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THERMODYNAMIC ANALYSIS OF PROCESS FLOW SHEET

FOR H2 PRODUCTION FROM BIOMASS VIA STEAM


GASIFICATION

POLYMER THERMODYNAMICS

DEPARTMENT OF POLYMER AND PROCESS ENGINEERING

5th Semester

Batch 2015-2019

Submitted to: Submitted by: Group#4


Dr. Rabia Nazar Hafiza Fizza Zahid 2015-PE- 04
Hafsa Afzal 2015-PE-10
Hafiz Tanveer Ashraf 2015-PE-20
Muhammad Afaq 2015-PE-38
Saba Ejaz 2015-PE-50

University of Engineering and Technology Lahore


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Polymer Thermodynamics

Table of Contents:
1. Abstract 3
2. Introduction 3
3. Technical Approach 3
3.1 Process Development 3
3.2 Assumptions 4
3.3 Model Formulation for Calculations 5
3.3.1 Energy balance around the gasifier 5
3.3.2 Thermodynamic efficiency of the process 6
3.3.3 Energy balance around the scrubber 6
4. Calculations 7
4.1 Matlab script for steam and superheated steam generator 7
4.2 Matlab script for Enthalpy Calculations around the gasifier 8
4.3 Matlab script for energy balance around the gasifier 9
4.4 Matlab script for Enthalpy Calculations around the scrubber 9
4.5 Matlab script for energy balance around the scrubber 10
4.6 Matlab script for thermodynamic efficiency calculations 10
5. Results and Discussion 11
5.1 Mass Balance 11
5.2 Energy Balance 12
5.2.1 Results of steam and superheated steam generator 12
5.2.2 Results of energy balance around the gasifier 12
5.2.3 Results of energy balance around the scrubber 13
5.2.4 Thermodynamic efficiency of the process 14
6. References 15
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Polymer Thermodynamics

1. Abstract:
The purpose of this report is to do thermodynamic analysis of process flow sheet for
hydrogen production from biomass via steam gasification with in-situ CO2 capture by calcium
oxide as sorbent. This analysis helps us to determine the thermodynamic efficiency of process.
This analysis incorporates mass balance and energy balance calculations. This report first gives
short introduction to the process and then methodology for the calculations is described
technically. And the final section of the report consists of results and discussion section.

2. Introduction:
Steam gasification is the method of converting carbonaceous materials into CO, CO2 and
H2 at high temperature without combustion using controlled amount of steam. Steam gasification
with in-situ CO2 capture by calcium oxide as sorbent is one of the most effective method to produce
H2 from biomass. Among all the processes steam gasification of biomass gives the highest yield
of H2. Moreover, using pure steam make the process economically feasible. There are many factors
on which the yield of H2 depends, which are given below. [1]
• Sorbent/biomass ratio
• Steam/biomass ratio
• Biomass type
• Biomass feed particle size
• Temperature

3. Technical Approach:
3.1 Process Development:
The process flow sheet for analysis is shown in Figure 1. Biomass is pretreated before
entering in the gasifier, i.e. the moisture is removed through drying and biomass is subsequently
grinded. At atmospheric pressure and temperature biomass and sorbent are fed to the gasifier. The
whole process is consisting of 3 sections that are
• Steam Generation
• Gasification
• Gas cleaning section
The steam that produced in steam generator is superheated to the 523K and fed to the gasifier. The
steam gasification reaction takes place in gasifier and the process is integrated with CO2 adsorption
step. Six major reactions take place in the gasifier that are listed in Table 1. Since steam
gasification is endothermic process so external energy Qr is supplied. Then the product gas is
filtered for the removal of ash and other solid particles. Next the gas is passed through the scrubber
for cooling. At last a pressure swing adsorption(PSA) unit is used to purify the H2 and we obtained
99.99% pure hydrogen. [1]
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Polymer Thermodynamics

Figure 1. Process flow sheet for H2 production from biomass via steam gasification [1]

3.2 Assumptions:
Process parameters and operating conditions are assumed for energy and mass balance of
flowsheet. These are [2]
1. Biomass is assumed as char (C) only.
2. Biomass feed rate is 72g/hr.
3. Steam to biomass ratio is 3.
4. Steam to sorbent ratio is 1.
5. The reactions take place at constant volume & adiabatically.
6. The gasifier operates under steady state conditions.
7. Pressure is atmospheric throughout the process.
8. No tar formation during process.
9. Temperature should be between 800 to 1300 K.
10. There is no work done.
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Polymer Thermodynamics

