Biomass and Bioenergy 20 (2001) 307315

Indirectly heated biomass gasication using a latent heat ballast. Part 2: modeling
R. Pletka 1 , R.C. Brown , J. Smeenk
Center for Sustainable Environmental Technologies, Iowa State University, 286 Metals Development Building, Ames, IA 50011, USA Received 28 November 2000; accepted 1 December 2000

Abstract Experiments carried out in an indirectly heated biomass gasier successfully demonstrated that throughput and gas heating value could be increased by using a latent heat ballast. A mathematical model describing heat transfer and chemical reaction in the system was developed. The heat transfer submodel is accurate to within 13 K for both ballasted and unballasted scenarios. However, the chemical submodel, based on thermodynamic equilibrium calculations, proved inadequate and underpredicted cooling times during the pyrolysis phase of the process by about 50%. Improvement was made by substituting the measured product gas composition for the calculated gas composition. c 2001 Elsevier Science Ltd. All rights reserved. Keywords: Latent-heat ballast; Indirect gasication; Modeling; Fluidized-bed; Gasication; Pyrolysis

1. Introduction Experiments carried out in an indirectly heated biomass gasier successfully demonstrated that throughput and gas heating value could be increased by using a latent heat ballast [1]. The ballast allows a single reactor to be used by storing heat during periods of combustion and releasing it during periods of pyrolysis. Tests carried out in a pilot-scale uidizedbed reactor showed that the time to cool the reactor during the pyrolysis phase increased 102% through use of the ballast system. This extended pyrolysis time allowed 33% more biomass to be processed compared
Corresponding author. Tel.: +1-515-294-2934; fax: +1-515294-3091. E-mail address: rcbrown@iastate.edu (R.C. Brown). 1 Presently with Black & Veatch Corporation, 11401 Lamar, Overland Park, Kansas 66211, USA.

to an unballasted reactor. Additionally, the total fuel fraction converted to fuel gas increased from 74 to 80%. Higher heating values of 14.216:6 MJ N m3 (382445 Btu scf 1 ) on a dry basis were obtained from the ballasted gasier. A mathematical model describing heat transfer and chemical reactions during the pyrolysis phase of the gasication cycle has been developed. The model is useful for two reasons. First, it provides evidence that the physical and chemical processes occurring in the gasier are well understood. Second, it allows exploration of the e ect of various process variables, allowing performance to be optimized. The model is composed of submodels for heat transfer and chemical reaction. Together, they simulate the system behavior during the pyrolytic phase of the cycle. This paper describes the submodels, presents model predictions, and compares these predictions to experimental results.

0961-9534/01/$ - see front matter c 2001 Elsevier Science Ltd. All rights reserved. PII: S 0 9 6 1 - 9 5 3 4 ( 0 0 ) 0 0 0 8 9 - 1

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Nomenclature A cp h h 0 hf k l m m nf n N p pmix ballast surface area of ballast (m ) specic heat (J kg1 K 1 ) heat transfer coe cient (W m2 K 1 ) enthalpy departure (J mol1 ) enthalpy of formation (J mol1 ) thermal conductivity (W m1 K 1 ) bed height (m) mass (kg) mass ow rate (kg s1 ) fuel molar ow rate (mol s1 ) moles of constituent per mole of fuel () number of moles of reactant () product gas partial pressure (decimal) product gas mixture pressure (atm)
2

Qpcm Qpyr r t T x

heat evolved from phase change material (J ) energy ow required to sustain pyrolysis reactions (J s1 ) radial distance (m) time (s) temperature (K) mole fraction (decimal)

Greek letters number of moles of product () Subscripts gas uidizing gas i internal e external P products R reactants

2. Heat transfer model A nite di erence model was developed to describe the unsteady heat ow between the uidized bed, ballast tubes, and ceramic wall. The reader is directed to Ref. [1] for a detailed description of the ballasted gasier. The model is a one-dimensional representation of the gasier; heat transfer in directions other than radial is ignored. A nodal network was developed with an energy balance written for each node. A diagram of the nodal network is shown in Fig. 1. The reactor wall is comprised of three di erent materials: refractory, mild steel, and insulation. The refractory makes up the inner wall and is 2.54 cm thick. It is followed by a 0.635 cm mild steel midsection covered with 2.54 cm of high-temperature insulation. Because of the large and dynamic temperature gradient across the wall, the wall sections are represented by multiple nodes. Other model elements are represented by single nodes, as shown in Fig. 1. 2.1. Heat transfer model assumptions Numerous assumptions were made to yield a relatively simple model. Major simplifying assumptions regarding heat transfer include:

