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**Ind. Eng. Chem. Process Des. Dev. 1985, 2 4 , 286-294
**

Weltkamp, A. W.; Gutberiet, L. C. Ind. Eng. Chem. Process Des. Dev. 1970. 9 . 386. William, 'R. 6 . Symposium on Composltlon on Petroleum Oils. Determination and Evaluation, ASTM Spec. Tech. Publ. 1958, 224, 168. Yang, H. S.; Sohn. H. Y. Ind. Eng. Chem. Process Des. Dev. 1985, Part 2 of the companion articles in this issue.

indebted to W. Smith for her NMR analysis work.

Literature Cited

Aiired, V. D. Cob. Sch. Mines 0.1984, 59, 47. Bae, J. H. SOC.Pet. Eng. J. 1989, 9 , 287. Brown. J. K.: Ladner. W. R. Fuel 1980. 39. 87. Burnham. A.' K.; Singleton, M. F., Lawrence Llvermore National Laboratory, Rept. UCRL-88127, 1982. Hill, G. R.; Johnson, D.J.; MIHer, L.; Dougan, J. L. Ind. Eng. Chem. Process Des. Dev. 1987. 8 , 52. McKay, J. F.; Latham, D. R. Anal. Chem. 1980, 52, 1618. Reich, H. J.; Jantelat, M.; Messe, M. 1.; Wigert, F. J.; Roberts, J. D. J. Am. Chem. Soc. 1989, 91, 7445. Shape, C. E.; Ladner, W. R. Anal. Chem. 1979, 51, 2189. Sohn, H. Y.; Yang, H. S. Ind. Eng. Chem. Process Des. Dev. 1985, part 1 of the companion articles in this issue.

**Received for review November 7, 1983 Revised manuscript received April 19, 1984 Accepted May 21, 1984
**

This work was supported in part by a Research Grant from the University of Utah Research Committee and the University of Utah College of Mines and Mineral Industries Mineral Leasing Fund.

**Steam-Methane Reformer Kinetic Computer Model with Heat Transfer and Geometry Options
**

Alexander P. Murray* and Thomas S. Snyder

Westinghouse RbD Center, Pittsburgh, Pennsylvania 15235

A kinetic computer model of a steamlmethane reformer has been developed as a design and analytical tool for a fuel cell system's fuel conditioner. Thls model has reaction, geometry, flow arrangement, and heat transfer options. Model predictions have been compared to prevbus experimental data, and close agreement was obtained. Initially, the Leva-type, packed-bed, heat transfer correlations were used. However, calculations based upon the reacting, reformer gases indlcate a conslderably higher heat transfer coefficient for this reformer design. Data analysis from similar designs in the literature also shows t s phenomenon. This is thought to be a reaction-induced h i effect, brought about by the changing of gas composition, the increased gas velocity, the lower catalyst temperature during reaction, and t e higher thermal and reaction gradients involved in compact fuel cell reformer designs. Future h experimental work is planned to verify the model's predictions further.

Introduction A joint program has been conducted by Westinghouse and Energy Research Corporation (ERC) to develop an integrated phosphoric acid fuel cell system. A key component in the fuel cell system is the fuel conditioner, which catalytically reforms methane by reaction with excess steam to produce the hydrogen-rich feed gas for the fuel cells. As a design and analytical tool, a computer model of the methane reformer was required. This model would also assist in the design and interpretation of pilot plant scale reformer data, and in the development of heat transfer correlations. Steam reforming of methane is a key operation in many refinery and petrochemical processes, and, as such, it has been the subject of previous models by Oblad (1967), Grover (1970), Hyman (1968), Singh and S a r d (1979), and Olesen and Sederquist (1979);the details were not available for use in the fuel cell program. Fuel cell system reformers are different from standard industrial units: they are more compact (-60% as large), have higher reaction and thermal gradients, require a large dynamic operating range (25125% of design), and can be small (- 10 kW) or large (- 10 MW). Typically, around 0.75 lb-mol of hydrogenlh is required for each 10 kW of electric power in a phosphoric acid fuel cell system. Therefore, fuel cell systems pose special design constraints, and a specific reformer model has been developed. The Westinghouse model allows the demethanation reaction to be kinetically controlled, rather than invoking the equilibrium assumption, and a great deal of flexibility has been incorporated into the programming. This model

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has the options of: (1)inclusion/deletion of the water gas shift reaction, (2) flat slab or tubular geometry, (3) cocurrent, countercurrent, or double countercurrent flow arrangement, (4) different heat transfer coefficients, (5) specified exterior reformer tube temperature profile, and (6) CALCOMP plotting routines. Model predictions have been compared to simple reformer tube data and were found to agree within 15% of the exit conversions and within -7% of the temperature profile, by use of an error norm analysis. Model calculations on the reacting reformer gases indicate that a heat transfer coefficient some two times greater than Leva packed bed correlations actually exists, in agreement with other fuel cell reformer data. This is apparently a reaction-induced effect. This work demonstrates the utility and applicability of unidimensional, kinetic modeling to complex reacting media, and how simplifying assumptions render an incalculable problem solvable. The good model agreement with experimental data is indicative of a causal modeling basis and has validated the model for similar designs and scale-up. Heat transfer effects profoundly influence reformer operation, and, consequently, these must be included in the design; for example, a flat slab geometry for low-pressure situations or the double countercurrent flow arrangement for intemal regenerative heat transfer. These designs have practical applications in other packed bed reactors operating on endothermic reaction systems.