3.3 Model Formulation for Calculations:


3.3.1Energy balance around the gasifier:
In gasifier following reactions are assumed to take place. [2]
No. Name of Reaction Reaction Equation ∆Hf (kj/mol)
1 Char Gasification C+H2O CO+H2 +131.5
2 Methanation C+2H2 CH4 -74
3 Boudouard C+CO2 2CO +172
4 Methane Reforming CH4+H2O CO+3H2 +206
5 Water Gas Shift CO+H2O CO2+H2 -41
6 Carbonation CO2+CaO CaCO3 -178.3
Table 1. Reactions that take place in gasifier
All the calculations are based on the first law of thermodynamic.
Energy balance equation is
Q+W=∆H+∆EK.E+∆EP.E (1)
With the assumptions given in section 3.2 the mass and energy balances around the gasifier are
represented by the following equations (2) and (5) respectively [3].
mChar+mCaO+mH2O = mH2+mCO2+mH2O+mCO+mCH4+mCaCO3 (2)
Since there is no work done, K.E and P.E are zero, so energy balance equation becomes
Q = ∆H (3)
Qs= Hout -Hin (4)
HChar+HCaO+HH2O+Qr = HH2+HCO2+HH2O+HCO+HCH4+HCaCO3 (5)
Here m and H represent mass and enthalpy of components. Qr represents the external energy
required for the process because steam gasification of biomass is an endothermic reaction. And it
is obtained by performing energy balance as given in equation (5).
The enthalpy of each component is obtained from equations (6) and (7).
H=m*(Hf +∆H) (6)
𝑇2
∆H=∫𝑇1 𝐶𝑝𝑑𝑇 (7)

Where m is the mass of component and Hf is standard enthalpy of formation of respective


component. ∆H of each component is calculated using the heat capacity equations (8) and (9). [4]
Cp=A+B*T+C*T2+D*T3+E/T2 (Shomate Equation) (8)
By integrating this equation between two temperature limits we get the following expression
∆H=A*(T2-T1)+(B/2)*(T22-T12)+(C/3)*(T23-T13)+(D/4)*(T24-T14)-E/(T2-T1) (9)
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Where T=temperature(K)/1000
And ∆H=kj/mol
To convert the value of ∆H and Hf into kj/g we must divide it with molar mass(g/mol) of each
component. Molar mass of each component is given in Table 3.
The coefficient A, B, C, D and E for each component are obtained from the website NIST
Chemistry WebBook [4], given in Table 2.

3.3.2 Thermodynamic efficiency of the process:


The thermodynamic efficiency of the process is calculated using equation (10). [5]
𝐿𝑜𝑤𝑒𝑟 ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑔𝑎𝑠
η = 𝐿𝑜𝑤𝑒𝑟 ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑏𝑖𝑜𝑚𝑎𝑠𝑠+(𝑄𝑟+𝑄𝑠𝑠𝑡+𝑄𝑠𝑡) (10)

Here Qsst and Qst is the energy required for the generation of super-heated steam and steam
respectively. And it is calculated by using eq. (11) w.r.t temperature change. [1]
Qst or sst = mH2O* ∆HH2O (11)
For Qst we must add enthalpy of vaporization in above relation due to the phase change of water
i.e. 40.7kj/mol.
The lower heating values (LHV) of biomass and product gas are obtained from equations (12) and
(13) respectively. [1]
LHV of biomass= mChar*LHVChar (12)
LHV of product gas= (mH2*LHVH2)+(mCO*LHVCO)+(mCH4*LHVCH4) (13)
LHV of product gas and char are given in Table 3. [6]

3.3.3 Energy balance around the scrubber:


Then Energy balance calculations are performed around the scrubber using equations (1) and (14).
If there is no work done, no heat loss and no change in K.E and P.E. Then energy balance equation
becomes
∆H=0 (14)
HH2+HCO2+HH2O+HCO+HCH4 = HH2+HCO2+HH2O+HCO+HCH4 (15)
The enthalpy of each component is obtained from equation (16).
H=m*∆H (16)
And ∆H is obtained from equations (7), (8) and (9).
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Tables for different data are given below.