Heat transfer is one-dimensional and occurs only in the radial direction. Variations in radial conduction along the axis of the wall were accounted for by use of an adjustable height, l. If heat loss was conned to the vertical extent of the uidized-bed, then l would be equal to the uidized-bed height (about 0.6 m). However, a conduction height of 1 m was required to reproduce experimental results. The bed-to-wall heat transfer coe cient and bed-to-tube heat transfer coe cient are equal. A subsequent sensitivity analysis showed simulations were not strongly a ected by these parameters, making a more detailed treatment unnecessary. The uidized bed is uniform in temperature. The phase change material melts at constant temperature and completely releases its latent heat of fusion. The initial temperature of the inner refractory wall is 30 K less than that of the bed. This is based on measurements with thermocouples in contact with the inner wall and a steady-state heat transfer analysis of the system. The steel wall o ers negligible resistance to heat transfer, thus, nodes 9 and 10 are initially at the same temperature.

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Fig. 1. Nodal network for the model.

Initial temperature gradients are linear across the ceramic and insulation. The temperature of the ballast is initially equal to that of the bed. This assumption is supported by experiments that showed the ballast temperature closely followed the bed temperature during transients. Based on these assumptions, all the initial conditions can be xed by experimental temperature measurements of the uidized bed, the outer steel wall, and the outer insulation.

All gases (including superheated steam) were modeled using the ideal gas relationship. For gases obeying the ideal gas law, specic enthalpy, and thus specic heat, depends only on temperature. Values for specic heat were determined by curve ts [3]. 2.3. Mathematical formulation of the heat transfer submodel 2.3.1. Unballasted system By writing an energy balance for each of the nodes shown in Fig. 1, a set of di erential equations in cylindrical coordinates was developed. A system of 12 equations is required to model heat transfer in the unballasted reactor. The temperature of the uidized bed (T1 ) is a ected by uidizing gas and the inner surface of the refractory wall (node 2). The rate of change in the bed temperature is given by mgas cp; gas dT1 2 r1 lhi = (Tgas T1 ) + (T2 T1 ): dt m1 cp; 1 m1 cp; 1

2.2. Thermodynamic properties Whenever possible, thermal properties for materials used in the construction of the reactor were obtained directly from the material manufacturer. Other properties were taken from the literature [2]. When available, temperature-dependent properties were employed. Some of the nodes in the model lie on the interface between two materials. In these cases, values for nodal specic heat were obtained from a mass-weighted average of the two interface materials. The phase change material used as ballast was LiF. This salt melts at 1121 K and has a heat of fusion of 1050 kJ kg1 .

(1)

At the interface between the uidized bed and the refractory wall the rate of temperature change

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is dT2 2 r1 lhi 2 k2 l (T1 T2 ) + = (T3 T2 ): dt m2 cp; 2 m2 cp; 2 ln(r2 =r1 ) (2) The energy balances for the interior wall nodes (j =3 11) are similar and can be written in the general form: dTj 2 kj1 l = (Tj1 Tj ) dt mj cp; j ln(rj1 =rj2 ) + 2 kj l (Tj+1 Tj ): mj cp; j ln(rj =rj1 ) (3)

