CHEMICAL REACTION ENGINEERING

Activity 2 A/B
Ideal reactors calculation with multiple reactions
Isothermal and Non-Isothermal study

Nicolas Garcia Scaglioni

 Contents

Introduction and Purpose: ............................................................................................................... 2

Methods........................................................................................................................................... 2

Results and Discussion ................................................................................................................... 4

Isothermal ................................................................................................................................... 4

Non-Isothermal ........................................................................................................................... 8

Conclusion and Acknowledgements: ............................................................................................ 15

References ..................................................................................................................................... 16

Appendices .................................................................................................................................... 17

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Introduction and Purpose:
The hydrogen production by steam conversion of methane is a well-known industrial process
that can be produced from renewable or fossil resources. Beside some studies to try to improve the
large-scale production of hydrogen via ethanol 90% of the H2 production still happens in the
methane process, according to Haryanto, et al. (2005) review (Marino, et al. 2004). This is a
process that usually have a reaction carried out in nickel catalysts, with a several studies on their
activity, deactivation and kinects (Xu and Froment 1989) (Bernardo, Alstrup and Rostrup-Nielsen
1985).
The purpose of this assignment is to reproduce the data of the kinect reaction of hydrogen
production on 15.2% nickel catalyst developed by Xu and Froment (1989). Their artigle consider
a large number of reactions on the mechanism, and after some assumptions, based on information
well accepted in the literature they ended up with the three global reactions below:
1. 𝐶𝐻4 + 𝐻2 𝑂 = 𝐶𝑂 + 3𝐻2 (methane steam reforming)
2. 𝐶𝑂 + 𝐻2 𝑂 = 𝐶𝑂2 + 𝐻2 (water-gas shift)
3. 𝐶𝐻4 + 2𝐻2 𝑂 = 𝐶𝑂2 + 4𝐻2 (methanation)
The software MATLAB® calculates the material and energy balance for a simulation on a Plug-
Flow Reactor carrying these three reactions using the kinect parameters calculated by Xu and
Froment (1989). There is two parts in this work: the first one for an ideal isothermal reactor and
the second one for an ideal non-isothermal reactor.

Methods
This simulation assumes a steady state reactor, unidirectional tubular reactor flowing through
a catalyst packed bed and constant pressure. In the first case also assumes an isothermal reactor,
but the second study has the temperature and energy transfer effects.
The software MATLAB solved the mass and energy balance for this reactor, by calculating the
ordinary differential equations with the present function “ode15s”. All the algorithm is available
on the appendices 1 and 2. The equations 1 describes the mass balance for a packed bed plug flow.
The equation 2 refers to the rate of reaction, and has the kinetics “R” extract from the Xu and
Froment (1989) article. The volumetric rate was calculated through the ideal gas equation of state
described in the equation 3.
𝜙𝑐𝑎𝑡 𝑑𝑁̇
. 𝑑𝑉 =𝑟 (1)
𝜌𝑐𝑎𝑡 𝑐𝑎𝑡

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 𝑟 = 𝜈. 𝑅 (2)
̇
𝑁 .𝑅𝑔 .𝑇
𝑉̇ = 𝑃 (3)

For the second part of this assignment the energy balance equations 4 and 5 were calculated
simultaneously with mass balance. For an adiabatic reactor the uses 𝑄̇ = 0.
𝜌
𝑄𝑟̇ = ∑𝑁𝑅
𝑗 (𝐻𝑅 𝑗 ∗ 𝑅𝑗 ) ∗ 𝜙
𝑐𝑎𝑡
(4)
𝑐𝑎𝑡

𝑑𝑇 𝑄̇ − 𝑄𝑟̇
= (5)
𝑑𝑉𝑐𝑎𝑡 𝑁𝑖 ∗𝐶𝑝

According to Fogler (2006), for multiply reactions, selectivity tells how one product favors
over another in the reaction process, so is the amount of the desired product by the amount of the
undesired product. So, for this process, I used the overall selectivity of H2 flow by CO flow at
along the reactor volume, described in the equation 4 below.
𝑁̇𝐻2
𝑆𝐻2 ⁄𝐶𝑂 = 𝑁̇ (4)
𝐶𝑂

