Increasing the temperature in the Gibbs reactor from 800°C to 5000°C:
- Hydrogen production increases significantly, reaching a maximum around 1600°C then decreasing.
- Carbon monoxide production also increases to a maximum at 1600°C then decreases with further temperature rise.
- Carbon dioxide production decreases steadily as temperature increases.
- Methane production increases slightly with temperature over most of the range tested.
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Produce Hydrogen from Coal Gasification with Low Carbon Emissions
1. Production of Hydrogen From Fossil Fuels
along with Analysis of Carbon Footprint
Coal Gasification
2. INTRODUCTION:
Energy demand is increasing day by day at national and international level. In view of limited
liquid fuel in terms of crude oil reserves, researchers are attracted towards finding different
renewable energy sources. As a solution there is to produce hydrogen and use it as a energy
source.
Hydrogen is basically a non-toxic and much lighter compared to air, it dissipates rapidly when it is
released, allowing for relatively rapid dispersal of the fuel in case of a leakage which makes it
relatively safer. However, some properties of hydrogen require additional safety requirements
like wide range flammable concentrations in air (4-75%) and lower ignition energy (lower than
gasoline). In addition to that metal hydride formation and ability to damage materials while
leaking needs attention. Hydrogen contains a higher gross-calorific value of 141.8 MJ/kg at 298k
which is much higher that most of the fuels in market. however, liquid hydrogen has less energy
density by volume than other hydrocarbon fuels.
Although, Hydrogen is a flammable gas with relatively low ignition temperature which creates a
large portion of the risk associated with its usage. Also, it has the ability to escape through
materials due to its small molecule size and its destructive capability (hydrogen embrittlement)
which can lead to mechanical degradation and failure to the point of leakage in certain
materials.
3. PROPERTIES OF HYDROGEN:
SPECIFICATIONS TEMPERATURE(°C) PRESSURE MEASUREMENTS
EQUIVALENCES 20 981 mbar 1 kg=14104 l=12126 m³
MOLECULAR WEIGHT 1.00794
VAPOUR PRESSURE -252.8 101.283 kpa
DENSITY AT BOILING POINT 1 atm 1.311 kg/m³
SPECIFIC GRAVITY 0 1 atm 0.0696
SPECIFIC VOLUME 21.1 1 atm 11.99 m³/kg
SPECIFIC GRAVITY OF THE LIQUID AT BOILING POINT 1 atm 0.701
DENSITY OF THE LIQUID AT BOILING POINT 1 atm 67.76 kg/m³
BOILING POINT 101.283 kPa -252.8°C
FREEZING POINT 101.283 kPa -252.2°C
CRTICAL TEMPERATURE -239.9°C
CRITICAL PRESSURE 1296.212 kPa, abs
CRITICAL DENSITY 30.12 kg/m³
TRIPLE POINT -259.3 °C at 7.042 kPa, abs
LATENT HEAT OF FUSION AT TRIPLE POINT 58.09 kj/kg
LATENT HEAT OF VAPORIZARION AT BOILING POINT 445.6 kj/kg
SOLUBILITY IN WATER(VOL/VOL) 15.6 0.019
DILUTE GAS VISCOSITY 26 0.000009 Pa s
MOLECULAR DIFFUSIVITY IN AIR 0.000061 m²/s
Cp 14.34 kj/(kg) (°C)
Cv 10.12 kj/(kg) (°C)
RATIO OF SPECIFIC HEAT (Cp/Cv) 1.42
NET CALORIFIC VALUE 120 Mj/kg
GROSS CALORIFIC VALUE 141.12Mj/kg
NET CALORIFIC VALUE 1 atm 11 Mj/m³
GROSS CALORIFIC VALUE 1 atm 13 Mj/m³
STOICHIOMETRIC AIR TO FUEL RATIO 27 1 atm 34.2 kg/kg
FLAMMABLE LIMITS IN AIR 4%-75%
EXPLOSIVE LIMITS 13.2 to 58.9 vol% in air
MAXIMUM COMBUSTION RATE IN AIR 2.7/3.46(m s -1)
MAXIMUM FLAME TEMPERATURE 1526.85 °C
AUTOIGNITION TEMPERATURE IN AIR 400 °C/571 °C
5. COAL GASIFICATION:
Coal gasification is the process of reacting coal with oxygen, steam and carbon dioxides to form a
product gas containing hydrogen and carbon monoxide. Gasification essentially an incomplete
combustion of coal. Gasification refers to a group of process which highlight the conversion of
solid or liquid fuels into a combustible gas in presence or absence of gasification agents. It
generally carried out by reacting fuels such as coal, biomass etc. The product is used here is
mainly coal. The heat liberated from the exothermic reactions of fuel and oxygen maintains the
gasifier at the operating temperature and drives the endothermic gasification reactions taking
place inside the gasifier. We can use steam as the gasifier agent only if we can provide an
external source of heat that drags the endothermic reactions forward. The concern for the
climatic variation the fluidised bed gasifier is used here as a popular option, as it has certain
advantages over direct combustion.
