exchanger containing a tube bundle (CO₂ stripper), isobaric with said synthesis, the amount of ammonium carbamate in the solution leaving the bottom of the CO₂ stripper being substantially equal to the amount of ammonium carbamate in the solution entering the same stripper, characterized in that: a) the global NH₃ : CO₂ ratio, in the solution fed to the CO₂ stripper, is from 2 to 8 b.w.; b) heat is substantially supplied only to the uppermost portion of the tubes of the CO₂ stripper, wherein the ratio between the surface of the lowermost portion and the sur­ face of the uppermost portion of the tubes is at least 1 : 1 and wherein the ratio between the residence time of the solution to be stripped in said lowermost portion and the residence time in said uppermost portion is at least 1 : 1, said res­ idence time in the lowermost portion of the tubes being at least 3 s and said residence time in the uppermost portion being at the most 3 s.

Description: A PROCESS FOR THE DISPLACEMENT FROM THE LIQUID TO THE GASEOUS PHASE OF THE EXCESS OF NH3 CONTAINED IN AQUEOUS SOLUTIONS OF UREA The invention is an improvement of the process disclosed in U.S. patent 4,208,347 and of other analogous processes. Said U.S. patent concerns a synthesis of urea by reacting NH3 and CO2 in the presence of an excess amount of NH3, with intermediate formation of ammonium carbamate, and provides for the displacement of the non-reacted reactants from the aqueous urea solution leaving the synthesis reac tor by means of two subsequent strippings, isobaric with the synthesis; in the first step the synthesis product is heated and optionally brought into contact with an NH3 stream and in the second step the same product is heated and brought into contact with a CO2 stream. In the first step a major proportion of carbamate and part of the free (non-reacted) NH3 are removed by supplying heat and by injecting an NH3 stream as stripping agent; it is thus possible to obtain an urea solution containing a relatively low amount of C02, but a huge amount of residual NH3, bound just to the operating conditions, which provide for an excess of NK . In the second step nearly all the residual NH still present is removed by a second supply of heat 3 and by using, as a stripping agent, the C02 feed required by the synthesis, while no appreciable change does occur in the carbamate percentage, already brought to a sufficient ly low level in the first stripping step, and this is proved by the experimental tests reported in said U.S. patent. In said first isobaric stripper, heat is supplied by means of condensing steam but also by exploiting the heat content of the solution, which undergoes therefore a cooling.U.S. patent 4,208,347, which has marked a basilar turning-point in the technology of the urea synthesis, is valuable for having shown, first in the world, that the elimination of the NH3 excess, independently from the destiny of the last traces of carbamate, is the primary and natural purpose of said second stripping (CO2 stripping), subsequent to the preceeding (first) stripping, all this being contrary to the teachings of several other patents, filed also later than said U.S. patent, which strongly recommend to consider, as main object and purpose of the second stripping (CO2 stripping), the other (actually minor) concomitant effect of the C02 tratment, namely the decomposition of the still present carbamate. An object of the present invention is to improve the manufacturing loop described in said U.S. patent 4,208,347 frequently reported as "I.D.R." loop or 111.D.R.11 cycle (it is however possible to employ successfully the invention for other analogous loops); other objects will be evident from the disclosure hereinafter. In its most general form, the invention concerns a process for the displacement, from the liquid to the gaseous phase, at pressure from 80 to 250 Kg/cmê, of the excess of NH3 contained in aqueous urea solutions having a temperature from 150 to 2300C and coming from a former stripping (isobaric with the synthesis of urea from NH3 and CO2), said former stripping being performed in the presence of NH3, with or without an injection of fresh NHD from the exterior, wherein said solutions contain also C02 (as ammonium carbamate), the CO2 amount being equal to or lower