The Yield, for Fogler (2006), is the ratio between the product formed at the end of the
reactor to the number of moles converted of the key reactant. As well, I used the total produced
flow rate of H2 by the converted flow rate of CH4 and total produced flow rate of CO by the
converted flow rate of CH4, described in the equations 5 and 6 below.
𝑁̇𝐻2
𝑌𝐻2 = 𝑖𝑛 𝑜𝑢𝑡 (5)
𝑁̇𝐶𝐻4 −𝑁̇𝐶𝐻4

𝑁̇𝐶𝑂
𝑌𝐶𝑂 = 𝑖𝑛 𝑜𝑢𝑡 (6)
𝑁̇𝐶𝐻4 −𝑁̇𝐶𝐻4

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 Results and Discussion

Isothermal
The equilibrium composition was defined when the variation of the products by the
variation of the volume achieved zero. MATLAB software calculates the dry products molar flow
and the molar fraction presented on the Table 1. The Table 2 compare the molar fraction
equilibrium calculated by CEA NASA software, which uses the Gibbs free energy method.

Table 1 – Molar flow of all components and molar fraction of the dry products at the equilibrium.

CH4 H2O H2 CO CO2

Molar Flow (kmol/h) 71.275 360.947 405.976 38.396 70.328
Molar Fraction (dry products) 0.122 -- 0.693 0.066 0.120

Table 2 – Equilibrium molar fraction composition calculated with MATLAB and CEA NASA software.

CH4 H20 H2 CO CO2

MATLAB 0.0753 0.3812 0.4287 0.0405 0.0743
CEA NASA 0.0754 0.3816 0.4283 0.0407 0.0740

Results presented in Table 2 reveals a maximum difference of 0.004 between the two
methods, which is an acceptable proximity.
By linear interpolation of the calculated data from MATLAB the volume of catalyst needed
for conversion of 0.5 of CH4 is 4.168dm3 and the reactor volume is 6.946dm3. All the other
parameters for conversion of 50% of CH4 is presented on Table 3.

Table 3 – Moles fraction, gas flow, gas flow ratio, residence time, selectivity and yield for conversation of 50% of methane.

Composition: dry products Gas Flow ( 𝑉̇) ̇

𝑉𝑖𝑛 Residence time Selectivity: Yield Yield
𝑅=
CH4 H2 CO CO2 m3/s
𝑉𝑜𝑢𝑡 ̇ ϑ(s) H2 by CO H2 CO
0.173 0.653 0.059 0.114 3.878 0.802 0.0018 11.0739 3.7652 0.3400

The axial profile of the dry products molar fraction the along the reactor volume is
presented on the graphic of the Figure 1.

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 1.000

0.900
Molar fraction of the dry products

0.800

0.700

0.600
CH4
0.500 H2
0.400 CO
0.300 CO2

0.200

0.100

0.000
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035
Reactor Volume m3

Figure 1 – Graphic of molar fraction of dry products through the reactor volume.

By the Figure 1, is possible to see the equilibrium being achieved at the volume of 0.02m3,
after that the composition is constant. The Figure 2 presents the graphic of residence time along
the reactor volume, which was predictable to have a linear growth.
0.010

0.008
Residence Time ϑ (s)

0.006

0.004

0.002

0.000
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035
Reactor Volume m3

Figure 2 - Graphic of residence time through the reactor volume.

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 The gas velocity was calculated based on ideal gas equation of state presented on equation
3, the ratio between the inlet velocity and outlet velocity along the reactor volume is presented on
the graphic of the Figure 3.
1.00

0.95
Ratio: inlet / outlet gas velocity

0.90

0.85

0.80

0.75

0.70

0.65

0.60
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035
Reactor Volume m3
Figure 3 - Graphic of velocity ration through the reactor volume.