Previous Kinetic Modeling Work Oblad (1967)and, later, Grover (1970) discussed a steam methane reformer computer model that includes heat

0 1985 American Chemical Society

and an exterior tube wall temperature profile is used in place of furnace gas flow rates. Double countercurrent flow (DCCF) reformer tube. A unidimensional model is developed and solved using numerical techniques. and it is the same as the gas temperature in that section of the catalytic bed. No. and general design purposes. Singh and Saraf (1979) have developed a model for side-fired steam-hydrocarbon reformers. Harth et al.. High hydrocarbon reforming can also be accommodated. The combustion gas flow arrangement can be countercurrent (Figures 2 and 31. it f o r m the basis for the model. Good agreement with actual reformer data is obtained. and radial temperature profiles are neglected. The kinetic expression represents a "global" or overall rate and hence includes reactivity differences found within the catalyst particles. with the water gas shift reaction (eq 2). This is the combination of a steammethane reformer with a high-temperature. However. The model assumes the following reactions as the basis for the mass balance (Akers and Camp. Equation Development Table I outlines the basic assumptions of the model. as a tubular geometry option. a more flexible reformer model was desired. Both methane and naphtha feedstocks are accommodated in the model algorithm. and. This design is also described by Smith and Santangelo (1980). Chem. 3. 5. the agreement appears to be no better than for the previous plug flow models. which provides an excellent means for long distance transport of thermal energy. as optimum performance of an integrated fuel cell system does not necessarily imply optimum reformer performance. 2. transfer and reaction kinetics in the analysis. Carbon formation effects are included.Ind. Eng. Extensive attention is given to radiative heat transfer from the burner gases to the reformer tube surface. Reaction 1 is kinetically controlled. or. and therefore they are limited in their flexibility. instead of the first-order rate equation. thus minimizing overall heat duty. do not involve explicit modeling. and. (1978) introduce a novel application for reformer technology. Again.e. The reaction kinetics are adequately described by a pseudo-first-order rate equation. No carbon deposition is allowed in the reformer. No heat transfer occurs between the product and reforming gases. Reformer Model Assumptions 1. These literature models have all been developed for specific.. Allen et al. 1975) CH4 + 2Hz0 = COz + 4Hz (4) CO + HzO = COZ + Hz (2) . In this design.-Annular Catalyst Bed 287 Burner Cavitv Exhaust I Gas Reformer Gases Gas Reiormer Gases Table I. Process Des. An interesting facet of this work is the use of a DCCF reformer design. or DCCF (Figure 4). Olesen and Sederquist (1979) consider a double countercurrent flow (DCCF) tubular geometry reformer (Figure 1). 11. reformer designs. experimental. 1955. as are heat losses to the environment.. 8. Figures 2. Equations 1and 2 represent the reaction basis. Equations 4 and 2 represent the reformer reactions. Thus. although. The rate equation uses an expression derived from the law of mass action. all the tubes in the reformer behave independently of one another. and kinetic expressions are developed for both reactions. the model closely agrees with reformer plant data. All gases behave ideally in all sections of the reformer. The reforming gases flow up through the catalytic bed and react. 3. Dev. Calculations are based upon overall balances and catalyst data and. A uniform temperature exists throughout each catalyst particle. 1985 Product Gas Insulating Cap . 24. Heat transfer is primarily by forced convection. A single reformer tube is analzyed. gas-cooled nuclear reactor (HTGR). The exit reforming gases leave via a manifold arrangement a t the top. Good agreement was obtained with pilot plant reformer studies. The demethanation reaction choice becomes CHI + 2H20 = C02 + 4H2 (4) instead of eq 1. Hyman (1968) developed a similar model. Figure 1. Close agreement is obtained between the model and operating reformer plants at different sites. Vol. 7. RostrupNielsen. The reverse reaction rate is also included to account for equilibrium effects. as such. Their model analyzes a fuel cell system reformer and includes radial and axial mixing terms. 9. 6. it differs in several important areas. 10. and 4 display the tubular geometry and variables involved. This reformer model is described herein. for all the model's complexity. Plug flow of the reformer gases is also assumed. multiple reformer designs might evolve. Distributor and manifold entrance effects are negligible. Reforming and combustion gases flow with complete radial but no axial mixing (i. existing. 2. cocurrent. Specific radiant heat transfer terms are neglected. 1975. 4. plug flow). Heat is supplied by the combustion gases flowing through the outermost duct (this is normally a section of the furnace around the reformer). hence. 2co = c02 + c (3) This model assumes unidimensional (plug) flow of gases in the reformer tube and considers the kinetic rate equation to be first order in the methane partial pressure. while Figure 5 shows the corresponding flat slab situation. the reforming reactions can be reversed (methanation) and the energy released. Bed pressure drops are neglected. while Reaction 2 is equilibrium controlled. For analysis. At the consuming site. they can leave through the center tube depicted in Figure 2. Only axial temperature changes are allowed. This model is based upon the following reaction choices CH4 + HzO = CO + 3H2 (1) CO + H2O = COP + H2 (2) Carbon formation by reactions such as eq 3 is usually very small and can be neglected under normal industrial operating conditions. existing reformer gases transfer heat directly back into the catalyst bed. producing hydrogen. A pseudo-first-order rate expression describes the kinetics of eq 1.