than 25% and preferably 22% by weight, with respect to urea, and wherein said displacement is performed by means of a stripping in countercurrent with a C02 stream, in a falling-film heat-exchanger containing a vertical tube bundle (hereinafter CO2 stripper), isobaric too with said synthesis, the amount of ammonium carbamate in the solution leaving the bottom of the C02 stripper being substantially equal to the amount of ammonium carbamate in the solution enetering the same stripper, characterized by the fact that: a) the global No, : C02 ratio, in the solution fed to the C02 stripper, is from 2 to 8, preferably from 3 to 6 and even better from 4 to 5.5 b.w.; b) heat is substantially supplied only to the uppermost portion -of the tubes of the C02 stripper, wherein the ratio between the surface of the lowermost portion and the surface of the uppermost portion of the tubes is at least 1:1 and wherein the ratio between the residence time of the solution to be stripped in said lowermost portion and the residence time in said upper most portion is at least 1.:1, said residence time in the lowermost portion of the tubes being at least 3 se conds and said residence time in the uppermost por tion being at the most 3 s. Said solutions, containing less than 25% b.w. of carbamate, come from at least one preceeding isobaric stripping, for instance an NH3 isobaric stripping; the invention however can be used not only in those double stripping loops in which the strippings are isobaric with the syn thesis, but also in those manufacturing loops in which one or both the strippings are at a lower or anyhow different pressure, always with respect to the synthesis. In any case the instant invention is always valuable when the main purpose is to transfer into the gaseous phase the free NH3 contained in an aqueous urea solution, at a rather high pressure, while using, as stripping agent, part or all of the carbon dioxide required by the urea synthesis. The teching of Canadian patent 1,113,961 is to heat strongly the uppermost portion of the tubes of a CO2 stripper and to keep the residence time of the process fluid,in said heated uppermost portion,at a much higher level (5 seconds) with respect to the residence time (-from 1 to 2 s) in the underlying portion, cooled or adiabatic, just in order to decompose as much residual carbamate as possible. According to the present invention,on the contrary, the residence time in the uppermost and heated portion must be lower(from 1 to 3s)with respect to the underlying adiabatic portion (from 3 to 5 s ) and the temperature drops, in said underlying portion (partially because of the C02 addition), down to a level between l50 and 210, preferably 160 and 190 and even better 160 and 1750 C, the temperature of the C02, injected as a stripping agent, being preferably from 80 to 111000. All this can be carried out, by heating only a. small portion of the length of the tubes, namely a portion equal to or lower than 1/2 (preferably 1/3) and even better from 1/5 to 1/3 of the whole length, the underlying adiabatic portion being obviously the complement to 1. The invention allows to reach excellent and unexpected results as to thermal balance, steam requirement and absence of corrosion; it allows further to stop completely and safely the degrading hydration of urea to ammonium carbamate, which can occur according to the known equation: EMI5.1 Best results are reached when the ratio between the exchanging surface of the CO2 stripper (SCO2) and the exchanging surface (SNH3) of the preceeding stripper is given by the expression: A = ScO / 5NH > 1. 2 3 Summarizing,a preferred ambodiment of the invention is a process for the displacement, from the liquid to the gaseous phase, at pressures from 130 to 220 kg/cmê, of the excess of NH3 contained in aqueous urea solutions having a temperature from 190 to 220 C and coming from a former stripping (isobaric with the synthesis of urea from NH3 and CO2), said former stripping being performed in the presence of NH3, wherein said solutions contain also C02 the CO2 amount being equal to or lower than 22% b.w., with respect to urea, and wherein said displacement is performed within a CO2 stripper, isobaric too with said synthesis, the amount of the carbamate in the solution leaving the bottom of