Vol. 4, No. 2 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) 1989 STEADY-STATE SIMULATION OF AMMONIA. SYNTHESIS LOOP Yu Yusuo* (¢r# AND WANG CHANGYING (££ 3) (College of Chemical Engineering, Dalian University of Science and Technology, Dalian, Ligening) Abstract The performance curves of the synthetic gas compressor of a Kellogg-type ammonia plant are fitted by polynomial models, and regression models are also presented for the vapor-liquid equilibrium of ammonia separa- tion process and the loop pressure drop. The refrigeration duty required for the separation of ammonia is also estimated. Steady-state simulation of ammonia synthesis loop is carried out by a combination of se— quential modular and equation-solving approach. The con.parison of the simulation results with the actul plant records shows in good agreement. Effects of main operation variables on process performance are stud- ied by simulations under 53 operation conditions. 1. Introduction Investigation of steady-state simulation and optimization of operation conditions of ammonia sythesis process is essential for better understanding of the effects of process variables ‘on the process performance and for further improving the economic profits. Gainst"? reported fa steady-state simulation of ammonia synthesis loop containing two identical parallel quench— type converters. Taletskayat? presented mathematical control models of the process. Biegler et al. using Q/LAP technique carried out the simulation and optimization of the process. Reddy et alii") described the modeling and simulation of the synthesis process with Casale type converter. In this work, Kellogg type of ammonia synthesis process is used as an example, Il. Process Description ‘As shown in Fig. 1, the fresh compressed feed gas, mixed with the recycle gas is further compressed in the 3rd stage of the compressor to about a pressure of 15 MPa and then enters into the synthesis loop. This gas flows through the water cooler 2 and ammonia refrigerators 3, 4, 5 successively for the condensation of ammonia. Liquid ammonia is separated in sep- arator 6, while the gas passes through the heat exchanger 8 for recovery of its refrigeration and is then fed to the converter 9 after preheating (not shown in the figure). Converter effluent passes through a heat recovery system, and specified portion of the stream is further cooled in refrigerator to condense ammonia (not shown in the figure). Liquid ammonia is recovered in Received April 23, 1986, Journal of Chemical Industry and Engineering (Chinese Edition), 39(2), 129 (1988) * Author to whom correspondence should be addressed, he.196 | JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) separator 10, where the gas purges to a fuel system. ‘The major portion of the converter effluent loop. is recycled to the 3rd stage of compressor, thus completing the synthe: purge makeup gas NE product . Fig. 1 Flow diagram of NH, synthesis loop 1—compressor; 2—water cooler; 3,4,5—animonia refrigerator; 6,7,10—ammonia separator; S—heat exchanger; 9—ammonia synthesis converter II, Mathematical Models 1. Compressor and pressure drop of the loop The regression model of the performance data of the Ist stage of compressor can be formu- lated as follows (compressor speed 117—183 r/s, suction volume 0.8—1.9 m*/s): KW,=By+BiuMi N +BuMN?+ Bi MiN* (1) Pet aC tC Mit Cu +CuMiN +CuME+CuMiN +CysM\N?+C,,MiN* (2) Models of the 2nd and 3rd stages of the compressor are similar, but with different sets of con- stants. Models of the loop pressure drop can be obtained by regression from plant data (with flow rate ranging from 75 to 100% of design value). AP=4,+4, >) (FMW )*0 (3) The calculated loop pressure drop must equal to the pressure increase across the 3rd stage of compressor (Py,~P.,) at certain recirculation rate and fresh feed rate. Convergence criterion on loop pressure drop calculation is defined as follows:SIMULATION OF AMMONIA SYNTHESIS LOOP 197 ) (Pas—Pa)-AP , Parka <0 ) i With a given initial value of compressor speed V4, the new speed can be computed as follows aPhic (5) N =No~C(Pas~ Pas 2. Ammonia converter Considering one dimensional pseudo-homogeneous model for ammonia synthesis convert- er, the rate of synthesis in a modified form of the Temkin-Pyzhev equation expressed in activities as suggested by Dyson and Simon! is given as follows: mobel pe( Oak on . remand) -(30)] 6) The concentration of ammonia and the temperature profile in the catalyst bed are given respectively as follows!