The second additional di erential equation is an energy balance on the ballast during phase change. It describes heat loss, Q, from the ballast to the uidized bed: dQ=dt = hi A(T13 T1 ); (8) where the integrated value of Q equals the total latent energy stored by the ballast. At this point the phase change material has completely solidied and the temperature history of the ballast is once again described by Eq. (6). 2.4. Computational methods The equation set was solved numerically with a non-sti di erential equation solver. This program employs a fourth-order RungeKutta method to integrate the equations. The program is written in the Visual Basic programming language. 2.5. Heat transfer submodel results Validation of the heat transfer submodel was accomplished by comparing model predictions to simple cooling experiments performed in the ballasted gasier. The reactor was brought to 1170 K, high enough to melt the ballast, by burning biomass fuel, as described in Ref. [1]. At this point, the ow of fuel and air were shut o and steam at approximately 720 K used to uidize and cool the bed. Fig. 2 compares cooling curves obtained both experimentally and computationally for two cases: the reactor contains no ballast tubes (unballasted trial) and the reactor contains 48 ballast tubes with a total latent heat storage capacity of 15.21 MJ (ballasted trial). In the case of the unballasted reactor, the simulations show instantaneous cooling rates very comparable to those obtained experimentally except during the rst 4 min when the experiment shows a more rapid cooling than predicted. We think this small discrepancy arises from the pyrolysis of residual fuel in the reactor remaining from the heat-up period using biomass fuel. Such an endothermic reaction would contribute to more rapid initial cooling than predicted by the heat transfer submodel. Nevertheless, the temperature discrepancy was only 13 K and the overall cooling rates essentially identical. The agreement between experimental and simulated temperature proles for the ballasted trials was

The temperature of the outer surface of the insulation is given by 2 k11 l dT12 = (T11 T12 ) dt m12 cp; 12 ln(r11 =r10 ) + 2 r11 lhe (Tamb T12 ); m12 cp; 12 (4)

where Tamb is the ambient air temperature. 2.3.2. Ballasted system When the ballast is included in the heat transfer submodel, the equation for the bed node is modied to re ect the in uence of the ballast temperature (T13 ). The equation for the uidized-bed node becomes dT1 mgas cp; gas (Tgas T1 ) = dt m1 cp; 1 + hi A 2 r1 lhi (T2 T1 ) + (T13 T1 ): (5) m1 cp; 1 m1 cp; 1

Moreover, two additional di erential equations must be added to the system. The rst expresses the temperature change of the ballast. While the ballast remains above the melting point of the phase-change material, its temperature is determined by the specic heat of the phase change material: dT13 hi A = dt mpcm cp;
pcm

(T1 T13 );

(6)

where subscript pcm denotes properties of the phase change material, lithium uoride (LiF). Once the temperature of the ballast falls to the melting point, the LiF begins to change phase. It is assumed that this phase transformation occurs at constant temperature; thus, dT13 =dt = 0: (7)

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Fig. 2. Comparison of experimental data and heat transfer model.

excellent for the sensible heat changes of the process. However, the model predicts strictly isothermal operation of the bed during the latent heat release from the ballast whereas the experiment shows in ections in the cooling curve but not isothermal cooling. The isothermal cooling predicted by the model is premised on the absence of any signicant thermal barrier between the solidifying phase change material and the surface of the ballast tubes. In fact, the phase change material solidies from the outside inward producing a relatively low thermal conductivity barrier in its wake. This barrier impedes the ow of heat from the ballast to the uidized bed and smooths the cooling curve. Sensitivity analysis on the e ect of convection coe cients on cooling curve proles conrmed this e ect. 3. Chemical equilibrium model A simple chemical equilibrium model was formulated to simulate the pyrolysis of biomass in the presence of ballast tubes. Chemical equilibrium is typically thought to exist in biomass gasiers [4]. Certainly, it represents a signicant simplication over the inclusion of a chemical kinetic model of pyrol-

ysis reactions. We hoped that equilibrium chemistry could predict the heating value of the product gas as a function of gasier operating conditions. In this case, it could be combined with the heat transfer submodel to simulate the overall performance of the ballasted gasier. 3.1. Chemical equilibrium submodel assumptions Assumptions employed in formulating the chemical equilibrium submodel include: The fuel (seed corn) can be represented by the formula CH1:99 O0:96 (29:8 g mol1 molecular weight). Fuel-borne nitrogen, sulfur, and ash were assumed insignicant. The system reaches chemical equilibrium at every computational time step. No solid carbon (char) is produced in the equilibrium composition. An independent equilibrium analysis showed that solid carbon is only expected at low temperatures and low steamfuel ratios. Because these char-generating conditions are present only infrequently in our experiments (0.671 steam fuel ratio below 930 K), solid carbon was excluded as a potential product.