2. Eng. Equation 2 represents an equilibrium redistribution of the products of reaction 4 and goes in reverse as eq 2 is written. These have been found to influence industrial reformers strongly. Dev. Heat transfer surfaces (major heat flux denoted by arrow Q. The two parameters.PCH4. -rCH4 kOe-EA/RTAP = (5) (6) AP = PCHl . along with experimentally determined parameter values. Dimensions and variables for the flat slab reformer (countercurrent flow). in this model. PCo. Single-tube kinetic reformer model (countercurrent flow). the total pressure. Vol. tubular geometry reformer model (regenerative gases flow on the inside). is assumed to be equilibrium controlled. ) =z k D3 Combustion Gases 'Hz' MH Combustlon Gases @ Z = O K n w T C O . and the reaction conversion. Thus. the water gas shift conversion is always negative. a pseudo-first-order rate equation was used for the computer model (eq 5). the total molar flow rate. an equilibrium term was included in the model.can be varied to represent catalysts of any reactivity. carbon deposition is precluded by reactions such as eq 4. Carbon formation by reactions such as eq 3 is neglected. 2co = c + c02 (3) C + HzO = CO + H2 (4) Table I1 summarizes some of the previous kinetic equations used in the literature for the demethanation reaction.) and the activation energy (EA).X E ) -rCH4 Pkoe-EA/RT = F + 2XlF1 F + 2XEFl ] (7) . I F i I .X 1 ) . 1985 Center Line . MH I+1 I_ Primary Heat Flw Q - Reactant FlwR - Combustion Gas Flowc 2 Figure 2.288 Ind. as normal fuel cell reformer operating conditions include a sizable steam excess ( 3 1 steam/carbon molar ratio). XEZ0 Figure 4.. the frequency factor (k. Denoting X 1 as the methane conversion by reaction 1 and X E as the equilibrium conversion.the demethanation reaction. because of the large steam excess. Several of the rate equations include a term to account for equilibrium effects. No. Figure 5. Hence. Double countercurrent flow.5 . Therefore. Chem. The methane partial pressure is written in terms of the methane molar flow rate. while eq 2. Figure 3. then the rate equation takes on the form Fl(1 . Process Des. Know THZ.E AP represents the difference between the actual and equilibrium methane partial pressure. 24. Also. is considered to be kinetically controlled. Reaction 4.i Square Duct for Combustion Gas Fiw I @ Z= Z . the water gas shift reaction.Fl(1 .

19 X 10' E A = 26000 or ko = 4. +C=0 A = (K2 . and the definition of conversion in a flow system of uniform cross section (eq 9). and the conversions for each reaction. the equilibrium constants.43 X lo6 E A = 20000 Grover (1970) ko = not reported E A = 8778 KE2 = equilibrium constant of the reaction.X2 (F3 + XlF1) F3 + XlFl + X2 (F3+ XlF1) F4 . water (steam).XlFl F2 . Table 111. carbon dioxide. the mole fractions can be expressed in terms of component molar flow rates. as has been done previously (Grover. The capability of adding a diluent (nitrogen) requires the sixth component balance.Ind. the total molar flow rate. Five components are involved in the two-reaction scheme (methane.XE) uoCo F + 2 X l F l .F3 . X1 and X2). No. Therefore.X2 (F3+ XlFI F4 + 4X1F1+ X2 (F3 + XlFl F6 F + 2XlF1 This is then combined with the plug flow design equation (eq 8)." Summary of Kinetic Equations and Parameters Found in the Literature workers expression -rCH4= k0e-EAIRTPCH4 k o = 127 Akers and Camp (1955) E A = 8778 (commercial cat. For both equilibria.all molar flows in the reformer can be represented in terms of the two conversions and the initial molar flow rates (Table 111). Denoting the water gas shift conversion as X2 (based upon carbon dioxide).F5) (15) C= K2F2F4 . Dev. atm]. Process Des.K2F2 -K2F4 5XlF1 . the demethanation reaction equilibrium becomes PCOzPH: K1= 2 - yCOzyH: P2 (11) PCH~PH~O YCH4YH~02 The water gas shift reaction equilibrium is dX1 -= dz [ pBPkOe-EA'RT Fl(1-Xl) Fl(1. providing a convenient iterative calculational sequence (eq 13-16).) Bodrov et al. and hydrogen). then. (1964.04 X IO4 E A = 20000 (assumed) ko = 2. CH4 + HzO = CO + 3Hz KE1 = equilibrium constant of reaction 4 Hyman (1968) this work ko = 100-1 X IO5 E A = 10000-26000 PcH4.2K2F2XlFl. E A [cal/mol]. 24. Assuming ideal gas behavior (fugacity coefficientsof unity). 2. Vol. a t specified temperature (fixed equilibrium constants) and boundary conditions (feed rates). F1 -XlFI 0 F2 0 -X2 (F3+ XlF1) F3 XlFl X2 (F3 + XlF1) F4 -2XlF1 -X2 (F3 + XlF1) F5 4XlF1 X2 (F3 + XlFI) F6 0 0 totals F 2XlF1 0 mol present F 1 .1 X IO6 E A = 19400 Allen et al. Chem. 1970). to yield the reactor material balance (eq 10). (1975) Rostrup-Nielsen (1975) ko = 1.2XlF1. eq 12 can be rearranged to yield a quadratic equation in X2 as a function of X1. B = (F3 + XlF1) (2XlFlK2 .(F3 + XlF1) (F5 + 4XlF1) (16) . 1985 289 Table 11.1) (F3 + XlF1)' AX22 + BX2 (13) (14) Equilibrium Calculations The equilibrium conversion required in the rate expression (eq 10) necessitates the solution of the combined equilibrium expressions for the two reactions (eq 1and 2).E is the methane partial pressure at equilibrium "Units Ko[lb-mol/(h lb of cat. carbon monoxide. Molar Flow/Rates as a Function of Reaction Conversions (Basis: 1-h Flows) mol produced by reaction 2 component mol in feed mol produced by reaction 1 CH. eq 11 and 12 reduce to only two unknown variables (the conversions. 1967) -rCH4= kOe-EA/RTP CH4 value for nickel foil ko = 1 X IO6 E A = 31 000 for commercial cat.. Furthermore.F 2XEFl ][ + (10) 1 The model describes the reformer using six-component material balances. Eng. k o = 6.