the C02 stripper being substantially equal to the amount of carbamate in the solution entering the same stripper, characterized in that: a) the NH3: C02 ratio, in the solution fed to the C02 stripper, is from 3 to 6 (preferably from 4 to 5.5) b) heat is supplied only to the uppermost portion of the tubes of the C2 stripper, wherein the ratio between the surface of the lowermost portion and the surface of the uppermost portion of the tubes is at least 2:1 (preferably from 2:1 to 4:1) and wherein the ratio bet ween the residence time of the solution to be stripped in said lowermost portion and the residence time in said uppermost portion is at least 2:1 (preferably from 2:1 to 4: :1), said residence time in the lowermost portion of the tubes being at least 3.5 (preferably from 3.5 to 5) s and said residence time in the uppermost portion being at the most 2.5 (preferably from 1.5 to 2.5) s. The improved process of the present invention is still further illustrated by the accompanying figure 1, representing a simplified flow-sheet of the process itself. According to figure 1, urea is synthesized in a reactor subdivided into two overlying sections, fitted with sieve trays. The liquid product flows over by gravity into the underlying section through downcomer (18) and then it passes, through pipe (4), in a falling-film isobaric exchanger (NH3- stripper), containing a tube bundle, where the residual non-reacted carbamate is almost totally decomposed by help of an NH stripping stream (21); the decomposition 3 gases (NH3 and CO2; and part of the NH3 excess) flow back to the reactor (line 3). The solution (6) leaving the bottom of the NH3 stripper is transferred to an isobaric eo stripper, similar to the former (NH3) stripper but having a greater number of exchanging pipes; in the C02 stripper part or the whole of the C02 amount required by the synthesis is injected, usually at 800-1400C,to the bottom of the stripper and removes nearly all the last traces of NH . The solution (7) leaving the stripper's 3 bottom is conveyed to further and usual steps of the manufacturing process, while the vapor stream (9) leaves the head of the C02 stripper and is conveyed to a condenser, in admixture with the gases (13) coming from the reactor's head and with an aqueous solution (8) coming from further and usual low-pressure process steps. A purge of residual gases (14) leaves the condenser, while a carbamate solution (5) is recycled to the reactor merely by means of gravity and without needing any huge and complicated recycle pump. The NH3 requirement is pre-heated and fed to the reactor (line 1); in some cases a prefixed proportion of the NH3 feed (19) is super-heated and fed to the lowermost section of the reactor. It is thus possible to obtain a final urea solution (7) -reach in urea and having biuret percentages satisfactorily low. The following examples illustrate furtherly the invention, without limiting however the scope thereof. EXAMPLE 1 Following figure 1, urea is synthesized in 9 reactor subdivided into two each other overlying sections, fitted with sieve trays. The liquid product flows over by gravity into the underlying section through downcomer (18) and then it passes, through pipe (4), into a falling-film isobaric exchanger containing a tube bundle, where the non-reacted carbamate is almost totally decomposed by help of an NH3 stripping stream; the decomposition gases (NH3 and CO2) and part of the NH3 excess flow back to the reactor (line 3). The solution (6) leaving the bottom of the NH3 strippercontains 22% by weight of C02, with respect to urea (the 22% figure refers to C02, also if actually CO2 is present as ammonium carbamate), and is then transferred to an isobaric C02 stripper, similar to the NH stripper but having 3 a greater number of exchanging pipes; in the CO2 stripper the whole CO2 amount required by the synthesis is injected to the bottom of the stripper and removes nearly all the last traces of NH . The solution (7) leaving the stripper's bottom is conveyed to further and usual steps of the manufacturing process. The vapor stream (9) leaves the head of the C02 stripper and is conveyed to a condenser, in admixture with the gases (13) coming from the reactor's head and with an aqueous solution (8) coming from further and usual