Components A B C D E
H2 33.066178 -11.363417 11.432816 -2.772874 0.158558
CO 25.56759 6.09613 4.054656 -2.671301 0.131221
CO2 24.99735 55.18696 -33.69137 7.948387 -0.136638
H2O 30.092 6.832514 6.793435 -2.534480 0.082139
CH4 -0703029 108.4773 -42.52157 5.862788 0.678565
Table 2. A, B, C, D, and E values for each component [4]

Components Hf(kj/mol) LHV(kj/g) Molar mass(g/mol)


H2 0 120.971 2.01588
CO -110.5271 10.112 28.0101
CO2 -393.5224 44.0095
H2O -241.826 _____ 18.0153
CH4 -74.8731 50.009 16.0425
CaO -635.09 56.0774
Char 9.1253 18 12
CaCO3 -1206.9 100.087
Table 3. Hf, LHV and Molar Mass of each component [4], [6], [7], [8]

4. Calculations:
We take the basis of 1 hour for all the calculations. All calculations are done in Matlab. Matlab
scripts for calculations are given below.

4.1 Matlab script for steam and superheated steam generator:

%Calculations for steam and superheated steam generation.


clear
clc
Cp=4.184; %Cp of water in J/g_K
T1=298; %in K
T2=373; %in K
m=216; %in g
Qst=m*Cp*(T2-T1); %in J
Qst=Qst/1000; %in KJ
Qv=40.7; %heat of vaporization of water in KJ/mol
M=18; %molar mass of water in g
Qv=Qv/M; %Qv in KJ/g
Qv=Qv*m; %Qv for 216g of water
Qst=Qst+Qv;%energy required for steam generation.
disp('Energy required for steam generation is')
fprintf('\n Qst= %5.4f KJ\n',Qst)
CP=2.02; %Cp of steam in J/g_K
T3=523; %in K
Qsst=m*CP*(T3-T2); %in J
Qsst=Qsst/1000; %in KJ
disp('Energy required for superheated steam generation is')
fprintf('\n Qsst= %5.4f KJ',Qsst)
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4.2 Matlab script for Enthalpy Calculations around the gasifier:

%Enthalpy calculations for each component in and out of the gasifier.


clear
clc
disp('Enthalpy calculations for output components ')
A=input('Enter the value of A');
B=input('Enter the value of B');
C=input('Enter the value of C');
D=input('Enter the value of D');
E=input('Enter the value of E');
T2=input('Enter the value of T2');
T1=input('Enter the value of T1');
T2=T2/1000; %formula requirement
T1=T1/1000; %formula requirement
deltaH=A*(T2-T1)+(B/2)*(T2^2-T1^2)+(C/3)*(T2^3-T1^3)+(D/4)*(T2^4-T1^4)-E/(T2-
T1); %in KJ/mol
Hf=input('Enter the value of Standard heat of formation of component in
KJ/mol');
M=input('Enter the molar mass of component in g/mol' );
H=deltaH+Hf; %in KJ/mol
H=H/M; %in KJ/g
m=input('Enter the mass flow rate of component in g/hr');

disp('Enthalpy of the component in KJ is')


H=m*H %in KJ

%Enthalpy of CaCO3 is calculated as


m=96.7978; %mass flow rate of CaCO3 in g/hr
cp=0.00076; %cp of CaCO3 in KJ/g_K
Hf=-1206.9; %Standard heat of formation in KJ/mol
M=100.08; %molar mass in g/mol
T2=1150; %in K
T1=298; %in K
deltaH=cp*(T2-T1); % in KJ/g
Hf=Hf/M; %in KJ/g
H=Hf+deltaH;%in KJ/g

disp('Enthalpy of CaCO3 in KJ is')


H=m*H %in KJ

%These calculations are for outlet streams of the gasifier input


%calculations are given below.
%Since we use the heat of formation only for enthalpy
%calculations of reactants so we calculate the enthalpy of reactants as

disp('Enthalpy calculations for input components')


M=input('Enter the molar mass of component in g/mol' );
Hf=input('Enter the value of Standard heat of formation of component in
KJ/mol');
m=input('Enter the mass flow rate of component in g/hr');

disp('Enthalpy of the component in KJ is')


H=m*(Hf/M) %in KJ
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4.3 Matlab script for energy balance around the gasifier:


%Energy Balance around the gasifier
%%All values are in KJ
clear
clc
%Enthalpies of input stream
HChar=54.7518;
HCaO=-815.4173;
HH2O=-2899.4;
%Enthalpies of output stream
HH2=86.7678;
HCO2=-196.0803;
HH2O1=-2123.2;
HCO=-117.9135;
HCH4=-0.9756;
HCaCO3=-1104.6;
Hin=HChar+HCaO+HH2O; %Total enthalpy of input stream
Hout=HH2+HCO2+HH2O1+HCO+HCH4+HCaCO3;%Total enthalpy of output stream
Qr=Hout-Hin;
%Qr is the energy supplied to the gasifier because it is an endothermic
%reaction, So sign for this heat is +ve.
disp('Energy required for steam gasification reaction is')
fprintf('\n Qr= %5.4f KJ',Qr)

4.4 Matlab script for Enthalpy Calculations around the scrubber:

%Enthalpy calculations for each component in and out of the scrubber.


clear
clc
disp('Enthalpy calculations for output components ')
A=input('Enter the value of A');
B=input('Enter the value of B');
C=input('Enter the value of C');
D=input('Enter the value of D');
E=input('Enter the value of E');
T2=input('Enter the value of T2');
T1=input('Enter the value of T1');
T2=T2/1000; %formula requirement
T1=T1/1000; %formula requirement
deltaH=A*(T2-T1)+(B/2)*(T2^2-T1^2)+(C/3)*(T2^3-T1^3)+(D/4)*(T2^4-T1^4)-E/(T2-
T1); %in KJ/mol
Hf=input('Enter the value of Standard heat of formation of component in
KJ/mol');
M=input('Enter the molar mass of component in g/mol' );
H=Hf/M; %in KJ/g
m=input('Enter the mass flow rate of component in g/hr');

disp('Enthalpy of the component in KJ is')


H=m*H %in KJ
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Polymer Thermodynamics

4.5 Matlab script for energy balance around the scrubber:


%Energy balance around the scrubber
%All values are in KJ
%Enthalpies of input stream
HH2Oi=324.2373; %at 1150K
HH2i=86.7678;
HCO2i=23.5383;
HH2O1i=10; %at 298K
HCOi=36.7213;
HCH4i=1.6347;
%Enthalpies of output stream
%Since there are two output streams at different temperatures so out put
%enthalpies are obtained by adding them.
HH2O=56.6047; %from 1150K
HH2=84.6335+0.0049;
HCO2=15.2319+1.7125;
HH2O1=287.1102; %from 298K
HCO=35.7056+0.0363;
HCH4=1.6061+0.001;
%Total enthalpy of input stream
Hin=HH2i+HCO2i+HH2O1i+HH2Oi+HCOi+HCH4i;
%Total enthalpy of output stream
Hout=HH2+HCO2+HH2O1+HH2O+HCO+HCH4;
fprintf('\n Hin=% 5.4f KJ \n Hout=%5.4f KJ\n',Hin,Hout)

4.6 Matlab script for thermodynamic efficiency calculations:


%Thermodynamic efficiency calculation of the process
clear
clc
%mass flow rate of components in g/ hr
mH2=6.8659;
mCO=38.9329;
mCH4=0.5566;
mChar=72;
%LHV of components in KJ/g
LHVH2=120.971;
LHVCO=10.112;
LHVCH4=50.009;
LHVChar=18;
%Q for steam, superheated steam and for gasification process in KJ
Qst=556.1808;
Qsst=65.4480;
Qr=204.0639;
%Thermodynamic efficiency calculation
n=((mH2*LHVH2)+(mCO*LHVCO)+(mCH4*LHVCH4))/((mChar*LHVChar)+(Qst+Qsst+Qr));
n=n*100;
fprintf('\n Thermodynamic efficiency=%5.4f percent',n)
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5. Results and Discussion:


5.1 Mass Balance:
Mass balance results of the process are shown in the Figure 2. These results are obtained from an
article [2].

H2=6.8688g
CO=39.1880g H2=6.8688g
CO2=24.561g CO=39.1880g H2O=200g
CO2=24.561g H2=6.8659g
CH4=0.5593g F8
CH4=0.5593g CO=38.9329g
CaO =72g H2O=182.3251g
H2O=182.3251g CO2=16.1919g
F3 Ash=9.7000g
Char=72g CH4=0.5566g
Sorbent
F1 F5=263.2022g F7=253.5022g (99.99%)
F10=62.5473g H2=6.8659
Biomass
F12

Steam
F2
H2O=216g

F4
CaCO3=96.7978 F6 F9=390.9549g F11=37.979g
g Ash=9.7000g H2O=382.3251g CO=38.9329g
H2=0.0029g CO2=16.1919g
CO=0.2551g CH4=0.5566g
CO2=8.3691g
CH4 =0.0027g

Figure 2. Mass balance results of process


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5.2 Energy Balance:


Energy balance results are obtained by running the above mfiles in Matlab. These are given below.