.12. thus substantially boosting the unit’s efficiency. D1 = 0 in Figure 2). Vol. the countercurrent flow arrangement is more efficient. 1973).+. That is ( T H .TC). equation (17) has to be modified to C(FACPA) dTC = UI(TH .. Therefore. Cocurrent flow. This requires iteration loops on X E and the reformer gas temperature.(TD~)dZ + Fl(-AHRi)dXl + (F3 + XlFl)(-AHR*) dX2 + UO’(TR . and more can be added as necessary. Three correlations are available within the program from standard references (Smith. a unique solution can be obtained for each set of input data. Hence. are completely defined. the solution is also defined but the energy balances require an iterative solution. Thus. for countercurrent flow reforming gas energy balance C(FACPA) dTC = UI(TH .5-kW reformer tube profiles..290 Ind. 1985 These equations complete the reformer’s material balance description. This is particularly true of small volume reformers in fuel cell systems. Eng.) (23) where subscripts i and i + 1refer to the bottom and top of the reformer section as shown in Figure 3. = (1/2)(TR1+1 . This solution algorithm has been programmed onto a Univac 1100 series computer. and Perry and Chilton. These two equations can be solved explicitly for TC. In actual operation. TC (i + 1).(aD2) dZ Fl(-AHRJ dX1 + (F3 + XlFl)(-AHEJ dX2 (17) combustion gas energy balance (MH)CH dTH = UI(TH . 7. Touloukian et al.) (22) - Chang. 1973). eq 18 becomes (MH)(CH)d T H = UI(TH .TC). = (1/2)(TH. Chem. Figure 8 displays ( T R . 2. the countercurrent flow profiles (Figure 7) display nearly constant driving forces over the reformer’s height.TC). for co.. with thermal and reaction equilibrium achieved at the exit..). Solution Algorithm The co. X2. 20. Process Des. providing milder conditions for the reformer’s structure and extending reformer tube life. the arithmetic mean temperature difference is used in eq 17.17.. and TH. + TC. Flow rate changes and fluctuations have practical significance for reformers. TH. XE.(TDl) d Z (174 The latter term accounts for product gas heat transfer to the catalytic bed.TC). 18. the cocurrent flow arrangement keeps the metal surfaces -200 O F cooler. two energy balances can be written for the reformer. and TC). + TR. and differences are quickly converged using secant methods.and.or countercurrent flow arrangements. Thus.(rD2) dZ M Reformer Gas Temperature 10 I + Equilibrium Conversion Conversion i 1 I (18) Actual ( k i net I C ) Conversion A cocurrent flow arrangement changes the sign of the left-hand side of eq 18.. . End values are checked against actual input values and boundary conditions. where the off-peak flow rate is 25% of the design flow rate.. 24. Physical property and equilibrium data are included in the program as fitted correlations of published data (Perry and Chilton. 11.and countercurrent reformer models consist of a system of five basic equations (eq 10. Alternatively.TC). 17a. Energy Balances Neglecting heat transfer from the product gases. hence. provided all the other terms have been assigned values from the material balances. .TC. using the dimensions displayed in Figure 5. All differentials in the equations are expressed as finite differences across a small height increment (a).TC). the energy balances represent two equations in two unknown variables (TC.. These are accurate to within 2% over the temperature range (425-1315 “C). Dev. and 18) containing five independent variables (Xl. 1970. Figures 6. eq 17 and 20.. and 21. This is repeated sequentially for all height increments in the reformer.(2)(ASLAB + BSLAB) dZ (21) Similar heat transfer area changes would have to be made in the other two energy balances.after conversion to finite difference forms. On the other hand. as shown by comparing Figures 6 and 7. For example. Model Results The computer model has been tested over a wide range of input variables and model choices. the cocurrent flow profiles (Figure 6) show continually decreasing driving forces for temperature and conversion as the gases proceed through the reformer.. A higher activity catalyst will increase the conversion further. The equations are then rearranged and solved for all exit variables in terms of the input variables to that increment.+.. and 8 display results obtained on conventional 5-kW reformer tube analyses (no central plug. 1970.. this can amount to as much as 25% of the reformer’s heavy duty. 21). the combustion gas energy balance can be replaced by an exterior tube wall temperature profile of the form TW(Z) = A I 2 3 4 5 6 7 t / Z Fractional Height 8 0 1 0 + B(Z) + C ( P ) + ~ ( 2 3 ) (19) Figure 6.+land TH. The DCCF models (Figure 4) require the inclusion of a product gas energy balance (MR)CR dTR = UO’ (TR . However. The DCCF models add one equation and one variable and are also completely defined. The DCCF models add an extra variable and an extra equation (no. As expected.+1 TC. Physical Property and Heat-Transfer Calculations The heat-transfer calculations require correlations and physical property data. The solution is generated by a finite difference/incremental approach.TC).(aDl) dZ (20) Also. 1973.TC. A flat slab geometry design necessitates adjustments to the heat transfer area term. These two points have to be considered in reformer design. This accuracy is within the error band of the original measurements.+1 + TH.TC). For this work. achieving a higher exit temperature and conversion. No. Hence. as intuition suggests.