low-pressure process steps; a purge of residual gases (14) leaves the condenser, while a carbamate solution (5) is recycled to the reactor merely by means of gravity and without needing any recycle pump. The NH3 requirement is pre-heated and fed to the reactor (line 1); it is thus possible to obtain a final urea solution (7) reach in urea and having a biuret percentage satisfactorily low. 34513 kg/h of an aqueous urea solution (6), the composition of which is reported in Table 1, leave at 2050C 2 and 200 absolute kg/cm , the bottom of the first isobaric stripper (NH stripper), heated by saturated steam (10) 2 at 25 absolute kg/cmê ; 9694 kg/h of C02 (line 2) enter at 130 C and 200 absolute kg/cmê, the bottom of the second isobaric stripper (CO2 stripper), heated too bX steam at 25 absolute Kg/cmê only in the uppermost section of the tube -bundle; 25580 Kg/h of a final aqueous solution (7), the composition of which is in Table 1, leave, at 1720C and 200 ab 2 solute Kg/cm , the bottom of the same C02 stripper. Furtherly 18627 Kg/h of the fluid (9), the composition of which is in table 1, leave, at 2000 C, the head of the same CO2 stripper; the ratio between the amdunt of carbamate (CBRU) leaving the CO2 stripper and the amount of carbamate (CBRE) entering the same CO2 stripper is: CBRU:CBRExl0O = 2930:2698x10O = 108,6%. The small amount of steam (11), required for the heating of the CO2 stripper, is such as to comply with the thermal ba lance. The low-pressure steam (12) generated in the condenser 2 is at about 6 kg/cm (absolute) and its amount is such as to satisfy nearly all the steam requirements downstream of the I.D.R. loop. Data and results are in the following Table 1. EMI9.1 <tb> Line <SEP> (from <SEP> 2 <SEP> 6 <SEP> 7 <SEP> 9 <tb> figure <SEP> 1) <SEP> (0) <tb> T <SEP> (OC) <SEP> 130 <SEP> 205 <SEP> 172 <SEP> 200 <tb> P <SEP> (Kg/cm2) <SEP> 200 <SEP> 200 <SEP> 200 <SEP> 200 <tb> <SEP> kg/h <SEP> % <SEP> kg/h <SEP> % <SEP> kg/h <SEP> % <SEP> kg/h <tb> NH3 <SEP> - <SEP> - <SEP> 12466 <SEP> 36,1 <SEP> 3550 <SEP> 13,9 <SEP> 8916 <SEP> 47,9 <tb> CO2 <SEP> 9694 <SEP> 100 <SEP> 2698 <SEP> 7,8 <SEP> 2930 <SEP> 11,5 <SEP> 9462 <SEP> 50,8 <tb> H20 <SEP> - <SEP> <SEP> - <SEP> <SEP> 6849 <SEP> 19,9 <SEP> 6600 <SEP> 25, <SEP> 249 <SEP> 1,3 <tb> Urea <SEP> - <SEP> - <SEP> <SEP> 12500 <SEP> 36,2 <SEP> 12500 <SEP> 48,8 <SEP> - <SEP> <SEP> - <SEP> <tb> T <SEP> O <SEP> T <SEP> A <SEP> L <SEP> 9694 <SEP> 100 <SEP> 34513 <SEP> 100 <SEP> 25580 <SEP> 100 <SEP> 18627 <SEP> 100 <tb> (O) The balance is approximated because of the exclusion of inerts and biuret; percentages are by weight. EXAMPLE 2 (COMPARATIVE) The test of example 1 was repeated, while totally suppressing the injection of heating steam to the second (CO2) stripper, operating therefore, in other words, in a fulladiabatic way; data and results are reported in Table 2 hereinafter. The CBRU:CBRE ratio (in percentage) is = = 4646 : 2698 x 100 = 172.2% EMI10.1 <tb> Line <SEP> (from <SEP> 2 <SEP> 6 <SEP> 7 <SEP> 9 <tb> figure <SEP> 1) <tb> T <SEP> ( C) <SEP> 130 <SEP> 205 <SEP> 165 <SEP> 200 <tb> P <SEP> (kg/cmê) <SEP> 200 <SEP> 200 <SEP> 200 <SEP> 200 <tb> <SEP> kg/h <SEP> % <SEP> kg/h <SEP> % <SEP> <SEP> kg/h <SEP> % <SEP> kg/b <SEP> <tb> NH3 <SEP> - <SEP> <SEP> - <SEP> <SEP> 12466 <SEP> 36,1 <SEP> 4365 <SEP> 15,5 <SEP> 8101 <SEP> 50,5 <tb> CO2 <SEP> 9694 <SEP> 100 <SEP> 2698 <SEP> 7,8 <SEP> 4646 <SEP> 16,5 <SEP> 7746 <SEP> 48,3 <tb> 2 <SEP> - <SEP> <SEP> - <SEP> <SEP> 6849 <SEP> 19,9 <SEP> 6650 <SEP> 23,6 <SEP> 199 <SEP> 1,2 <tb> Urea <SEP> <RTI ID=10.11> - <SEP> <SEP> - <SEP> <SEP> 12500 <SEP> 6,2 <SEP> 12500 <SEP> 44,4 <SEP> - <SEP> <SEP> - <SEP> <tb> TOTAL <SEP> 9694 <SEP> 100 <SEP> 34513 <SEP> 100 <SEP> 28161 <SEP> 100 <SEP> 16046 <SEP> 100 <tb> It is clear that the satisfactory removal of NH is stric 3 tly bound to a considerable formation of carbamate, which (residual) carbamate must be then decomposed in the subsequent low-pressure usual sections of the plants, what implies a strong and disadvantageous supply of heat. The downstream low-pressure steps would require therefore apparatuses having much greater dimensions and it is well known how difficult the recovery is at a sufficiently; satisfactory thermal level, of the heat supplied for the lowpressure decomposition of the carbamate.

