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F. A. N. Fernandesa, ABSTRACT

C. P. Souzab Partial oxidation of methane is one of the most important chemical processes
b for the production of syngas. In recent years, the abundant availability of
and J. F. Sousa natural gas and the increasing demand of hydrogen have led to high interest to
further develop this process increasing the yield of syngas. In this work the
Universidade Federal do Ceará
partial oxidation of methane was studied from a modeling point of view in a
membrane reactor and in a conventional reactor. A mathematical model of a
Departamento de Engenharia Química membrane reactor used for partial oxidation of methane, assuming steady-
Campus do Pici, Bloco 709 state conditions, was developed to simulate and compare the maximum yields
60455-760 Fortaleza, CE, Brasil
and operating conditions in the reactor with that in a conventional reactor.
Simulation results show that different parameters affect methane conversion and H2/CO ratio, such as temperature, operating conditions, and membrane
Universidade Federal do Rio Grande do Norte parameters such as membrane permeance. In a membrane reactor an increase
Departamento de Engenharia Química
in the operating pressure corresponds to an increase in methane conversion,
since allows for a greater partial pressure gradient between the reaction and
Campus Universitário permeate zone, thus contributing to shift the equilibrium towards the products.
Natal, RN, Brasil As such, the membrane reactors are a good alternative to produce syngas
especially for GTL processes. Operating conditions can be set to control the
H2/CO ratio to a desired value, and high conversions at mild temperatures can
be achieved reducing capital and operational costs.

Keywords: membrane reactor, partial oxidation, methane, modeling

NOMENCLATURE studied for the production of syngas (Ashcroft et al., 1990;
Disanayake et al., 1991; Rajaput & Prabhakar, 1992;
A tube sectional area [m2] Hickman & Schmidt, 1993). Partial oxidation of methane
CP heat capacity [J/g.K] involves one non-reversible reaction (methane
Fi flow rate of component i [mol/h] combustion) and two reversible reactions (steam
ki rate constant of reaction i reforming and carbon dioxide reforming). Methane
Ki equilibrium constant of reaction i or adsorption combustion is a very fast and highly exothermic reaction,
coefficient of component i which releases a great quantity of energy demanding a
Pi partial pressure [atm] good temperature control as not to compromise the reactor
and reaction tubes structure. So a membrane reactor offers
PT total pressure in the reaction zone [atm]
the possibility of supplying oxygen for the reaction
Ri rate of reaction i [mol/h.gcat]
throughout the entire reactor length controlling the
rm radius of the membrane [m] combustion reaction in the reactor and spreading the heat
rT radius of the reaction tube [m] release throughout the reactor not only at its beginning.
T temperature [K] The development of oxygen permeable membranes
uS superficial velocity [m/h] has opened up a new possibility to enhance the partial
z distance from the inlet of the reaction tube [m] oxidation of methane process. New improvements are
been done in membrane materials and structures, which
Greek symbols supports the selective compound in porous alumina,
porous ceramic substrate, and in nanostructured carbides,
b catalyst density [g/m3] and several works suggests the oxygen-permeating dense
membranes have potential applications in partial oxidation
Superscripts of methane (Balachandran et al., 1997; Tsai et al., 1997;
Kao et al., 1997).
AZ air flow zone The modeling and simulation of catalytic
RZ reaction zone membrane reactors for methane conversion to syngas has
been done by some authors, specially on steam reforming
of methane and oxidative coupling of methane (Shu et al.,
1994; Wang and Lin, 1995; Kao et al., 1997; Assaf et al.,
INTRODUCTION 1998; Chen et al., 2003; Lin et al., 2003; Gallucci et al.,
2004). Very few works have dealt with partial oxidation of
Partial oxidation of methane has attracted methane in membrane reactors (Tsai et al., 1997; Jin et al.,
substantial interest over the years for the production of 2000) and none dealing with the production of syngas for
syngas and hydrogen. In recent years, the abundant gas-to-liquid (GTL) processes.
availability of natural gas and the increasing demand of This work presents the mathematical modeling of a
hydrogen have led to high interest to further develop this one-dimensional, isothermal membrane reactor operating
process increasing the yield of syngas. at steady-state, comparing and discussing reactor and yield
The partial oxidation reaction has been extensively improvements.
Engenharia Térmica (Thermal Engineering), Vol. 5 - Nº 01 - July 2006 40