Heat transfer strongly affects reformer design and performance (Hyman. except the conversion crossover point occurs within the range of study a t the design length (2 = 4 ft).7 t I I Counter-Current Flow Figure 7. Eng. w Fractional Height i . This effect is due to the heat transfer/recovery from the product gases. Perry and Chilton.40 I 0. while the countercurrent flow arrangement provides a consistently higher conversion.8 . However. under off-peak circumstances.01 I I I I 1 I . etc. but does not change the basic shape of the curves. kW 1 0 Figure 8.g. 2. and hence. As Figure 8 shows. 5 . temperatures. These curves are similar to those of the tubular design (Figure €9.. Process Des. This is due to the better heat transfer. 9 1. too much hydrogen may be produced.7 i' I I I I 2 4 6 8 Flw Rate. the flat slab reformer exit conversion is some 5% higher. it also displays greater flow rate dependence. Hence.9 40 60 kW Flow Rates m 100 120 Figure 9. Model parametric studies on DCCF designs show similar flow rate trends as Figure 8. the correlations in the model predict overall heat transfer coefficients in the range 2-5 Btu/h ft2 OF.% Actual (kinetic) Conversion .00 I I I 0. Double countercurrent flow. tubular geometry temperature profiles (arrangement of Figure 4). .0 . showing the product gas effect. Flat slab geometry reformers have been suggested as possible alternatives to tubular designs for low-pressure systems (<75 psig). Figure 9 shows the predicted flow rate sensitivities of both flow arrangements for a 60-kW slab reformer design.9 Reformer Gas Temperature Equilibrium Conversion L - V s . when calculated at similar conditions (e. Figure 10. 1985 291 . using two Leva packed bed correlations from Smith (1970) Nu = 3.60 . hydrogen production rate. 4 .' exp (24) .20 . L l i !. Standard correlations (Smith. Decreasing the space velocity pushes this crossover point to a higher flow rate (curves at Z = 6 in Figure 91.6 I 1 1 20 Counter-current Flw . 1973. Golebiowski and Wasala.. 1973). Dev. Golebiowski and Wasala. Figure 10 displays sample DCCF temperature profiles. However. Countercurrent flow. No. 1968. 0. Chem. 7 L I Z Fractional Height . 1. 1973).hl predicted conversion dependence on flow rate for the two flow arrangements in a 5-kW tube. predicts a conversion slightly higher (5% maximum) than the countercurrent flow case. although the DCCF model 7 w 1 4w 0.6 . 1. Conversion dependence on flow rate and flow arrangement (60-kW flat slab reformer).. primarily due to their superior heattransfer characteristics.Ind. space velocity. 1970. The model predicts conversion and temperature profiles for the flat slab reformers to be similar to the tubular profiles presented in Figures 6 and 7. Conversion dependence on flow rate (10 kW = 295 SCF/h H) 2. Vol.). 5-kW reformer tube profiles.3 . 0. presenting a control problem. 24. .2 .I .5(ReJ0. and these should be experimentally determined for the reformer design of interest. 1973) give predicted local heat-transfer coefficients that vary by several hundred percent (Golebiowski and Wasala.m .