5.2.1 Results of steam and superheated steam generator:


These calculations are done in Matlab script given in section 4.1. The results obtained are

Figure 3. Results of steam and superheated steam generator

5.2.2 Results of energy balance around the gasifier:


Results of energy balance around the gasifier are given below.
Enthalpies of input and output components are obtained by putting the values of respective
components in Matlab script 4.2. The results obtained are given below.
Enthalpies of input components:
HChar=54.7518 kj
HCaO= -815.4173 kj
HH2O= -2899.4 kj
Enthalpies of output components:
HH2= 86.7678 kj
HCO2= -196.0803 kj
HH2O= -2123.2 kj
HCO= -117.9135 kj
HCH4= -0.9756 kj
HCaCO3= -1104.6 kj
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Polymer Thermodynamics

Energy balance around the gasifier:


Energy balance around the gasifier is performed in Matlab script given in section 4.3 that yields

Figure 4. Energy balance results around the gasifier


Since steam gasification of biomass is an endothermic process and consumes a lot of energy. So,
Qr is the energy required for gasification process. And it is supplied to the gasifier by an external
source. Qr value is +ve in this case.
5.2.3 Results of energy balance around the scrubber:
Enthalpies of input and output components are obtained by putting the values of respective
components in Matlab script 4.4. And the results obtained are given below.
Enthalpies of input components:
HH2= 86.7678 kj
HCO2= 23.5383 kj
HH2O at 1150K = 324.2373 kj
HH2O at 298K = 10 kj
HCO= 36.7213 kj
HCH4= 1.6347 kj
Enthalpies of output components:
Since there are two streams out from the scrubber at different temperatures so, enthalpies at each
temperature are given below.
Enthalpies of output components at 1004K
HH2= 0.0049 kj
HCO2= 1.7125 kj
HH2O from 298K = 287.1102kj
HH2O from 1150K = 56.6047kj
HCO= 0.0363 kj
HCH4= 0.0010 kj
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Polymer Thermodynamics

Enthalpies of output components at 318K


HH2= 84.6335 kj
HCO2= 15.2319 kj
HCO= 35.7056 kj
HCH4= 1.6061 kj
Energy balance around the scrubber:
Energy balance calculations around the scrubber are performed in Matlab script given in section
4.5. The results obtained are given in the figure 5.

Figure 5. Energy balance results around the scrubber


From the above results it is proved that there is no energy loss during the cooling of the product
gas. It is an ideal case in actual cases it’s not happened.

5.2.4 Thermodynamic efficiency of the process:


Thermodynamic efficiency calculations are provided in matlab script section 4.6 and the results
obtained are given in the figure 6.

Figure 6. Thermodynamic efficiency of the process


Almost 60% efficiency shows that the process is economically and thermodynamically feasible.
And its yield the high amount of pure H2.
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Polymer Thermodynamics

6. References:
[1] Abrar Inayat, Murni M Ahmad, M I Abdul Mutalib, Suzana Yusup. Flowsheet Development
and Modelling of Hydrogen Production from Empty Fruit Bunch via Steam Gasification. Chemical
engineering transactions Volume 21, 2010
[2] Abrar Inayat, Murni M Ahmad, M I Abdul Mutalib, Suzana Yusup, 2010. Flowsheet Modelling
of Biomass Steam Gasification System with CO2 Capture for Hydrogen Production.
[3] Mahishi, M. R. and Goswami, D. Y. 2007. Thermodynamic optimization of biomass gasifier
for hydrogen production. International Journal of Hydrogen Energy, 32,3831-3840.
[4] NIST Chemistry WebBook
[5] Mahishi, A. R., Sadrameli, M. S., Vijayaraghavan, S. and Goswami, D. Y. 2008. A novel
approach to enhance the hydrogen yield of biomass gasification using CO2 sorbent. Journal of
Engineering for Gas Turbines and Power, 130, 011501.
[6] https://en.wikipedia.org/wiki/Heat_of_combustion
[7] https://en.wikipedia.org/wiki/Standard_enthalpy_of_formation
[8] https://www.engineeringtoolbox.com/specific-heat-solids-d_154.html