The Figure 3 shows that the gas velocity in the outlet increases till the equilibrium, making
the ration below 1. Because the pressure, temperature, geometry are constants, the gas velocity
increases if the number of moles increase.
The Figure 4 shows the Yield of hydrogen and carbon monoxide from the consumed
methane, calculated from equation 5 and 6. And the Figure 5 presents the Selectivity of the desired
product H2 by the undesired product CO.
10.000 0.500
9.000 0.450
8.000 0.400
7.000 0.350
6.000 0.300
Yield CO

0.250
Yield H2

5.000
Hydrogen
4.000 0.200 CO
3.000 0.150
2.000 0.100
1.000 0.050
0.000 0.000
0.000 0.005 0.010 0.015 0.020 0.025
Reactor Volume m3
Figure 4 - Graphic of Yield of Hydrogen and Carbon Monoxide through the reactor volume.

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 20.000
18.000
Overall Selectivity of H2 by CO

16.000
14.000
12.000
10.000
8.000
6.000
4.000
2.000
0.000
0.000 0.005 0.010 0.015 0.020 0.025
Reactor Volume m3
Figure 5 - Graphic of Selectivity of Hydrogen by Carbon Monoxide through the reactor volume.

The Figure 4 shows that the hydrogen yield after 0.001m3 is a constant straight line in 3.7.
The carbon monoxide has a smaller value and oscillated in the beginning, caused because it is
product from the first reaction and then reagent of the second, at the first increase by its production
and the reduced by its consumption. This is also shown at Figure 5, of selectivity of hydrogen by
carbon monoxide.
The Figure 6 shows axial profile of the kinects of each reaction, direct and inverse, along
the reactor volume.

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 Figure 6 –Kinects axial profile of the three reactions along the reactor volume

In the Figure 6 it is possible to see the direct and inverse profile of the kinects of the three
reactions considered. For reaction 1 and 3, the inverse profile, happens all the time close to zero,
this way both reactions can be considered irreversible.

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Non-Isothermal
The non-isothermal reactor simulation algorithm is described at appendix 2. The MATLAB
calculated the mass and energy balance defined by equations 1 to 5 simultaneously, and with that
was possible to plot the graphic from Figure 7 and 8, which describe the moles fractions and flow
rate profiles along the reactor volume, which is correlated with the catalyst volume.
0.300

0.250

0.200
Mol Fraction

CH4
0.150
H2
CO
0.100
CO2

0.050

0.000
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040
Catalyst Volume (m3)
Figure 7 - Graphic of the axial molar fraction profile of dry products along the catalyst volume of an adiabatic reactor.

900.00

800.00

700.00

600.00
CH4
Flow Rate (kmol/h)

500.00 H2
CO
400.00
CO2
300.00 H2O
Total
200.00

100.00

0.00
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040
Catalyst Volume (m3)
Figure 8 - Graphic of the axial flow rate profile along the catalyst volume of an adiabatic reactor

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 The reaction was considered at equilibrium when the variation of flow rate by the variation
of the volume was zero. By that, the Figure 7 and 8 shows that the volume of catalyst needed to
achieve the equilibrium reaction is 0.053m3. And the dry mol fraction of CH4 at equilibrium is
0.465, for H2 is 0.433 and only 18% of CH4 conversion. The volume of catalyst needed to
equilibrium increased, and the conversion of CH4 decrease in the non-isothermal reactor, being a
less effective reactor operation for this kind of reaction.
The Figure 9 is a graphic that describe the temperature profile along the reactor volume,
described in the graphic by the catalyst volume.
950.00

900.00

850.00
Temperature K

800.00

750.00

700.00
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040
Catalyst Volume (m3)
Figure 9 - Graphic of the axial temperature profile along the catalyst volume of an adiabatic reactor.

The reaction 1 and 3 are endothermic reactions and the reaction 2 is exothermic (Xu and
Froment 1989). Endothermic reactions decrease the temperature of adiabatic systems and
exothermic increase. The Figure 6 showed that the kinetics from the reactions 1 and 3 are much
bigger than reaction 2 at the beginning of the reactor. And because the heat of reaction is
proportional with the kinects rate the temperature drops until establish the equilibrium.
This is also shown in Figure 10, which describe the heat flow rate profile of the system
along the reactor volume. The negative value, means that the flow heat is leaving the system. The
minimum bound of the y-axis was reduced to -1000kW/Lreactor to provide a graphic more visual,
but the lowest value of the lost heat rate is -77196.9 kW/Lreactor.