Table IV compares the program predictions with data on a conventional reformer tube in the hydrogen plant of the Phillips Avon Refinery in California (Hyman. Dev. in. corresponds to F = f42/08 O lb-mol/h.246 I I 0.9 exp - [E] (25) Limited internal Westinghouse data predicts an overall heat transfer coefficient in the range 5-10 Btu/h ft2 OF for the fuel cell reformer system. Catalyst particle size effecta upon hydrogen production rate (10-kWdesign). I 1700 tube wall outlet temperature. 24. indicate an almost linear flow dependence and a very strong particle size dependence. using the wall temperature profile approach. f t tube i. F1 = 5..308 I 0.5 2 4 6 8 I O 1 2 Catalyst Particle Sire ( m m l Measured kinetic conversion = 98.292 Ind. eq 25 only). Chem.M8 I 0. .369 Table IV. catalyst particle size. As Table IV shows. Catalyst particle size effects on heat transfer (10-kW design). 0.0 . Eng. 1985 0.185 0. lb/ (h ft2) 5476 (superficial) steam/methane ratio gas mix inlet temperature. tube wall thickness.1 1514 (calcd) 86. open literature data exist for evaluation of the tubular geometry models. Fortunately. (wall thickness = . entire tube 172 . derived from flowing air experiments. Only limited data are available on DCCF designs.813 (Re. This is supported by analyses of small reformer experimental data in the next section. inlet. and these are insufficient for running the model. DP/D Ratio 0.d. in. 2 p heated (first. affects the conversion and hydrogen production rate (Figure 12). double that predicted by eq 25. Doubling the heat transfer coefficient increases the predicted exit conversion by around 10%.. 1968) using catalyst data derived from the literature (Allen et al.062 0. F4 = 36.369 .185 0.4%.)0. used for the combustion gas side film coefficient) Nu . atm ab output 1460 gas mix outlet temperature. 1975). Phillips Petroleum Reformer Data (from Hyman. 3 ft unheadted..123 . using the wall temperature profile model (Le. 1968) input height. the predicted heat transfer coefficient sharply declines on either side of the maximum (Figure 11). x 5/s x used in the model 2 = 40 0 2 = 5 in.7 % TW = 1300 + same. (Leva correlation for heating used for the reforming gas/catalytic bed side film coefficient). [ I Figure 12. For example.. OF. O F tube wall temperature 7:l 687 2 4 6 8 1 0 1 2 Catatyst Particle Size ( mml Figure 11.246 1 O. given (from the article) 40 5 17/32 51. Process Des..123 I I . atm abs outlet pressure. predicted kinetic conversion = 88.062 I 0.e. Vol. (Leva correlation for cooling. of course.26. Comparison of the Model Predictions with the Available Data No data is presently available for a flat slab reformer design as a means of evaluating the model's accuracy. Z in ft) P = 13 atm 14.82 7:l 687 (rings) mass flow rate. amply demonstrating the strong heat transfer effects on compact reformer design. " in. O F (cat.1 (calcd) 1660 (calcd) 4270 (calcd) 0. These correlations. DP/D Ratio inlet pressure. i.2%. O F inlet particle Reynolds 5000 number I Table V. 2.3 throughout 12. This. bed) feed carbon converted. No. in.0. cm measured temp. such as would be required for fuel cell systems. using 7:l steam/methane ratio.) 'Iz (spheres) same. the agreement is remarkable: within F 6% on conversion and 60 O on the exit temperature. predicted 653 0 653 738 770 5 809 851 10 914 873 15 20 954 935 995 25 995 1040 1052 30 1109 1103 25 1168 1175 40 1274 1238 45 1328 1327 41. used 0 3 = 6 in. Westinghouse/ERC Reformer Tube Dataa distance from gas gas bed. 91.

