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    The primary reformer is one of the most important process units in a natural gas based ammonia plant, and the largest energy consumer in the plant. Therefore, it is imminent to carry out simulation analysis of the reforming system to find ways for sa ving energy.

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    The primary reformer is one of the most important process units in a natural gas based ammonia plant, and the largest energy consumer in the plant. Therefore, it is imminent to carry out simulation analysis of the reforming system to find ways for sa ving energy.

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    37 views10 pages

    19950405

    Uploaded by

    Mohamed Tarek
    The primary reformer is one of the most important process units in a natural gas based ammonia plant, and the largest energy consumer in the plant. Therefore, it is imminent to carry out simulation analysis of the reforming system to find ways for sa ving energy.

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    Attribution Non-Commercial (BY-NC)
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    Chinese J. of Chem. Bng., MA) 223-232 1998) SIMULATION ANALYSIS AND OPTIMIZATION OF STEAM REFORMING PROCESS FOR A LARGE-SCALE AMMONIA PLANT Zhang Shuwei( iit {i )tand Yu Yuguo( § # | School of Chemical Enginsering, Dalian University of Technology, Dalian 116012, China Abstract The present paper shows how the Schuster Schwarzschild method developed originally in astrophysics can be adopted to simulate the performance of the primary reforming furnace in an em: rmonia plant, This method facilitates the simulation of heat transfer and teuetion in the furnace and improves the computational efficiency, Simulation analysis is carried out to find ways of saving ener gy. Appropriate reduction in fuet pas Primary (0 the secondary reformer by regulating the operating conditions can result in substantial ergy saving. Optimization calculations with various object iding and partially shifting of the reforming loud from the fe functions and constraints required are performed. The optimization results may serve as guideline for plant operation snd control Keywords. simulation, optimization, energy saving, reformer 1 INTRODUCTION The primary reformer is one of the most important process units in a natural gas based ammonia plant, and the largest energy consumer in the plant. Therefore, it is imminent to carry out simulation analysis of the reforming system to find ways for sav- ing energy. Ravi. K., et al. [1] did the simulation of the reformer circuit in a naphtha based plant for improving energy performance. By using detailed models of each reactor sys- tem, the tube wall temperature of the primary reformer was calculated with known plant data. To achieve a better understanding of the temperature distribution in the firebox and in the reactors, Patrick M., et al. (2] applied the zone method to simulate heat transfer and reaction in a steam reforming furnace. However, the algorithm bused on zone method was rather complicated and the calculation was rather time consuming In the present study, the Schuster-Schwarzschild method [3, 4], developed originally in astrophysics and reported by Chandrasekhar et al. [5, 6), is adopted to treat coupled simulation of the firebox and the reactor, As compared with the algorithm based on zone method, this method has the advantage of high computational efficiency, and thus provides a reliable base for further optimization 2 DESCRIPTION OF THE STEAM REFORMING SYSTEM ‘The system includes two important process units, the primary and the secondary reformers. The endothermic steam reforming reaction of hydrocarbons takes place in the catalyst filled tubes suspended in vertical rows in the radiant section of the prima- Received 1994-01 ~ 10, aecepted 1994 -O8~ 23 + To whom correspondence should be adldresed. 224 Chinese J. Ch. (Vol.3, No.4) ry reformer furnace. The reaction heat required is supplied by down firing of fuels be- tween the rows of tubes. Most of the reforming reaction (akes place in the primary reformer, The partially reformed gas enters into the secondary reformer where preheated compressed air is fed to supply the nitrogen required for ammonia synthesis. Combus- tion and reforming reaction of the remaining unconverted methane are simultaneously occurring in this reformer. The heat liberated by combustion supplies the energy re- quired (© complete the endothermic reforming reaction Figure 1 Sehematie di of the stant I-burner flame; 2~catalyst filled tube: 3 rehactory wal: 4 primary reformer; $~secondary relorme 