Paper No.513 MASS BALANCE CALCULATION METHOD IN METHANE-STEAM REFORMING. BY ‘Mrs, ZULEKHA Soomro B.SC.(HON) M.Se. ASSISTANT PROFESSOR, PETROLEUM & GAS ENGINEERING -MEHRAN UNIVERSITY OF ENGINEERING & TECHNOLOGY JAMSHORO. 145Paper No.613 MASS BALANCE CALCULATION METHOD. IN METHANE - STEAM REFORMING. BY Mrs ZULEKHA Soomro* B.Sc. (Hon), MSe. MASS BALANCE CALCULATION METHOD IN METHANE-STEAM REFORMING. ABSTRAC’ ‘An attempt was made to calculate the reaction product compositions in moles on a ‘wet basis obtained from experimental work were substituted into equilibrium expression for the methane-steam and the watergas-chift reactions and equilibrium constant calculated. A mass balance calculation method has been developed for the reformed gas composition obtained experimentally from methene-stoam reforming at the molar ratio 1:x.(7] INTRODUCTIO! Methane represents the simplest alkane capable of being reformed. The design of methane-steam reforming processes and the product compositions are calewlated using a combination of two equations representing the methene-steam and the carbon-monoxide Shift reaction (1,2,8) Endothormic Hy + Hy0 Exothermic CO + HO CO+aH, a -CO+H, @) ‘The equilibrium compositions will depend on temperature, operating pressure and steam-methane ratio, For equilibrium at ¢ particular temperature, the equilibrium constants for the reactions (1) and (2) are es follows: _ 3 3 PCO PtH, For reaction (1) Kl = BEY COR Gia) PCHp Hye 2 GH nH0 Assistant Professor Petroleum & Gas Enginesring ‘Mehran University Of Engineering & Technology Jamshoro. 347Madam Zulekha Qazi For reaction (2) K2 = re oe BGo plo n00_afi,0 ‘The guocs are assumed tobe ideal, u is the sum of meles of gas at equilibrium and Ps the total pressure. If values ofK1 and K are known st a given temperature then for a specified total prossure and initial methane-stem ratio tho number of molos of each component at equilibrium may be determined (4). A mess balance calculation method has heen developed for the rofocmed gas composition obtained experimentally from methanesteam roforming st the molar rato Lx, DEVELOPMENT OF EQUATIONS: ‘Suppose, initially, S moles of steam are present per mole of methane. If X is the conversion of methane by reaction (1) and Y is the conversion of carbon-monoxide by reaction (2), then the number of moles of each component present at equilibrium can be calculated as follows: umber of CH, + HO = CO + 3H, moles Tax sxy xy Sxty CO +H,0 = H+ C0, number of % moles xy sxy Sxty Y ie Now equations (3) and (4) may be written (ey) Gxty)> © (a9 (sry) and @ Gxr+y) Kz —— © &y) xy) Itis customary to report the produce composition data in steam reforming reactions on a steam free basis (dry basis) since the steam is not a constituent in any of the synthesis gases produced or in the reformed gas when used as a fuel. The above equations are then solved 148,‘Paper No513 simultancously for and y. Solution is best done by an iterative technique (5). ‘The ealculations mentioned above ean be used to predict the theoretical reformed product gas composition at equilibrium for methane-steam reforming for any range of steam ratio, temperature and pressure. Then the number of moles of each component is cbtsined at equilibrium constants (9) & (4) for a specified temperature, since these equilibrium constants are not affected by steam ratio or pressure except the temperature. ED _GAS COMPOSITIONS: ‘Tho caleulation of the reformed gas composition for any type of process and for any ‘set of operating variables can be carried out by the three element balances equations for C-atom balance, H-atom balance, O-atom balance and two equilibrium relationships (6). Mags balance calculation for methane-steam reforming. ‘Mass balance caleulation of the reformed gas composition for methane-steam reforming at the molar ratio 1x CH, + 3H0- CH,+H,+C0)+H,0+cCO =) For Carton-free operation, let the output be: Methane CH: moles Hydrogen, Hy :b moles Carbon dioxide: €0g = ¢ moles, ‘Steam 1,0: d moles, Carbon monoxide CO : emotes. ‘The element balances give the following relations: Catom balances satetesl @) H2-mole balances rdatb+d=x+2 o O-atom balances sQe+dte-x ao Equation (10) can be written as ugMadam Zulekha Qazi dex 2e-e (20) Equation (11) is obtained by subtracting equation (6) for equation (2). atbtdeo=xs1 ap Put the value of d from (10) in equation (11) atbtx-2e¢0-K41 atl=8ct2ee1 ay On dry basis (water-free) the reformed gas composition as mole % is as follows: Equations (15) end (16) ean be written as atbdtete co2 e CO =atbicve coz 1D 190 as ay as a6) as) ae) =co = coz coPaper No.o13 Ive equaltion (15) substitute the value of (a+b) from equation (12) into (16). ae sc42etirere © C02 = 4e + Se 41 as) ‘Then, from the experimental infrared analysis the values for COp and CO (on dry Dasis) can be put into equation (17), to give the value of ¢ in terms of e, This value of ¢ is further substituted in equation (18) to give the value of e, wiieh is then substituted in equation (17), to give the valve for e, The values of cand e exe then substituted in oquation (8), to give a value for a atete=l 8 ‘The values of cand e are further substituted into equation (10) this gives the value ford. a= - 20-8 ao Now the equation (9) gives the value for b by substitution of a and d. The values oblained for a, b, ed, and 0 are divided by the totsl number of moles and multiplied by 100. This gives the mole percentage on a wet kasis for an equilibrium gas composition, To check whether tho reaction approaches equilibrium the valwes for the above five species are substituted into the equilibrium constants for the reactions (1) and (2). CONCLUSIONS: ‘The following conclusions can be drawn from the procont study: oy A. mass balance calculation method has beon doveloped and presented for the reformed gas composition obtained experimentally from methane steam reforming at the molar ratio Lx. By putting the values for CO2 and CO (on dry basis) from the dry product gas compasition (experimental results) im the Mass balance equations, the wet product gas composition can be ealeulated. 151‘Madam Zulekha Qazi Git ‘The data for the reaction product composition on a wet basis obtained from the ‘Mass balance equations can be substituted into equilibrium expressions for the ‘methane-steam and the water ges-shift reactions and thus equilibrium constants may be calculated, ov) ‘Tho Mase balance calculation method can be employod to analytical results obtainod from the product ges compositions in moles on a dry basis for elkene-steam, reforming for any range of steam ratio, temperature and pressure ‘The preseiit work may prove to be of perticular use to Process Engineers who are involved with reformer design or estimating the output (the reformed product ges composition) from ‘a steam reformer as feed stock for down-steam processing. REFERENCES: 1. GM, Hampson; The Chemical Engineer, July (1979), : 2. P, Balabrahman, P.D. Sunavale, Chemical Hagincoring World. Docombor (1978) 3, MCF. ROGERS, W.M. CROOKS Journal applied Chemistry. September (1966). 4. D.A. Liholi, Chemical Process Engineering March (1985), 5. T.K. Sherwood, "A course in Provess Design’ The M.LT. Press, Cambridge. Massachusetts, U.S.A. (1963). 6, MY. SOOMRO, PhD. Thesis, University of Salford, ULK., September, (1984). 7. MY, Soomro, Mehran University Research Journal of Engineering & ‘Technology, Jamshoro, ‘Velume 6 April 1987, NO-2. 152