10 [mol/s.2Fe0. Air è K 2 × PCH 4 × PH 2O ø flows in the outer tube and oxygen permeates to the inner tube through the membrane.5] 66200 (1990) and Xu and Froment (1989). are given by: inserted in a radiant furnace chamber. 5 . Methane and optionally O2 are 2 2 continuously fed into the catalytic zone. Yamada and Eguchi 2. 1989). Ciência/Science Fernandes.26×10 +1.. the Parameter Pre-Exponential Factor Ea or DH assumption of an isothermal reactor is reasonable (Jin et [J/mol] al. The simulated operating conditions process (Xu & Froment. Table 1.gcat.37 ×10 -8 × T 2 × ) é P RZ ×10 -5 -(2. ë O2 û · Intrinsic kinetics for methane combustion.5 that the reactor can support is limited by the metallurgical R1 = (4) limitations of the tubes. Engenharia Térmica (Thermal Engineering).19 x10-9 [mol/s.gcat.. CO2 and H2O along the reactor length are given by: dFi = r b × A × ån ij × R j (7) dz j The changes on the component O2 along the reactor length are given by: dFO 2 = r b × A × (. ê (O2 ) ù ú (9) · Plug-flow on both reaction and air zones. are presented in Table 2. ÷÷ (5) inner membrane wall tube which contains the catalyst. CH 4 + CO2 « 2CO + 2 H 2 (3) Commercial catalyst is composed of zirconium and platinum supported in alumina or nickel supported in The kinetic model for the reaction on a Ni/Al2O3 alumina and the reactor is composed of vertical tubes catalyst is based on a Langmuir-Hinshelwood reaction (between 10 and 900 tubes inside the reactor) with internal mechanism which rate expressions for reactions (1) to (3) diameters from 7 to 16 cm and lengths from 6 to 12 m. The basic assumptions made for the membrane reactor were: ( FM = 9.77 x105 [Pa-0.8O3 membrane described by Jin et al. which k3 were thoroughly studied by Arai.62×10 ×T ) - -3 -5 · · Steady-state operation.2 × R1 )+ 2p × rM × FM (8) dz Figure 1.65 x10-4 [Pa-1] 103500 (1986). 2000). Richardson and Paripatydar KO2 1.3Co0. Modeling of Partial . (2000) who correlated the permeation to MATHEMATICAL MODEL oxygen partial pressure and temperature. Scheme of the membrane reactor. k1 1. ê P AZ ×10 -5 -(2. The kinetic parameters for the reaction are · Adsorption is the determinant step of the kinetic presented in Table 1. Vol. Isothermal conditions. Oxygen permeation was calculated based on the permeation of a La0. A scheme of the æ PCO 2 × PH 2 ö reactor and mathematical model is shown in Fig. Since the partial oxidation of methane is a mildly exothermic reaction and diluted feed is used. ÷÷ (6) è K 3 × P CH 4 × P CO 2 ø The changes on the components CH4. · The catalyst active sites have different adsorption capabilities for CH4.26×10-3 +1.6Sr0. H2O and CO2. carbon dioxide reforming and steam reforming reactions. MEMBRANE REACTOR CH 4 + O2 ® CO2 + 2 H 2O (1) CH 4 + H 2O « CO + 3H 2 (2) In partial oxidation of methane.Nº 01 . ç R3 = k3 × PCH 4 × PCO 2 × ç1 .Pa1. The membrane reactor configuration is quite æ PCO × PH3 2 ö simple and consists of an external steel tube (shell) with an R2 = k 2 × PCH 4 × PH 2O × çç1 . The feed temperature is about 800C. k2 4.gcat. The maximum temperature k1 × PCH 4 × PO02. Souza and Sousa et al.044ú ( ) · No boundary layer on membrane surfaces.. since at higher temperatures the (1 + K CH 4 × PCH 4 + K O 2 × PO 2 )2 metal tubes can creep under stress.42 x10-9 [mol/s. 1. the catalytic fixed- bed reactor is fed with a gas mixture of CH4 and O2.77 ×10 -6 × T + 1.Pa2] 23700 KCH4 6. H2.5] 166000 Partial oxidation of methane involves one non. CO. Ross & Steel (1973). O2.Pa2] 29000 reversible reaction and two reversible reactions.0. Kinetic parameters for partial oxidation of methane.July 2006 41 .62×10-5 ×T ) .