better than expected heat transfer. Radiative heat transfer effects are not included in the model. (1980). and chromatograph and concentration measurement errors probably add another 3%. although the predicted conversion is 153 too low. and. reaction-induced heat transfer improvement over nonreacting gas heat transfer. The model kinetic.8% 9. because these effects can usually be included by an appropriate. experimental reformer tube (-0. 1. the heat transfer. Currently. which increases the gas velocity. Therefore. Finally.859 0.6% 8. such as the following. bed wall 6. doubling) heat transfer improvement is a reaction related effect. heat transfer increases. kmol/m3 co = initial methane molar concentration. BSLAB = flat slab reformer width dimensions (Figure 5 ) .5% 7. Chem. suggest that the anomaly is real.851 0. J/mol K CR = product gas molar heat capacity. as suggested by the analyses of Hoover et al.6% 7. No.821 0.g. Again.695 0. Table V shows a sample experiment vs. and. Young of Westinghouse for his assistance and guidance during this program. However. Hoover et al.2 kW design capacity) and reported by Christner (1979). This may be due to uncertainties in the ’% catalyst parameters or the heat transfer. A unidimensional model would tend to obscure all these effects and combine them into a larger. - Acknowledgment The work described in this paper was performed under NASA Contract DEN3-161. Dev. Heat losses are not included in the model. Project Manager: Robert B. hence. while the kinetic conversion errors are approximately double. DCCF reformer design has larger thermal and reaction gradients as compared to conventional reformers. global rate expression (e. Presumably. which result in lower intraparticle temperatures and reaction rates. but may be significant for small systems.751 “From the data of Christner (1979). Hence. As indicated before. the temperature and equilibrium conversion errors are approximately equal to the experimental uncertainty range. The compact. 3. resulting in a greater temperature driving force than expected. Vol. and there is also experimental evidence of an activation energy change in the higher temperature end of the reformer (-1100 OF). and the previous literature reports. William E. Good agreement is obtained between the measured and predicted temperature values. King. Process Des. and in turn.851 0. Unfortunately. Westinghouse/ERC data have been produced by an electrically heated.891 0.859 0. and Table VI provides a summary. J/mol K . there is little catalyst data above this temperature to fully document the transition. Nomenclature AASLAB. As the reaction proceeds. The endothermic reformer reaction cools the catalyst particles. diffusion resistance control. and to Dr. 2. 1970). (1980) analyzed both convective and radiative heat transfer to a fuel cell reformer tube under otherwise identical conditions and concluded there was little difference between the two cases (<20 O F difference in wall temperature). the heat-transfer coefficients appear to be in the right range. These model calculations used a heat transfer coefficient double that of eq 25.730 0.834 x1 0. the compact spacing of fuel cell reformer tubes and the high flow rates of relatively “low” temperature (2000-2500 O F ) gas past the tubes would minimize any radiation effects present. 2. Given the close agreement of the temperature profiles.644 0. However. m BBSLAB. Diffusion effects are not explicitly included in the model. Additionally.883 0. experimental variations include temperature and concentration errors and heat losses to the environment. 4. using the same experimental unit. The reaction produces a net mole increase.. 24. apparent heat transfer coefficient.612 XE 0. However. Additional data from Hoover (1982) support this approach and also indicate a similar.. Comparison of Model Predictions with the Experimental Data” conversions run 1 2 3 4 5 temperature error norms cat. insufficient data were presented for conversion and temperature profile comparisons. 1985 293 Table VI. Larry G. kmol/m3 CH = combustion gas molar heat capacity. it seems reasonable to assume that a combination of low catalyst activity and experimental errors is responsible for the model deviations. and physical property calculations have been thoroughly checked and validated.818 0. this effect is greatest near the hot tube wall. the model calculations.876 0. Discussion Analysis and validation of the model’s fit of the experimental data fall into three areas: the heat transfer doubling factor. these were determined for a slightly different version of the catalyst. ih This would be particularly true near the hot tube wall where the reaction rate and hydrogen concentration are greater. and experimental data variations/errors. Thermocouple reading and location errors probably contribute about 3%. However. This has been analyzed using the wall temperature model. Intraparticle diffusion should not be significant in this system. no plans exist to develop a two-dimensional model. m c = methane molar concentration. ASLAB = flat slab reformer length dimensions (Figure 5). hydrogen is produced. the sheer magnitude of the anomaly.706 0. the increased reformer heat transfer and its magnitude have been previously reported in the literature. The authors also wish to express their appreciation to Dr. see Smith. equilibrium. electrical heating should minimize this effect. The model’s kinetic equation is a simplification but should be representative of the experimental conditions because of the excess steam.822 0. funded by DOE and administered by the Lewis Research Center.. Measured catalyst activity parameters are used. due to the highly endothermic nature of reformer reactions. w t ita better transport properties. prediction comparison. Eng. and hence. this dramatic (i. cannot be analyzed by a unidimensional model.869 0. This marks the beginning of a transition from a surface reaction-controlled rate to external gas film.e.759 x1 ~~ ~ 0. Christner of ERC for the small reformer experimental results.8% <1% <1% <1% <1% <1% measured predicted XE 0.Ind.759 0.