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 0
-100
-200
Heat Flow kW/Lreactor

-300
-400
-500
-600
-700
-800
-900
-1000
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0
Reactor Volume (L)

Figure 10 - Graphic of the axial heat flow profile along the catalyst volume of an adiabatic reactor.

The second reaction, can not be considered irreversible, as shown before. The direct
reaction kinects is bigger than the inverse reaction kinects, and because of that, there is a small
exothermal gradient. This gradient can cause an effect on reactor with larger volume, increasing
the temperature. The Figure 11 shows the graphic that describe the temperature profile along the
an extrapolated reactor volume.
950.0

900.0

850.0
Temperature K

800.0

750.0

700.0
0.0 1000.0 2000.0 3000.0 4000.0 5000.0 6000.0
Reactor Volume (m3)
Figure 11 - Graphic of the extrapolated axial temperature profile along the catalyst volume of an adiabatic reactor.

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 The Figure 11 exhibit the effect on the temperature caused by the exothermal reaction.
When the temperature rises, the other reactions are influenced, and their reaction rate goes up as
well. This causes a variation in the equilibrium previously established, thereby increasing the
conversion of CH4. This new conversion profile is present in the graphic of the Figure 12 below.
0.700

0.600

0.500
Conversion XCH4

0.400

0.300

0.200

0.100

0.000
0.0 1000.0 2000.0 3000.0 4000.0 5000.0 6000.0

Catalyst Volume (m3)

Figure 12 - Graphic of the axial conversion of CH4 profile along the catalyst volume of an adiabatic reactor.

The equilibrium established previously has the CH4 conversion of 18%, but it is possible
to see in Figure 12 that the conversion can be up to 60% proximally. And to achieve 50% of
conversion, for a non-isothermal reaction need 1235.9m3 of catalyst, much more than the
isothermal. The Figure 13 show the comparative graphic between isothermal and non-isothermal
flow rate of CH4 and H2. These key components were chosen to obtain a cleaner graphic.
450.0

400.0

350.0

300.0
CH4 isothermal
Flow Rate (kmol/h)

250.0 H2 isothermal
CH4 Non-isothermal
200.0
H2 Non-isothermal
150.0

100.0

50.0

0.0
0.00 5.00 10.00 15.00 20.00 25.00 30.00
Reactor Volume (dm3)
Figure 13 - Graphic of the compared axial flow rate profile along the isothermal reactor and non-isothermal adiabatic reactor.

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 The Figure 13 and the Table 4 below, show the comparative data between the two reactors
studied in this assignment. And by the data it is possible to visualize that this reaction works much
better in an isothermal reactor. Not only by the catalyst volume needed but also the conversion of
CH4 and the mol fraction of H2 have better results in the isothermal reactor.
Table 4 – mol fraction, conversion and catalyst volume between the isothermal and non-isothermal reactors
Catalyst volume mol fraction CH4 CH4 conversation mol fraction H2
Isothermal 0.032 m3 0.122 60% 0.693
3
Non-Isothermal 0.053 m 0.465 18% 0.433

Because of that, it is important to verify the theoretical quantity of heat necessary to make the
non-isothermal reactor isothermal. The graphic in Figure 14 presents the quantity of heat flux
profile along the reactor volume. As expected, because the rate of reaction is larger at the inlet of
the reactor, a much higher amount of heat is required at the beginning. The heat flux goes to
77196.90kW/Lreactor at the beginning to 342.82kW/Lreactor at the end.
9.0

8.0

7.0
Heat Flux (kW/Lreactor) (x104)

6.0

5.0

4.0

3.0

2.0

1.0

0.0
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0
Reactor Volume (L)
Figure 14 – Graphic of the axial profile of heat flux required to keep the reactor isothermal.

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 This is a very large heat gradient between the beginning and the end of the reactor. it is
practically impossible to provide a heat flux profile as foreseen in Figure 14. But it is possible to
provide a constant heat flux along the reactor volume, such as a heat blanket that provides a
uniform amount of heat along the reactor volume. And to see this effect, was suggested for this
assignment, simulate a uniform heat supply of 300kW/Lreactor to the reactor. The Figure 15 and 16
shows the mol fraction and flow rate for this new situation.
0.800

0.700

0.600

0.500 CH4
Mol Fraction

H2O
0.400
H2
0.300
CO
0.200 CO2

0.100

0.000
0.00 0.02 0.04 0.06 0.08 0.10
Reactor Volume (m3)
Figure 15 - Graphic of the axial molar fraction profile of the reactor supplied with uniform external heat.