pos processing of the syngas is required in order conditions as function of the reactor length (T = 1173 K.0 around a conversion of methane of 40 to 60%. Fig. the conversion of methane also increases. FCH40 = 0. which requires H2/CO ratios near 2:1.1016 on reaction temperature. 2 to 4). The effect of temperature on the H2:CO ratio is complex but it decreases when temperature increases. (2000) over the range of temperature T = 1000 to 1200 K at pressure of P = 1 atm.30 A maximum production of hydrogen is obtained Reactor Length [m] 20. which occurs only to a certain extent. 2. and H2:CO ratio and CO2:H2 synthesis (Fig. Vol. to remove the excess of hydrogen in the syngas if it is to be FCH40 = 0.50 mol/s). After validation with literature data..2 reaction selectivity to carbon monoxide is low..1322 reactions (2) and (3) take a major shift towards the Membrane external radius [m] 0. The production of carbon dioxide is considerable due to the combustion of methane.0 dioxide reforming are responsible for the formation of Total Pressure [atm] 1. range of temperature and pressure employed in the present study. and H2:CO ratio and CO2:H2 ratio (b) for membrane reactor operating at isothermal conditions as function of the reactor length (T = 1123 K. Engenharia Térmica (Thermal Engineering). Influence of Temperature Temperature plays an important role in partial oxidation of methane both in the conversion of methane and in the H2:CO ratio. Ciência/Science Fernandes. which has studied this reaction over the entire consumed by the equilibrium reactions (Fig. 4a).0150 monoxide in the reactor. Partial pressure (a).Nº 01 . 3.0 syngas. Table 2. The oxygen permeation rate through the membrane was studied and validated by Jin et al. 5 . the oxygen is fed continuously through the reactor giving an almost linear consumption of methane (Figs. Bed Porosity 0. Souza and Sousa et al. and for temperatures above 1250 K. (2000) was used to test the membrane reactor program and the responses of the membrane. used in Fischer-Tropsch synthesis. Below 1000 K. Partial pressure (a). decreases rapidly.1500 reactants reducing the amount of hydrogen and carbon Membrane thickness [m] 0. 2b to 4b). (1997) over a traditional fixed bed reactor and the data presented by Jin et al. At a methane conversion of The differential equations 7 and 8 were solved by 90% the shift towards the production of CO2 and H2O is numerical integration using a 5th order Runge-Kutta-Gill especially high and the amount of H2 and CO in the reaction method. ratio (b) for membrane reactor operating at isothermal Any way. The computational program used in the present study was tested with the data presented by Tsai et al. As the temperature increases.July 2006 42 . 4b). the conversion per pass is very low and product recycling is needed. So. RESULTS AND DISCUSSION The major advantage of the membrane reactor is to spread the combustion of methane throughout the reactor length not letting the combustion occur solely at the beginning of the reactor what could damage the reactor due to the amount of heat released by the reaction. the model was used to simulate industrial like conditions for syngas production.50 mol/s). Steam and carbon Methane flow rate [mol/h] 5200. the conversion of methane is total even for high gas loads (Fig. Operating conditions and reactor parameters. Modeling of Partial . Using a membrane. so higher temperatures favors lower H2:CO ratios which can be needed for processes such as the Fischer-Tropsch Fig. and the Catalyst Density [gcat/m3] 2355. the partial oxidation of methane should not proceed to its completion (total consumption of methane). after which the equilibrium of the Tube external radius [m] 0. conversion of 90% when these products tend to be (1997). depending Tube internal radius [m] 0. The H2/CO ratio is high and tends to The kinetic data were obtained by Xu & Froment increase as the reaction proceeds up to a methane (1989) and validated for a fixed bed reactor by Tsai et al.