Fig- Fluidized Bed Reactor
6. WHY FLUIDIZED BED GASIFICATION?
ADVANTAGES:
1. Air to fuel ratio can be maintained as it helps to control the bed temperature
2. It provides a different variety of feedstock as compared to another gasifier
3. Maintaining uniform radial temperature and avoid slagging problems is much easy in
fluidized bed reactor
4. Higher output of fuel as compared to another gasifier
5. Higher heating value
6. Char production is less compared to another gasifier
DISADVANTAGES:
1. Oxidizing conditions are created when oxygen diffuses from bubble to the emulsion
phase thereby reduction the gasification efficiency.
7. METHODOLOGY:
In gasifier the coal undergoes a series of chemical reaction and physical changes. Like coal drying, pyrolysis, combustion and char
gasification. Coal drying is mainly used to remove moisture from coal. Most of the moisture particle is driven out when the particle
temperature is roughly around 105°C. As drying is a rapid process different temperature can be used based on coal sample and
heating method is used.
Pyrolysis accounts for a greater loss in weight for coal and it occurs rapidly during the initial stages of coal heating. During this
process fragile bonds in aromatic cluster of coal is broken and accounts in formation of much smaller fragments of coal. This lower
molecular weight fragments results in vaporizing and escape from the coal particle to form lighter gas and tar. The remaining higher
molecular weight coal fragments remains in the coal until they reattach to the char.
After pyrolysis comes char gasification where oxygen is consumed rapidly in the combustion zone occupying a small volume of the
reactor. Further conversion of char occurs very slowly and with reversible gasification reaction with CO2, H2O and H2.
𝐶 + 𝐶𝑂2 → 2𝐶𝑂
𝐶 + 𝐻2𝑂 → 𝐶𝑂 + 𝐻2
𝐶 + 2𝐻2 → 𝐶𝐻4
𝐶𝑂 + 𝐻2𝑂 → 𝐶𝑂2 + 𝐻2
As here we can see the production of synthesis gas and also formation of natural gas by partial oxidation or steam reforming can be
further converted into a variety of transportation fuels, for example gasoline, aviation turbine fuel and diesel fuel.
The following model is developed using Aspen plus as the process simulator. The following assumption is taken consideration while
modelling the gasification process:
Process is considered to be in steady state and isothermal.
Coal devolatilization takes place instantaneously and volatile products consists mainly of H2, CO, CO2, CH4, and H2O
Char only contains carbon and ash
8. PRODUCT USED:
The product used here is sub-bituminous coal. The proximate analysis and ultimate analysis is given
below for the coal sample.
PROXIMATE
moisture 13.54
ash 5.86
volatile 42.62
fixed carbon 37.98
ultimate
sulphur 0.99
carbon 54.41
hydrogen 5.19
nitrogen 1.15
oxygen 32.4
11. MODEL EXPLANATION:
COAL DECOMPOSITION:
RYIELD reactor is used here in ASPEN PLUS as yield reactor, and is
used to simulate the decomposition of the feed. Here the coal is converted to constituent
compounds like carbon, hydrogen, oxygen, sulphur, nitrogen, and ash. And it is specified by the
ultimate analysis of the coal sample.
VOLATILE REACTIONS:
RGIBBS reactor in ASPEN PLUS is used as the Gibbs reactor for volatile
combustion. It is based on the assumption that the volatile reactions follow the Gibbs
Equilibrium. The feed here consists mainly of C, H, N, O, S, Cl, ash and moisture. Here the
carbon will be in mixed phase means partly constitute the gas phase which in further process
takes part in the devolatilization, and the remaining part will be considered as char follows by
char gasification. SEPERATION COLUMN model is used before the Gibbs reactor in order to
separate the carbon solid and volatile materials for the coming volatile reactions. The amount of
volatile matter can be specified by the coal approximate analysis.
CHAR GASIFICATION:
RSTOIC is used as the fluidized bed gasifier in ASPEN PLUS. Here char
gasification takes place. Before the reactor a MIXER is used to mix the streams with flow of O2
and STEAM. The char gasification takes place by specifying the gasification reaction. After the
reaction takes place the outlet stream is separated using a SEPERATOR column in ASPEN PLUS
model separator. Here the gas components and the solid components are separated.
13. EFFECT OF O2 FLOWRATE ON THE PRODUCT
GAS:
In the mixer O2 and steam is injected and mixed with the streams coming from the
separator and Gibbs reactor.