700.0

600.0

500.0
CH4
400.0
Flow Rate (kmol/h)

H2O
300.0 H2
CO
200.0
CO2

100.0

0.0
0.00 0.02 0.04 0.06 0.08 0.10
Reactor Volume (m3)
Figure 16 - Graphic of the axial flow rate profile of the reactor supplied with uniform external heat

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 The Figure 15 and 16, shows the effect of a constant heat flux along the reactor volume. It is
possible to see a better result than other non-isothermal, with mole fraction and flow rate of H2
bigger, that is more desired product. Besides the results is not still good as the isothermal reactor,
this is a more realistic one. Industrially the heat exchange in the reactors are uniform along the
reactor.

Conclusion and Acknowledgements:

This assignment asked to simulate a Plug Flow Reactor with Packed Bed Catalyst using the
kinects parameter created by Xu and Froment (1989). The Matlab software was used to calulate
the mass and energy balance of the reactor. This way it was possible to creat ghapic from
operational information, like flow rate and molar fraction, along the reactor volume.
In the first part, the isothermal reactor presents good methane maximum conversion of 60%
and consistent equilibrium data, which was compare with the data from NASA software. The
second part shows that the reaction did not work very good in a non-isothermal reactor. The
conversion was 18% and the catalyst volume to achieve the equilibrium was bigger 0.053 m3. In
compare with more realistic reactor, the simulation was carried on a non-isothermal reactor with a
constant heat flux along the volume, and shows 100% of methane conversion not finding the
equilibrium for this reaction.
This assignment put forward the knowledge presented in class for chemical reaction kinects
and plug flow reactors. Also increased the Matlab familiarity with ode functions and did a
connection between theory presented and scientific articles that are used in the current industry.

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References
Bernardo, C. A., I. Alstrup, and J. R. Rostrup-Nielsen. "Carbon Deposition and Methane Steam
Reforming on Silica-Supported Ni-Cu Catalysts." Journal of Catalysis 96, 1985: 517-534 .
FOGLER, H. SCOTT. Element of Chemical Reaction Engineering. Fourth Edition. Pearson
Education, Inc., 2006.
Haryanto, A., S. Fernando, N. Murali, and S. Adhikari. "Current Status of Hydrogen Production
Techniques by Steam Reforming of Ethanol:  A Review." Energy Fuels, 5 19, 2005: 2098–
2106.
Marino, F., M. Boveri, G. Baronetti, and M. Laborde. "“Hydrogen Production via Catalytic
Gasification of Ethanol. A Mechanism Proposal over Copper-Nickel Catalysts." Int. J.
Hydrogen Energy, 29, 2004: 67-71.
Xu, J., and G. F. Froment. "Methane Steam Reforming, Methanation and Water-Gas Shift: 1.
Intrinsic Kinetics." AIChE Journal. Vol. 35, No. 1, 1 1989: 88-96.

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Appendices
Appendix 1: Isothermal
%Application 2 part A Ideal reactors calculation with NR>1
%i1.CH4 2.H2O 3.H2 4.CO 5.CO2
%j.1) CH4 + H2O <=> CO + 3H2 (methane steam reforming)
%j.2) CO + H2O <=> CO2 + H2 (water-gas shift)
%j.3) CH4 + 2H2O <=> CO2 + 4H2 (methanation)

clear all, clc, close all

%First Data
P = 5; %bar
T = (650+273.15); %K
Rg = 8.314; %kJ K-1 kmol-1
nu = [-1 0 -1
-1 -1 -2
3 1 4
1 -1 0
0 1 1];
Ninicial = [50; 3*50; 0.05*50/0.95; 0; 0]; %mol/s
No = 3.6.*Ninicial; %kmol/h

%5% of DRY feed

%NoCH4 + NoH2 = Ndry
%NoH2 = 0.05Ndry
%NoH2 = 0.05*NoCH4 + 0.05*NoH2
%NoH2 = 0.05*NoCH4/0.95