3) MATHEMATICAL MODELS AND CALCULATION METHODS The model adopted here is similar to that given by Roesler [7], but the present study takes a new calculation method coupled with optimization. It is assumed that the pro: cess tubes are uniformly distributed over the cross section of the furnace and the burners over the roof is located in-between the tubes as shown in Fig. 1. Transverse gradients of temperature and velocity in the furnace gas are to be neglected. Over most of the vertical section of the furnace, distance x from the top, plug flow of the fluc gas can be assumed, because the thermal stratification is strongly stable ard the mean velocity is low. The refractory surface and the tube surfaces are assumed to be optically grey, with specified emissivitis ¥ and 1 respectively. The heat transfer from the flue gas to the tube wall by simple conduction or by convection (of the order of | percent of the total heat load [7]) is omitted. Optical scattering effect, that changes in beam direction without intervening absorption and emission, is also omitted [7]. ‘The furnace structure may be specified by four quantities: @ height L; ® penetration depth D of the flame jets, which is related (o the structure of the burners; ® tube wall area per unit free volume 2y; @® area of refractory wall per unit free vol- ume, 26. (The term “free volume” refers to the internal volume of the furnace between and around the tubes.) The heat input to the furnace can be described by the term (NycT,). The temperature of process gas T;,(U) and the overall resistance to heat transfer between process gas and tube wall R(U) can be obtained from the mathematical models of the reactions and heat transfer in the tubes. in which U is the heat content per unit mass December, 1995 Simulation and Optimization of Steam Reforming Process for Ams of provess gas, In the literature [8], the representation of the flue gas emissivity refers to a mix- ture of gases, but in the present treatment the emissivity is interpreted as a partition of the radiation into only two colours:"band radiation” and “window radiation”. So the emissivity takes the special form ant [l-e w where rt is the band fraction of the spectrum. For convenience. x is expressed as fol- lows. waa /T Q) where a is a property of the furnace gas composition. The description of radiation properties of the gas is thus reduced (o (wo parameters t and 2. To fix t und Kk, two emissivity values [9] must be determined as being corresponding to mean beam length [10] and twice the beam length. Subsequently, x can be determined from x. T and T, Of the total radiation oT emitted by a black body, the fruction r is the band radi- ation and the fraction =1=+ is the window radiation, When a beam of band radi ation strikes the grey refractory or tubes. a fraction (11) will be reflected as band radi: ation, and a fraction 7 will be absorbed. On re emission, this will be further split into a fraction v of band radiation and a fraction wy of window radiation, The net af fects is: of the original beam, the fraction (1—y) +t remains as band radiation, whereas the fraction co becomes window radiation. So a colour shift into a beam of window radiation occurs Though the Stefan Boltzmann equation t paT* Qa) is well known, but the Koenigsberger equation which gives the amount of energy radi- ated by a volume element of gas dq=4e'oTUh 4) is also fundamental. Here «° is the differential emission coefficient, Based on Eq.(1). the quantity of «” becomes de ds ge (5) Applying the Schuster Schwarzschild method to the radiant section of the primary reformer. the radiation ficld can be decomposed into a finite number of beams. In this case, for simplicity, four beams are used to define the two colours of radiation and the two directions of propagation. Fach colour of radiation forms two directions of propagation, upwards and downwards. These beams. without being associated with streams of matter, are coupled with one another and with the two heat streams carried by the flue gas and the process gas in the tubes respectively. Then, the primary reformer can be treated as a multi stream heat exchanger. The intensities of these streams can be described by ordinary differential equations. The six heat streams are as Chinese J. Ch. B. 44) 223 (1998) 226 Chinese J. Ch. B, (Vol.3, Nod) follows; EG) heat imput stream transported by the flue gas F(x) band radiation downwards G(x) band radiation upwards A(x) window radiation downwards B(x) window radiation upwards H(o heat output stream transported by the process gas Based on heat balances, Stefan Boltzmann equation, Koenigsberger equation and the symmetric relations