Claims: CLAIMS: 1) A process for the displacement, from the liquid to the gaseous phase, at pressures from 80 to 250 kg/cmê, of the excess of NH3 contained in aqueous urea solutions having a temperature from 150 to 2300C and coming .from a former stripping (isobaric with the synthesis of urea from NH3 and C02), said former stripping being performed in the presence of NH wherein said so 3, lutions contain also C02 (as ammonium carbamate), the CO2 amount being equal to or lower than 25% b.w., with respect to urea, and wherein said displacement is performed by means or a stripping in countercurrent with a CO2 stream, in a falling-film heat-exchanger containing a tube bundle (CO2 stripper), isobaric too with said synthesis, the amount of ammonium carbamate in the solution leaving the bottom of said C02 strip- per being substantially equal to the amount of ammo nium carbamate in the solution entering the same strip per, characterized in that: a) the global NH C02 weight ratio, in the solution fed to the CO2 stripper, is from 2 to 8; b) heat is substantially supplied only to the upper most portion of the tubes of the C02 stripper, wherein the ratio between the surface of the lower most portion and the surface of the uppermost por tion of the tubes is at least 1: :1 and wherein the ratio between the residence time of the solution to be stripped in said lowermost portion rnd the residence time in said uppermost portion is at least 1:1, said residence time in the lowermost portion of the tubes being at least 3 seconds and said residence time in the uppermost portion being at the most 3 s. 2. A process according to claim 1, wherein the surface of said uppermost portion of the tubes of the C02 strip per is from 1/5 to 1/2, preferably from 1/5 to 1/3, of the total.surface of the tubes of the same stripper. 3. A process according to claim 1 or 2,wherein the pressure during the CO2 stripping, is from 130 to 220 (prefe 2 rably from 170 to 210) kg/cm , wherein the inlet temperature of the urea solution fed to the CO2 strip per is from 190 to 220 (preferably from 200 to 2100 C) and wherein the outlet temperature of the final solu tion, leaving th bottom of the CO2 stripper, is from 150 to 210, preferably from 160 to 190 and even better from 160 to 1750 C, provided the same outlet temperatu re be lower than the inlet temperature on the top of the CO2 stripper. 4. A process according to any of claims 1 - 3, wherein the temperature of the CO2 stream, injected as a stripping agent, is from 80 to 140 C. 5 A process according to any of claims 1 - 4, wherein the ratio A between the exchanging surface of the C02 stripper (SCO2) and the exchanging surface (SNH3) of the pre ceeding stripper is given by the expression A = SCO2 / SNH3 > 1. 6. A process for the displacement, at pressures from 130 2 to 220 kg/cm , of the excess of NH contained in 3 aqueous urea solutions having a temperature from 170 to 2100C and coming from a former stripping (isobaric with the synthesis of urea from NH3 and C02), said former stripping being performed in the presence of NH3, wherein said solutions contain also CO2 (as ammonium carbamate), the CO2 amount being equal to or lower than 22% b.w., with respect to urea, and where in said displacement is performed by means of a stripp ing in countercurrent with C02,in a falling-film heat -exchanger containing a tube bundle (CO2 stripper), isobaric with said synthesis, the amount of ammonium carbamate in the solution leaving the bottom of the CO2 Stripper being substantially equal to the amount of ammonium carbamate in the solution entering the same stripper, characterized in that: a) the global NH : C02 weight ratio, in the solution fed to the CO2 stripper, is from 3 to 6; b) heat is substantially supplied only to the upper most portion of the tubes of the C02 stripper, wherein the ratio between the surface of the lower most portion and the surface of the uppermost por tion of the tubes is at least 2:1 and wherein the ratio between the residence time of the solution to be stripped-in said lowermost portion and the residence time in said uppermost portion is at least 2: :1, said residence time in theAlowermost portion of the tubes being at least 3.5 s, and preferably from 3.5 to 5 s., and said residence time in the uppermost portion being at the most 2.5 s. and preferably from 1.5 to 2.5 s. c) The outlet temperature of the final solution, leav ing the bottom of the C02 stripper, is from 160 to 1900 C, provided the same (outlet) temperature be lower than the inlet temperature on the top of the CO2 stripper. 7. A process according to claim 6, characterized in that: a) the global NH3 : CO2 weight ratio, in the solution fed to the CO2 stripper, is from 4 to 5.5; b) heat is substantially supplied only to the upper most portion of the tubes of the CO2 stripper, wherein the ratio between the surface of the lower most portion and the surface of the uppermost por tion of the tubes is from 2:1 to 4:1 and wherein the ratio between the residence time of the solution to be stripped in said lowermost portion and the residence time in said uppermost portion is from 2:1 to 4:1, said residence time in the lowermost portion of the tubes being from 3.5 to 5 s, and said residence time in the uppermost portion being from 1.5 to 2.5 s. c) the outlet temperature of the final solution, leav ing the bottom of the CO2 stripper, is from 160 to 1750C, the temperature of the C02 stream, in necked as a stripping aaent being prAeferably from 80 to 1400C.

Inventors: PAGANI, GIORGIO
Applicants: MONTEDISON S.P.A.
Application year: 1983
Main classification: C07C126
IPC codes: C07C273