%%*****Parameters************************

%for A at kmol/(kgcat·h)
Aj = [4.225e15 1.955e6 1.020e15]; Ai = [6.65e-4 1.77e5 6.12e-9 8.23e-5];
%for E and H at kJ/kmol
E = [240.1e3 67.13e3 243.9e3]; H = [-38.28e3 88.68e3 -82.90e3 -70.65e3];

%kj adsorption equilibrium constants %Ki CH4 H20 H2 CO for the reactions
k = Aj.*exp(-E./(Rg*T)); K = Ai.*exp(-H./(Rg*T));

%Equilibrium constants based on partial pressure

Kp1 = exp(30.481-27.187e3 / T);
Kp2 = exp(-3.924+4.291e3 / T);
Kp3 = exp(26.891-23.258e3 / T);

%**************************************

%%Reaction Equations

Vf=0.05;
Vcat,N] = ode45(@BMi,[0 Vf],No,[],P,K,k,Kp1,Kp2,Kp3,nu);

V_reactor = Vcat./0.6; %m3reactor

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%conversion of methane
Xch4 = (No(1)-N(:,1))/No(1);
Xgoal = zeros(size(Xch4,1),1)+0.5;
figure(1);
plot(V_reactor,Xch4,V_reactor,Xgoal)

%1)
%Selectivity: S_H2 = N_H2 final - N_H2 inicial / N_COfinal- N_COinicial
S_H2CO = (N(:,3)-No(3))./(No(1)-N(:,1));
%Yields
Y_H2 = ((N(:,3) - No(3)) ./ (No(1)-N(:,1)))
Y_CO = ((N(:,4) - No(4)) ./ (No(1)-N(:,1)))

%2) composition (molar frac) of the dry products

Nt = sum(N,2); %kmol/h
Ntdry = sum(N,2)-N(:,2); %kmol/h
xi = N./Ntdry;

%3) ratio between inlet and outlet gas velocity

P_pa = P*10^5; %Pa
V_flowi = sum(No)*(Rg*(10^3/3600)*T / P_pa); %m3 / s
V_flow = Nt.*(Rg*(10^3/3600)*T / P_pa); %m3 / s
R_flow = V_flowi./V_flow;

%4) residence time % Volume / Volume_flow

tau = V_reactor ./ V_flow; %second

function dN = BMi(Vcat,N,P,K,k, Kp1,Kp2, Kp3, nu)

x = N./sum(N);
p = P.*x;

DEN = 1 + K(4)*p(4)+ K(3)*p(3) + K(1)*p(1) + (K(2)*p(2))/p(3);

R1 = ( (k(1)/p(3)^2.5)*(p(1)*p(2) - (p(3)^3)*p(4)/Kp1) ) / (DEN^2);

R2 = ( (k(2)/p(3))*(p(4)*p(2) - p(3)*p(5)/Kp2) ) / (DEN^2);
R3 = ( (k(3)/p(3)^3.5)*(p(1)*p(2)^2 - (p(3)^4)*p(5)/Kp3) ) / (DEN^2);
R = [R1 ; R2 ; R3];

dcat = 1900 / 0.6 ; %kgcat.m3reactor-1 / m3cat.m3reactor-1 -> kgcat/m3 cat

r = nu*R*dcat; % kmol/(kgcat·h ).kgcat/m3 cat - kmol.h-1 / m3cat

dN=r;
end

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Appendix 2: Non-Isothermal

clear all, close all, clc

P = 5; %bar
To = (650+273.15); %K
Rg = 8.314; %kJ K-1 kmol-1
No = 3.6.*[50; 3*50; 0.05*50/0.95; 0 ;0]; %kmol/h
nu = [-1 0 -1
-1 -1 -2
3 1 4
1 -1 0
0 1 1];
Yo = [No ; To];

%*******************************Parameters************************

%for A at kmol/(kgcat·h)
% 1 2 3 % CH4 H20 H2 CO
Aj = [4.225e15 1.955e6 1.020e15]; Ai = [6.65e-4 1.77e5 6.12e-9 8.23e-5];

%for E and H at kJ/kmol

% 1 2 3 % CH4 H20 H2 CO
E = [240.1e3 67.13e3 243.9e3]; H = [-38.28e3 88.68e3 -82.90e3 -70.65e3];

%Non-dimensional, species parameters in the following table.