8.6. 5. H2:CO ratio and CO2:H2 ratio (b) for membrane reactor operating at isothermal Influence of membrane permeability conditions as function of the reactor length (T = 1223 K.2 to 0. and Lower oxygen partial pressure inside the air zone can results for three different temperatures are shown in Fig 7.6. Recycling the CO2 produced by the combustion the use of membranes that allows the flow of a limited reaction and not converted to syngas back to the reactor amount of oxygen to the reaction zone. 4. In the latter case the feed can enhance the production of syngas shifting the membrane should be chosen during the project of the carbon dioxide reforming towards the production of reactor and can be used as to set a maximum permeability syngas.Nº 01 . H2:CO ratio and CO2:H2 ratio (b) for membrane reactor operating at isothermal conditions as function of the reactor length (T = 1223 K. Ciência/Science Fernandes. Fig.July 2006 43 . but at the expense of a higher H2/CO ratio which can be undesirable for GTL processes. Total conversion of methane increases as the Influence of CH4/CO2 ratio oxygen flow rate through the membrane increases. Modeling of Partial . The effect of molar carbon dioxide-to-methane affected by the highly exothermic combustion reaction and (CO2/CH4) ratio was examined by varying this ratio from temperature control can be attained by controlling the 0. Initial flow rate of CO2 = 0. Souza and Sousa et al. FCH40 = 0. Influence of CH4/H2O ratio Steam reforming usually proceeds in the presence of an excess of steam to enhance reforming and syngas production.50 mol/s). Initial flow rate of CO2 = 0. due to Carbon dioxide reforming usually proceeds in the the greater amount of oxygen available to the reaction (Fig presence of an excess of carbon dioxide to enhance 10). Engenharia Térmica (Thermal Engineering). and results for three different temperatures are shown in Fig 9. help to lower the H2/CO ratio and the amount of syngas produced is also higher. as well as. The effect of molar steam-to-methane (H2O/CH4) ratio was examined by varying this ratio from 0. 6. lower the oxygen flow rate to the reaction zone. Temperature inside the reaction zone is directly reforming. Partial pressure profiles for the reaction for two amount of oxygen that can flow to the reaction zone.. Adding steam to the reactor feed can enhance the production of syngas shifting the steam reforming towards the production of syngas.2 CH4 flow flow rate of oxygen from the air stream zone to the reaction rate. 5 . Vol. Membrane permeability is directly related to the FCH40 = 0. Fig. zone and therefore influences the rate of methane combustion.50 mol/s). Partial pressure profiles for the reaction for a H2O/CH4 ratio is shown in Figs.6 CH4 flow rate. Partial pressure (a). Methane conversion (a) and H2/CO ratio (b) for a membrane reactor as function of temperature and gas load.2 to 0. different CO2/CH4 ratios are shown in Figs. Partial pressure (a). Fig.. 5 and 6. Higher amounts of carbon dioxide in the reactor for the system.

Engenharia Térmica (Thermal Engineering). New simulations are needed to optimize the reactor and to study the reaction in multiple steps changing the temperature of each step as to produce a greater quantity of syngas and to reduce the amount of gas that has to be recycled. the ratio remains very high for use in GTL process and further processing is required to control the H2/CO ratio. In partial oxidation of methane.. CONCLUSIONS The partial oxidation of methane was studied from a modeling point of view in a membrane reactor. the membrane reactors are a good alternative to produce syngas for GTL processes or pure hydrogen. Partial pressure (a). 5 . which gives the lowest H2/CO ratio. Methane conversion (a) and H2/CO ratio (b) for a Controlling the H2/CO ratio is important.7 up to 3. especially membrane reactor as function of temperature and steam to gas-to-liquid processes (GTL) where the optimum ratio flow rate at the maximum hydrogen production point. varies from 0. steam and carbon dioxide recycling.50 mol/s). The membrane absorption unit can be shaped as a multitube heat exchanger where the syngas passes through the inner or outer side of the membrane tubes. Souza and Sousa et al. 7. Initial flow rate of H2O = 0. molar flow rate. Fig.6 CH4 Fig. Even so. function of temperature and oxygen flow rate through the membrane (conversion at reactor length = 20 m). Methane conversion (a) and H2/CO ratio (b) for a membrane reactor as function of temperature and carbon dioxide flow rate at the maximum hydrogen production point. Modeling of Partial .. H2:CO ratio and CO2:H2 ratio (b) for membrane reactor operating at isothermal conditions as function of the reactor length (T = 1173 K. 8. Vol. Controlling the H2/CO Ratio Fig.July 2006 44 . Hydrogen permeates from the syngas towards the hydrogen-poor sweep gas adjusting the H2/CO Fig. and influences hydrocarbon product distribution. An option is to pass the crude syngas through a membrane absorption unit so hydrogen can permeate through the membrane correcting the H2/CO ratio to the desired level. the H2/CO ratio is large and lowering this ratio would require operating in high temperatures. FCH40 = 0.0.Nº 01 . As such. Enhanced conversion of methane to syngas can be attained by recycling carbon dioxide and steam back to the reactor entrance as to shift the equilibrium reactions towards syngas. 10. Operating conditions can be set to control the H2/CO ratio to a desired value. removing H2 through the membrane. Simulation results show that different parameters affect methane conversion and H2/CO ratio. Ciência/Science Fernandes. such as temperature. 9. Methane conversion for a membrane reactor as ratio to a desired value.

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