m E A = Arrhenius activation energy. R. 54(16). J / h K Registry No. L. 116. 49(4). M. N. Kinet. kG of cat.. 47(7). 1979." NASA Contract DEN3-181. 38. 14. Eng. J. 0.d. 3. J. Y. YHz = component mole fractions 2 = reformer height. Pco." NASA CR-165193. 1978.F equilibrium methane partial pressure.. m 0 2 = outer tube's i. P. Eng. 80(8). 1. Temkin. m DE = equivalent (hydraulic) diameter. A. S . 1973. Starllng School of Chemical Englneering and Materials Science. Hydrocarbon Process. Gerhard. m/ h UI = overall heat transfer coefficient between the combustion and reforming gases. S. "The UTC Stream Reformer. R. 164. m AHR." 5th ed. kmol/h F1 = CHI feed molar flow rate. Katal. Norman. I. t Morgantown Energy Technology Center. Saraf. K. October-December 1979.= average temperature difference between TR and TC. Bottendahl. W. Perry. Touloukian. Smith. N. 147-178.. Nlessen. kmol/h F4 = H20 feed molar flow rate. Process Des. A. kJ/(h m2 K) UO' = overall heat transfer coefficient between the product and reforming gases./m3 of reformer C(FACPA) = heat capacity of the reformer feed gas. pp 493-547. Pco1. H. 1. 1984 Cotretations for Estimating Critical Constants. Smith. Y C O . Kugeler. 0. Received for review February 22. 696." Danish Technical Press. G. Dev. 1970. 0. and molecular weight. acentric factor. Therefore. D.. (Figure 2).: Copenhagen. = component mole fractions YHzo. kmol/h MR = product gas molar flow rate. M. V. No. 18. The present correlations extend the range of application to polar and associating fluids. 1980. Hoover. correlations for estimating these characterization parameters as functions of 0 1985 American Chemical Society . atm hp = difference between the actual and equilibrium methane partial pressure. Ser. 1970.) = Re. m D1 = inner tube's 0. F. m D 3 . C. Eng. 821. C. Inc. kmol/(h kg of cat. cal/mol F = total feed molar flow rate. Int. K (TR. 131. kJ/mol of C 0 2 pB = catalyst bed density. Sederquist. Temkin. atm P ~ PCH4. Hoover.d.. Methane. ACS Symp.. Theis.. Dev.. and Dipole Moment for Undefined Coal-Fluid Fractions Suphat Watanaslrl. and other characterization parameters for the fluids (or fractions) are necessary. K TR = product gas temperature. OCt 23-25. Currently available correlations are applicable only to petroleum and nonpolar coal-fluid fractions. kJ/mol of CH4 A H R 2 = water gas shift reaction enthalpy. Y. D. McGraw-Hlll: New York. T. K. Chem. N. W. Apel'baum. Grover. "TPRC Data Series". 256. 1968. pp 85-105. Olesen. H.WV 26505. M. P H ~ o . Inc. = demethanation reaction enthalpy. P.Yco. 8(4). Apel'baum.: New York. Techno/. 1967. Oblad. Christner. 1980.. The correlations express the characterization parameters as functions of normal boiling polnt.. atm2 K2 = water gas shift equilibrium constant M H = combustion gas molar flow rate. M. J. L. L. P. "Cell Module and Fuel Conditioner Development: Quarterly Report No. = particle Reynolds number T = absolute temperature.. kmol/h F5 = H2 feed molar flow rate. in order to predict thermophysical properties of these fluids using corresponding-states correlations. acentric factor. Chang. Singh.. 1975. R. normal boiling point (Tb). 1975. kJ/(h m2 K) X 1 = kinetic deme- thanation reaction conversion XE = equilibrium demethanation reaction conversion X 2 . K TC = reformer gas temperature. K (TH. 0. 1. 471. H = component partial pressure. 1984 Accepted May 7. A. "Steam Reforming Catalysts. Hyman. S. G. 133.. A. Literature Cited Akers. specific gravity. Universify of Oklahoma.TC). W. "Cell Module and Fuel Conditioner Development: Final Report: October 1979January 1982. which are the inspection data normally obtained for undefined petroleum and coal flulds. 0196-4305/05/1124-0294$01. kmol/h ko = Arrhenius frequency factor. S..: Saxena. W.. K TH = combustion gas temperature. it is a common practice that only inspection specific gravity data. 294-296 D = diameter. Plenum: New York. m/h uo = initial reformer gas velocity. H. m DP = particle diameter. m DELTA = flat slab reformer wall thickness. Goiebiowski. Hydrocarbon Process. average temperature difference between TH = and TC. Id.294 Ind. R. X E 2 = water gas shift reaction conversion YCH4.. Likens. However.. H. DOEINASAINASA CR165316. "Chemical Engineering Kinetics. C. 252. M. Process Des. 13(1).. E. L. Jr. Chem. 5(4). 1985. (Figure 2 ) . 4. Windsor. 1973." United Technologies Corporation.K T W = combustion tube wall temperature. G. H. M. Eng. Klnet.TC). Camp. Harth. Santangelo. D 5 = other reformer tube dimensions. E. Dec 1979.+ and Kenneth E. Chem. Chilton. kmol/h F3 = C02feed molar flow rate. Acentric Factor. Chem.. Katal. "Chemical Engineers Handbook. atm P C H 4 . 1970: Vol. Chem." 2nd ed. Eng. McGraw-Hill.. R.50/0 (SG). CT. namely. I d . et al. CA. atm = R = ideal gas constant.99 cal/mol K (-rCH4) demethanation reaction rate. 1979. D 4 . P. Q. 122. kmol/h Nu = Nusselt number P = total pressure. 109. Process Des. Morgantown. M. 1973. pp 10-12 to 10-17. Victor H. 1967. Nucl. D. kmol/h F2 = CO feed molar flow rate. "Technology Development for Phosphorlc Acid Fuel Cell Power Plant (Phase 11): 5th Quarterly Report". 1964. Allen. values of the critical constants. kmol/(h kg of cat. K u = reformer gas velocity. atm) K 1 = demethanation reaction equilibrium constant. 1955. Dev. Oklahoma 730 19 Correlations have been developed to estimate critical constants. Bodrov. Owens. Liley. AIChE J. Bodrov. Feb 1982. D. Rostrup-Nielson. Introduction For undefined petroleum and coal fluids (or boiling-cut fractions). OilGas J. Wasala. 2 4 . and dipole moment of model coal compounds and other hydrocarbons and thek derivatives. paper presented in Santa Barbara.. and molecular weight ( M W ) are experimentally measured. N. 74-82-8. 1. 1982 Revised manuscript received April 9.. R. D. kmol/h F6 = N2 (diluent) feed molar flow rate.