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POLYMER THERMODYNAMICS
5th Semester
Batch 2015-2019
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
3
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]
4
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.
5
Polymer Thermodynamics
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.
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]
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.
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
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