*?: dya_ CAYA)ET ea prs (Payer?) A pada] de 2hAn yg, KP ( Paya ) Je vie yii ) @™ aT AHs dy, xD “de Fy )G, de MC TT) (3) The temperature distribution in the annular space between shell and catalyst basket is aT, xD va WC 98 (T.—T) (a) Model for quench zone is -Mosesl” Cod? =fiMr| "Cora? (10) Tora P where j=1—4 is the catalyst bed number, and 7,. is the outlet gas temperature of heat exchanger. ‘As for heat exchanger, the model derived by Shaht” is adopted. The correction coefficient 1 of catalyst activity is determined by reverse calculation from plant operation data. A simplified gas flow diagram of converter is shown in Fig. 2. The feed gas enters into the converter and flows upward in annular space around the catalyst basket. The gas is then heated up in a feed-effiuent heat exchanger located at the top before passing down through four beds of catalyst. Cold feed gas is supplied to each of the four quench zones to obtain optimum temperature for conversion, With inlet gas temperatures for both sides and the inlet gas composition for the tube side of the heat exchanger assumed, numerical integration through the catalyst bed can then be carried out as an initial value problem, Ammonia concentration and temperature profiles in the catalyst bed as well as temperature distribution in the annular space can then be calculated.198 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) The calculation is proceeded by iteration until convergence between the test and calculated values is reached. Fig. 2. Block diagram of synthesis converter VN | 1—annular space for shell cooling: 2—heat exchanger; 3—quench zone; 4—catalyst bed 3. Separator * The flow rates and compositions of outlet streams from the separator are calculated from material balance and vapor-liquid equilibrium relationships. The vapor-liquid equi- librium constant of component i, K,, is calculated from the following regression models, oT Mb bau + asT* (1) (For NH,, N, and H,, the pressure range is 4.0 —3SMPa and temperature range ~S0—70°C) WgK = bio tba +O.2lg P+ bi + buT lg P (12) (For CH, and Ar, the pressure range is 0.7—3.0 MPa and temperature range -30—30°C) 4, Refrigeration duty requirement for the separation of ammonia wn of ammonia into liquid product from the recycle gas, the refrigeration For condens: duties required in refrigerator 3, 4, 5 with refrigeration recovered from exchanger 8 consid- ered are estimated by energy balance. The enthalpies of the gas component are calculated according to Rase") and that of liquid ammonia is calculated from the data presented by Joachim Ahrendts!”. 1V. Calculation Method and Computational Procedure The simulation of ammonia synthesis loop is carried out by combining the sequential modular approach with equation-solving.The computational procedure is shown in Fig. 3,SIMULATION OF AMMONIA SYNTHESIS LOOP 199 Assuming a set of itil values of feed rate and inlet composition of the gas to the converter, then calculate the approximate gas and liquid outlet compositions from all the separators. Solve the set of simultaneous equation of material balance for feed rate and inlet composi converter until convergence is obtained. ion of Estimate converter feed rate, composition, recirculation rate Calculate compressor power requirement , discharge pressure Calculate loop pressure drop aap (Pis-P.2)-P Bia Pas Regstimate compressor speed Call CONVERTER subroutine Calculate outlet gas — liquid