between band radiation F(x), G(x), as well as A(x), B(x), the complete expressions of the six differential equations are as follows dE/dx = — 2fotT*+ BF + BG (6) AF /dx=BorT*+(— B—Wy—n6 +198 /2)F + (18/2) 7) + (15 /2)A + (15 /2)B + Wot TS dG [dx = BorT*+ (15/2)F + (— B— by — nd + 8/2)G (8) +(293/2)A + (498 /2)B + WyorTS dA fdx= (cond /2)F + (cond /2)G + (— Wry = 5 + 095 /2)A 9) +(ond/2)B+ Wya@T? = dBldx= (on5/2)F + (cmd /2)G + (ond /2)A (0) +(— dy 16 +0095 /2)B+WyooTS dH [dx =F + pyG +WyA +HyB-2WryoTs ap For example, in the equation for dF/dx. there is a term-BF which describes the re-absorption of radiation by the gas. Where fi is a coefficient to be determined. There must also contain a term expressing the emission of band radiation in the equation These two terms must equal with each other and cancel in equilibrium state. At equilibrium F has the value o7*, Based on Koenigsberger equation, of the total emis- sion of a volume element, only half goes into F, and the other half goes into G Therefor 2tKoT*=proT* p=2« (12) By taking into account the absorption term by the tubes, —OYF, the emission term of the tubes, W073, and the cancellation of the two terms at equilibrium, the follow- ing relation holds wro4, (3) Similarly, for the beams of F, G, A, and B, in the equation for dF/dx there must be terms describing the absorption and re-emission of radiation by the refractory, n6F, SF, 18 /2G, 18/24, and 1m5/2B. Hence the Fq.(7) is derived The relation of flue gas temperature and its heat content is December, 1995 Simulation and Optimization of Steam Reforming Process for Ammonia Plant 227 E=NeT a4) By heat balance. the heat transfering through the tubes is equal to the heat content in- crement of process gas. The rckition between the surface temperature, 7, and the temperature of process gas, T,,. is (T= T,))R= WE +G + A+ BY? aT] as) The four boundary conditions used are as follows: If G and B are known at the top of the furnace, then F and 4 can be found from =(1=1G + MG +B) (16) I= m)B+onG +B) a7) If F and 4 are known at bottom of the furnace, then G and B can be found from G= (=F + mF + A) (18) B= (1~m)At+om(F +A) (19) Each pair of relations is subjected to the following equation of conservation of radiant energy PEA=G4B The fifth boundary condition is the initial value of H. It can be obtained from the inlet condition of the process gas Hy=Uy*N, (20) The sixth boundary condition is the initial value of E. At the top of the furnace, near the roof, it is assumed that most of the free volume is occupied by low velocity re circulating flue gas. The state of this gas reaches nearly equilibrium with the local radiation field. Hence an estimate for T, can be given by Ty=[F, +G,)/20e] Ql ‘The corresponding value of E is E,=NyeTy (22) In order to calculate the overall heat input £,,, the deficit, namely O=Nye(Ty~1,) (23) can be added to the heat stream F and can be evaluated by a source function g which should satisfy the integral condition [ qdx=Q (24) Considering the fact that q=0 when x=0, and smooth and normalized distribution, the source function can be expressed as [7] ‘Chinese J. Ch. B34) 223 (1995) Chinese J. Ch, B (Vol-3, Nod) a(x, D)=6(Q/D)(x/D ~ D (26) The differential equations shown above are nonlinear and can be treated as boundary value problems and solved as finite difference equations. For the simulation of the primary reformer tubes, one dimensional psuedo homogeneous fixed bed model is employed [11]. Based on the simulation of the fire box and the reactor, coupling of the calculations is carried out with estimated tube wall temperature distribution. Repeated iterations are performed until convergence is attained. 4 SIMULATION RESULTS AND DISCUSSIONS The structural parameters and inlet conditions of the furnaces needed for the calculations are taken from a design data and operating data of a top fired type reformer plant. The structural parameters of the primary reformer are as follows: furnace length 15.902m, height 9.582m, width 12.680m, distance between tubes 0.260m, number of tubes 378, tube diameter 114/71, tube length 9.582m. The structural parameters of the secondary reformer are as follows: diameter 3.277m, catalyst height 3.962m. Inlet stream conditions of the primary reformer are: process natural gas: temperature S10. pressure 3.34MPa, flowrate 5702.1kmol +h ! composition(mol/mol) CHy 18.57, CH, 0.67, CoH« 0.30, CuHw 0.19, CsHy 0.16, Ni 065, H: 1.08, CO; 0.10, 0; 0.10, H:O 78.18. fuel gas: temperature 163 . pressure 0.22MPa, flowrate 558kmol+h '. composition similar to process natural gas. Excess air coefficient is 1.15. Process air rate into secon- dary reformer is 1856.2kmol « h’', Calculated results are shown in Table 1 and Fig.2. Table 1 Calculated results versus design and operating data for the primary reformer at outlet parameter TK TK ‘design data 1316 1096 5.54 calculated value 1323 1109) 5.2 relative error, % oss Lis 0.36 operating data 1303 0 5.35 calculated value 1297) ross sa relative error. % 0.45 0.64 0.5 The effects of fuel gas loading and H.O/C ratio for the primary reformer on the outlet methane content (dry basis) are shown in Fig.3. As fuel gas rate decreases, outlet methane content increases when other conditions remain unchanged. This relationship provides a basis for the appropriate distribution of the load between the primary and sccondary reformers. Lower H,O/C ratio must be restricted to such an extent as to avoid carbon depositing on the catalyst. Besides, as December, 1995 é % 8 sof be soo a8 Loreto ee a0 TOT 0 KL /60) O/C 2 femperatore and compesition profiles Flgate 3 Fifxts of fuel yas loading and H,0(¢ slong the tubes ratio for the primary reformer on the betys 2-7 outlet methane content (dry basis) Fuck gas londings 190%; 2~ 100%: 3 110% shown in Fig.2, with optimum value of H,O/C ratio exists on its influence upon the residual methane content when the fuel gus loading remaining constant, the outlet methane content will decreases as H,O/C ratio increases when the H,O/C ratio is comparatively low, but as the H,O/C ratio exeeds the optimum value, undesirable in- crease in residual methane content may be observed. This is due to the overloading of steam leading to the decrease in process gas temperature in the tubes, thus influencing the reforming process of methane. Of course, at high H,O/C ratio, low residual methane content can be achieved if the required outlet temperature of the process gus can be guaranteed at the expense of high fuel gas consumption. As shown in Fig.3, fuel gas consumption can be reduced by any appropriate decrease in the H,O/C ratio However, the reduction of H,O/C ratio must be restricted to such an extent as to avoid carbon deposits on the reforming catalyst Any reduction in fuel gas rate will lead to the increase of methane content from the primary reformer, but increases in process air flowrate and its preheated temperature will be helpful for improving the methane conversion. Hence, optimal methane concentration of partially reformed gas for energy saving can be obtained by partially shifting the load from the primary to the secondary reformer and by appropriately increasing the process air rate and its preheated temperature. However, the extent of this shift is limited by the amount of residual methane in the outlet gas from the secondary reformer and the nitrogen required for the ammonia synthesis. § OPTIMIZATION OF OPERATION CONDITION The H,O/C ratio used in actual plant operation for the primary reformer is ubout 3.5 in present-day practice. So no optimization of this parameter is attempted in this pa- per. Besides this parameter, it is shown from the investigation of the actual plant oper- ation that the energy consumption of reformer units can greatly be effected by the fuel Chinese J. Ch. B. 344) 223 (1995) 230 a Je Oh. B, (VOL3, Nod) gas rate and the outlet methane content of the primary reformer as well as the process air rate and its preheated temperature for the secondary reformer. Hence optimizations of these parameters with different objective functions are studied in this paper. 5.1 Optimization of parameters and its constraints The fuel gas loading required at specified outlet methane content from the primary reformer can be calculated, thus Q,, the energy saving relative to the design condition can be obtained. Any decrease in fuel gas loading would lead to reduction of heat content in the flue gas from the radiant section of the furnace to the convective section. The increase in heat input Q; required for raising the heat content of flue gas as compared with the design value can then be calculated The increase of heat input Q, required for raising the preheated temperature of the process air as compared with the design value can then be calculated. The increase of work input Q, required for compressing the process air as compared with the design value can then be obtained. The constraints for optimization are: (a) outlet methane content from the secondary reformer should be <0.5%. (b) @ specified hydrogen to nitrogen ratio (H,+CO)/N; is required 5.2 Optimization method Optimization method of variable transformations is used with different objective func- tions. jons and optimization results lum energy consumption Min Q.=—(Q,-Q:-Q;—Q0 sit 9%

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