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CO, CO2 , CH4 , H2 and H2 O are the only signicant constituents in the product gas. 3.2. Mathematical formulation of the chemical equilibrium model A set of equations consisting of mass balances, partial pressure relationships, and equilibrium expressions were developed to describe the chemistry of the ballasted gasier. 3.2.1. Mass balances Based on the species present, material balances can be written for carbon, hydrogen, and oxygen, respectively: NC = CO + CO2 + CH4 ; NH + 2NH2 O = 2H2 + 2H2 O + 4CH4 ; NO + NH2 O = 2O2 + CO + 2CO2 ; (9) (10) (11)

3.2.3. Equilibrium constants To complete the formulation, equilibrium constants are required. Equilibrium constants from the literature were curve t for the three reactions [5]: pCO2 pH2 CO + H2 O CO2 + H2 ; Kp; 1 = pCO pH2 O =exp(4000T 1 3:5); (18) C + 2H2 CH4 ; Kp; 2 = pCH4 2 pH2 (19)

=exp(10; 000T 1 12:2); C + CO2 2CO; Kp; 3 =

2 pCO pCO2 1 =exp(19; 300T 19):

(20)

3.3. Computational methods A program was written to solve the set of 11 algebraic relationship represented by Eqs. (9) (20), which describes chemical equilibrium for the process. The program uses the NewtonRaphson iterative technique to solve this system of equations. 3.4. Chemical equilibrium model results The chemical equlibrium submodel was evaluated at a range of temperatures and steamfuel ratios before integrating it with the heat transfer submodel. The temperature was varied between 800 and 1200 K. The moisture (steam) addition ranged from zero to twice the fuel mass ow rate (steamfuel ratio of 0 2). The results of these calculations, shown in Fig. 3, agree well with other chemical equilibrium calculations reported in the literature [4]. These predictions are in qualitative agreement with experimental trends reported in Ref. [1]. In the temperature range of 950 1100 K and the steamfuel ratio of 0.671.2, the heating value decreases with increasing temperature. Both experiment and simulation show a relatively modest decrease in heating value. The heating value of the dry gas clearly decreases with increasing steamfuel ratio, as observed experimentally. A more detailed comparison shows a number of discrepancies between experiments and simulations. Table 1 is a comparison of predicted and measured

where Ni is the number of moles of reactant i, and j is the number of moles of product j. 3.2.2. Partial pressure, molar relationship From the partial pressure relationship, pi =pmix xi , a set of equations relating the constituent concentrations can be written as CO total = ; (12) pCO pmix CO2 total = ; pCO2 pmix CH4 total = ; pCH4 pmix H2 O total = ; pH 2 O pmix H2 total = : pH 2 pmix The total number of moles, total , is total = CO + CO2 + CH4 + H2 + H2 O : (17) (13) (14) (15) (16)

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Fig. 3. Variation in heating value model prediction with temperature and steamfuel ratio.

Table 1 Comparison of experimental and predicted gas compositions Sample description Average temp (K) H2 O=fuel H2 Exp. No. 5 Model No. 5 Exp. No. 6 Model No. 6 1080 1080 980 980 0.78 0.80 0.78 0.80 23.2 57.8 25.6 56.7 Dry, normalized gas composition (%) CO 40.8 23.0 41.2 18.6 CH4 10.8 1.3 10.5 3.2 CO2 18.8 18.0 16.3 21.5 C2 H2 0.5 0.0 0.5 0.0 C2 H4 5.37 0.0 5.37 0.0 C2 H6 0.5 0.0 0.5 0.0 Higher heating value (kJ m3 ) 15,600 9600 15,800 10,300 (Btu ft 3 ) 419 275 425 276

gas composition for two representative operating conditions. In general, the model overpredicts H2 production, underpredicts CO and CH4 production, and is relatively close in predicting CO2 production. The presence of higher hydrocarbons (C2 H2 , C2 H4 and C2 H6 ), which are very important contributors to gas heating value, are not predicted by the computer model. Additionally, the equilibrium model predicts that very little char (less than 1%) is formed at these operating conditions. The production of both char and higher hydrocarbons in the pyrolysis experiments indi-

cates that the process is strongly non-equilibrium in character. 4. Combined model Although the chemical equilibrium model did not well predict experimental gas compositions, it was still employed in the preliminary evaluations of the combined model of the ballasted gasier. To combine the two submodels, the e ect of enthalpy changes associated with pyrolysis chemistry on heat transfer must be calculated.