compos.tion of separater 10,6,7 Solve simultaneous equations for NH, production, recirculation rate, converter feed composition ete. Reestimate composition Calculate refrigeration; duty requirement Output of results Fig. 3 Computer procedure200 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) Y. Discussion of Simulation Results 1. Overall siraulation Result of overall simulation and design data are show in Table | for comparison. Table 1 Comparison of simulation results with design data ‘Comparison Converter NH, in ‘NH; in NH, item feed rate converter converter production kmoljh feed, % effluent, % ud design data 27785, 1000 simulation . result 29020 22 11,58 1000 relative error % 44 al —3.50 ° Comparison Flash gas Flash gas Recirculation Refrigeration item rate from rate from, rate duty separator 10 separator 7 Fequirrment kmol/h kmol/ht kmoi/h Gyn design data 423.1 15.2 2861 07.26 + simulation result 428.5 18.2 26086 102.24 ° 2.09 1.68 Comparison ‘Compressor Discharge Converter, Compressor iter power pressure inlet speed! pressure kW MPa MPa rmin design data vst? 15.48 ose? simulation result 15.18 14.09 ozes relative error = 15.39 =1.94 =2.89 It can be seen from the table that the simulation results agree satisfactorily with the design data.The relative errors are all within 5% except the compressor power. This diserep- ancy is mainly due to the fact that the gas suction volume of the recycle stage given on the performance curve is larger than the actual data, ‘Thus, one may consider that the mathematical models adopted in this work give more correct values. 2, Simulation analysis under various operating conditionsSIMULATION OF AMMONIA SYNTHESIS LOOP (1) Effect of feed rate ulation results under $3 operating conditions are given as follows: When the synthesis loop is operated at constant inert concentration and constant H,/Ny ratio, the effect of feed rate is shown in . 4 and 5, All process variables almost increase linearly with the feed rate However, the actual production rate is restricted by the compres- sor speed, capacities of heat exchanger and refrigeration, and converter stability. 32) 16.0 15.6 = > “ 8 45.2 2 3 14.8 z 6 eee Tr 80 100 110, Feed rate, % Fig, 4 Recirculation rate and discharge pressure vs. feed rate 2) Effect of inert content 1350 1250) 10504 950 10500 10300 10100 ‘9900 9700 a 1 ___}9500 80 90 To 110 Feed ra Fig. 5 NH, production and compressor speed vs. feed rate Compressor speed, r/min Effect of inert content upon plant operation at constant feed rate and H,/N, ratio is shown in Figs. 6—8. When the inert content increases, the power consumption increases too. This is primarily due to the inerease in recirculation rate. At the same time ammonia production 6.20 a an z 6.20 3 1000 s.10 3 = 990) 16.00 £ 2 0 A) zis ase a Inert content, % Power consumption, kW-h /kmol 6 NH,- production and power consumption vs. inert content202 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) also increases, however. with a different rate from that of power consumption, Therefore it is desirable to optimize the inert content with appropriate objectives. Simulation also shows that the converter may become unstable when inert reaches a sufficient high content. & ne 29 16.0 5 > - 3 £ E28, a = 58g é a = 27 15.6 § Fig. 7 Recirculation rate and g 4 discharge pressure Vs. = 2 inert content 3 26 - 415.49 £ 5 $ 5 % 25 1 L 15.2 & cn . o Inert content, 9% = 43576) 420 3 & 2 42738 4400 5 X 5 8 3 41900) 380 Fig. 8 Refrigeration duty g C requirement and purge 3 4162+ {360 = rate vs. inert content § 2 : a % 10224 340 @ 39386! 