%CH4, H2O, H2, CO, CO2
a = [5.529
1.558
0.370
0.716
1.593]/1000;

b = [3.292
3.409
3.266
3.269
4.925];

%******************************************************************

Vf = 1000;
[Vcat,Y] = ode15s(@BMiBE,[0 Vf],Yo,[],P,Ai,Aj,E,H,a,b,Rg, nu);

Ni = Y(:,1:end-1);
T = Y(:,end);
V_reactor = Vcat./0.6; %m3reactor

% Loop for reaction velocity

RRd=[]; RRr=[] ;Qd=[];
for k=1:length(Vcat)
YY = Y(k,:)';
[Yprimo,Rd,Rr,Qdotk] = BMiBE(Vcat(k),YY,P,Ai,Aj,E,H,a,b,Rg, nu);
RRd=[RRd ; Rd]; RRr=[RRr; Rr];

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 Qd = [Qd ; Qdotk];
end

Qd = Qd./(3600*1000); %Kj/s.L_reactor

function [Yprimo,Rd,Rr,Qdot] = BMiBE(Vcat,Y,P,Ai,Aj,E,H,a,b,Rg, nu)

N = Y(1:5);
T = Y(end);
x = N./sum(N);
p = P.*x;

%kj 1 2 3 adsorption equilibrium constants

k = Aj.*exp(-E./(Rg*T));
%Ki CH4 H20 H2 CO for the reactions
K = Ai.*exp(-H./(Rg*T));

%Equilibrium constants based on partial pressure

Kp1 = exp(30.481-27.187e3 / T);
Kp2 = exp(-3.924+4.291e3 / T);
Kp3 = exp(26.891-23.258e3 / T);

%Entalpy of Reaction kJ/kmol

Hr = [(-4.47*10^13) * T^(-4.459)+226.9
-271.4 * T^(-0.2977)
99.52 * T^(0.0937)]*1000;

Cp = (a*T + b)*Rg;

DEN = 1 + K(4)*p(4)+ K(3)*p(3) + K(1)*p(1) + (K(2)*p(2))/p(3);

Rd(1) = ( (k(1)/p(3)^2.5)*(p(1)*p(2)) ) / (DEN^2);

Rr(1) = ( (k(1)/p(3)^2.5)*((p(3)^3)*p(4)/Kp1) ) / (DEN^2);

Rd(2) = ( (k(2)/p(3))*(p(4)*p(2)) ) / (DEN^2);

Rr(2) = ( (k(2)/p(3))*(p(3)*p(5)/Kp2) ) / (DEN^2);

Rd(3) = ( (k(3)/p(3)^3.5)*(p(1)*p(2)^2) ) / (DEN^2);

Rr(3) = ( (k(3)/p(3)^3.5)*((p(3)^4)*p(5)/Kp3) ) / (DEN^2);

R1 = Rd(1) - Rr(1);
R2 = Rd(2) - Rr(2);
R3 = Rd(3) - Rr(3);

R = [R1; R2 ; R3];

dcat = 1900 / 0.6 ; %kgcat.m3reactor-1 / m3cat.m3reactor-1 -> kgcat/m3 cat

r = nu*R*dcat; % kmol/(kgcat·h ).kgcat/m3 cat - kmol.h-1 / m3cat

Qr = sum((Hr'*R)*dcat); %(kJ/kmol)*(kmol/kgcat·h)*(kgcat/m3reactor) -> kJ/h

m3reactor

% %Adiabatic 300 kW/L = kJ/ (s dm^3) = *3600s/h 1000dm^3/m^3- kJ/h m3reactor

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Qdd = 0;
%Qdd = 300*3600*1000; %kJ/h m3reactor %inlet constant heat
Qdot= (Qdd - Qr); %Too analyze the heat flow

dN = r; %kmol.h-1 / m3cat
dT = (Qdd - Qr)/(N'*Cp);

Yprimo = [dN ; dT ];

end

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