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Fig. 4. Comparison of experimental data with model results using the calculated equilibrium gas composition.

The temperature of the uidized bed will be controlled, to a large extent, by the pyrolyzing biomass, which are endothermic reactions. Thus, the temperature equation for the uidized bed must include a loss term representing heat absorption by pyrolyzing fuel: dT1 mgas cp; gas 2 r1 lhi (Tgas T1 ) + (T2 T1 ) = dt m1 cp; 1 m1 cp; 1 + Qpyr hi SA (T13 T1 ) + : m1 cp; 1 m1 cp; 1 (21)

to develop a time prole of gas composition and bed temperature. 4.1. Comparison of predictions with experiments (equilibrium gas composition) Fig. 4 compares predictions of the gasication model to experimental results obtained during pyrolysis of 91 kg h1 of biomass. One trial was performed with the reactor unballasted while the second trial included the latent heat ballast. Predictions for neither trial agree with experimental cooling curves. In both cases, the reactors cool more slowly than predicted by the model. Such a result might be expected in the presence of non-equilibrium pyrolysis reactions, which absorb signicantly less heat than occurs if equilibrium is reached. 4.2. Comparison of predictions to experiments (experimental gas composition) The production of char and higher hydrocarbons in the experimental trials indicated that chemical equilibrium was not attained in the ballasted gasier. Suspecting that model predictions of cooling curves would improve if the chemical composition was more

The heat required to pyrolyze the fuel, Qpyr , can be calculated from Qpyr = nf
P

ni (hf +

h)i
R

ni (hf +

h)i : (22)

Since Qpyr is dependent on temperature and T1 is dependent on gas composition, an iterative solution procedure is employed. Based on the initial specication of temperatures, gas composition and Qpyr can be calculated from the chemical submodel. These values are returned to the heat transfer submodel. The differential equations are integrated, and new values for temperature are determined. This process is repeated

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Fig. 5. Comparison of experimental data with model results using the measured gas composition.

accurately predicted, the measured gas composition was substituted for the equilibrium calculations. Although moisture could not be directly measured, it was estimated from a mass balance on hydrogen. Char production was approximately 10% (mass basis) of the incoming feed based on analysis of cyclone catch in the experiments. Predicted cooling curves using measured (non-equilibrium) gas compositions are compared to experimental cooling curves in Fig. 5. Very excellent agreement is obtained for both ballasted and unballasted reactors. 5. Conclusions A mathematical model of a latent-heat ballasted gasier was developed consisting of coupled heat transfer and chemical equilibrium submodels. The heat transfer submodel is accurate for both ballasted and unballasted operation of the gasier. A small discrepancy between initial cooling rates may be due to residual fuel in the reactor. The equilibrium submodel proved to be a poor predictor of actual gas composition in the ballasted gasier. The assumption of chemical equilibrium underpredicted the production of char and hydrocarbons.

Major gas constituents showed important discrepancies with experimental data. As a result, the combined model underpredicted the cooling time of the pyrolytic reactor by about 50%. Substituting the experimental gas composition for the calculated gas composition greatly improved the predictions. Acknowledgements The authors would like to thank the Catron family for their generous nancial support of this project. Some of the gasication trials were performed with support from the Iowa Energy Center. References
[1] Pletka R, Brown RC, Smeenk J. Indirectly heated biomass gasication using a latent heat ballast. Part 1: experiments. Biomass and Bioenergy 2001;20:297305. [2] Incropera F, De Witt D. Fundamentals of heat and mass transfer, 3rd ed. New York: Wiley, 1990. [3] Reynolds W. Thermodynamic properties in SI. Stanford University, Department of Mechanical Engineering, 1979. [4] Reed T. Biomass gasication and principles. Park Ridge, NJ: Noyes Data Corp., 1981. [5] Kuo K. Principles of combustion. New York: Wiley, 1986.