320 13 15 7 19 Inert content, % () Effect of H,/N, ratio in the converter feed The effect of H,/N, ratio in the converter feed at constant feed rate and constant ammonia concentration in converter feed is shown in Figs, 9 and 10. As seen from Fig. 10, the power consumption exhibits a minimum at H,/N, ratio of about 2.2—2.3, whereas a maximum. ammonia production may be achieved at the H,/N, ratio of around 2,0, In fact, the optimal H,N, ratio is influenced by a number of factors,SIMULATION OF AMMONIA SYNTHESIS LOOP 203 15.9¢—-—__ 30 8. —1020 ba owe a ee < = 3 22, . Sisd oo = 26 ove é £ Fs. 1008 S 15.3 v4 § s 2 5 5.8 jloo8 é 15.14 eof = 5.7] 1000 a 1.9 20 a LS 2.0 2.5 3.0 3.5, He/Ne ratio Hy /N; ratio Fig. 9 Discharge pressure and Fig. 10 Compressor power consumption and recirculation rate ys. H,/N, ratio NHy production vs, H,/N, ratio (4) Effect of ammonia Concentration in the converter feed The effect of ammonia concentration in the converter feed on the operation at constant feed, constant inert content and constant H,/N, ratio is shown in Figs. 11 and 12. Itis clear~ ly seen from the figures that recirculation rate, power consumption, and refrigeration duty requirement for separation of ammonia all increase with the ammonia concentration, and moreover, ammonia production is also increased. -— 1000 | 815 its & 4190 E = 6.10 Lois = 2 4 : g E61 azo 6.05) 00s 2 g E 3 2 2s.s4 5 : 5 3 as. use g 8 F 6.00 aos £ “=e + = g * E z * 35.1 a1 = 5.98 985 1a ar io aa ats NE content in converter feed, $5 NH content in converter feed, *% Fig. 11 Recirculation duty requirement vs. Fig, 12. Compressor power consumption NH, content in converter feed and NH, production vs. NH, content in converter feed201 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) VI. Conculsions m The simulation of ammonia preduction process under basic operating cond ees satisfactorily with the design data. Simulation under different conditions provides a better understanding of effects of process variables on ammonia synthesis operation, Nomenclature 4 cross-sectional area of catalyst bed, m*? AoA constants in Eq. (3) @x.0n.0% activities of NHs. Hs and Ns. Pa constants in Eq. (11), é refers to NH., Ns and H. . constants in Eq. (I) constants in Eq. (12), # refers to CH, and Ar constants in Eg, (2) constant in Eg. (5) heat capacity of reaction gas in the converter and feed gas to the converter, kJj(kmel,-*C) ‘outside diameter of catalyst basket, m gas component flow rate, kmol/h fraction of converter main gas stream and of quench stream heat of reaction .ki/kmol NH, equilibrium constant in terms of activities ‘gas-liquid equilibrium constant overall and Ist stage compressor power, KW rate constant for decomposition of ammonia thermal conductivity of catalyst basket insulation, kij(m-h-*C) molar flow rate, kmol/h converter flow rate (ammonia free basis) and converter feed rate, kmol/ inlet gas rate to Ist stage of compressor, m/min molecular weight of component, é refers to NH; No, H;, CH, and Ar outlet molar flow rate from catalyst bed of converter, kmol/h compressor speed and its initial valve for iteration, r/min pressure, Pal compressor discharge and suction pressure, Pa pressure drop of synthesis loop, Pa synthesis rate of ammonia, kmol NH, (h-m cat.) temperature, K temperature in annulus, K temperature of converter feed, K outlet and inlet temperature of catalyst bed, K » specific volume, m,/kmo! Yaryuvys mole fractions of NH, , H. and Nz in stream yaya calculated NH, mole fraction and its initial value 2 distance from the top of the catalyst bed, m YvarPurtn activities coefficient of NH, H. and 4 thinkness of insulation, m a activity correction coeffeient of catalyst References [1] Gaines, L.D., Chem. Eng. Sci., 341}, 37 (1979), [2] Tanmea.E.A.Xwx. Mpow. $7 (3), 177 (1981). [3] Biegler, L.T. and Huges, R.R., Chem, Eng. Prog., 7714], 761981).SIMULATION OF AMMONIA SYNTHESIS LOOP 205 Reddy, K.V. and Asghar Husain, Ind. Eng. Chem. Process Des. Dev., 24(3}, 359 (1982). Dyson, D.C. and Simon, J.M., Ind. Eng. Chem, Fundam, 14}, 605(1968). Gaines, L.D., Ind, Eng. Cham. Process Des. Dev., 16 (3}, 381(1977). Shah, M.J., Ind. Eng. Chem, 59 (0), 72(1967). Rase, H.F., “Chemical Reactor Design for Process Plants”, vol. 2, John Wiley and Sons Inc., New York, 6101977). Joachim Ahrendts und Hans Dieter Bacht, VDI-Forschungsh, $96(1979).