0
200
400
600
800
1000
1200
1400
1600
0 5 10 15 20 25
PRODUCTION
O2 INLET(kg/hr)
H2
CO2
CO
Here we can see from the trend line that the H2 composition in the feed decreases with a
very small deviation while the composition of CO2 increases by a good margin but the CO
concentration is increasing slightly with increase in oxygen rate. From here we can say
that the complete and partial oxidation of coal is taking place in the stoichiometric
converter.
14. EFFECT OF PRESSURE AND TEMPERATURE IN
THE GIBBS REACTOR:
While doing the simulation we have assumed that the reactions are taking place in Gibbs reactor are
following Gibbs equilibrium. Based on that changing the pressure while remaining the temp constant we
can see significant change in the output stream.
0
200
400
600
800
1000
1200
1400
1600
0 5 10 15 20 25 30 35 40 45
production(kg/hr)
pressure(atm)
h2 ch4 co2 CO
Here by observing the
trend lines we can
predict that at a constant
temperature and variable
pressure hydrogen
production is significantly
decreasing, as well as the
production of CO is also
decreasing. Meanwhile
the Methane production
is increasing.
Fig – Production w.r.t pressure and temperature
15. 0
50
100
150
200
250
300
0 200 400 600 800 1000 1200 1400 1600 1800
H2
production
Temp
H2 1atm h2 10 atm h2 20atm h2 30atm h2 40atm
The chart shows us the production of
hydrogen at different temperature
and pressure. From here we can see
that the production of hydrogen is
maximum while the temperature is
around 1600°C and the pressure is
1atm. From the trend lines we can
say that at a certain pressure
increasing the temperature will
results in increased production of
hydrogen.
0
200
400
600
800
1000
1200
1400
1600
0 200 400 600 800 1000 1200 1400 1600 1800
Production(kg/hr)
Temperature(C)
CO 1atm
CO 10atm
CO 20atm
CO 30atm
CO 40atm
Coming to this plot, we can see the
same trend as hydrogen that the
production of CO is maximum at
1600°C and 1 atm pressure. The trend
line shows us the exact same result
that with increase in temperature
while keeping the pressure constant
the production of CO will increase
significantly. To produce less amount
of CO we can keep the temperature
low while keeping the pressure high.
But as our main criteria is to produce
major amount of syngas so keeping
the pressure low while the
temperature high will be more
efficient.
Fig – hydrogen production at different temperature and pressure
Fig – CO production w.r.t pressure and temperature
16. 0
100
200
300
400
500
600
0 200 400 600 800 1000 1200 1400 1600 1800
Production(kg/hr)
Temperature(C)
CO2 1atm
CO2 10atm
CO2 20atm
CO2 30atm
CO2 40atm
For the above plot we can see that with increase in temperature at a constant
pressure the production of carbon dioxide will decrease at a significant rate. While at
high temp and low pressure will generate less CO2 so it will help us to reduce the
carbon footprint.
18. VARYING TEMPERATURE:
Here we have done the sensitivity analysis on the RGIBBS reactor column based on temperature and pressure variation. We
have checked the output change in molar-flowrate as well as the net change in the molar flowrate of the compounds we
are getting.
S-1 -Results Summary
VARY 1B3 PARAM TEMP C
H2OIN-H2
O
CO
IN-C
O
CO
2IN-CO
2
CH4IN-C
H
4
800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000
-18
-17
-16
-15
-14
-13
-12
-11
-10
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
-52.5
-50.0
-47.5
-45.0
-42.5
-40.0
-37.5
-35.0
-32.5
-30.0
-27.5
-25.0
-22.5
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
-21
-20
-19
-18
-17
-16
-15
-14
-13
-12
-11
-10
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
CH4IN-CH 4
CO2IN-CO2
COIN-CO
H2OIN-H2 O
S-1 -Results Summary
VARY 1B3 PARAM TEMP C
N2IN-N
2
O2IN-O
2
H2IN
-H2
CIN-C
800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
25.6515
25.6515
25.6515
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
25.6516
0
5
10
15
20
25
30
35
40
45
50
55
60
48.0
48.5
49.0
49.5
50.0
50.5
51.0
51.5
52.0
52.5
53.0
53.5
CIN-C
H2IN-H2
O2IN-O2
N2IN-N2
Fig – net change in production while varying the temperature
So as here we can see from the two graphs above that varying the temperature from 900˚C to 5000 ˚C we can see significant results in the net
change in molar flowrate for different component. While we can see that the net change in methane, carbon dioxide and water production is
increasing significantly and getting to a stabilized position after attaining a column temperature of 2400˚C, but the net change in carbon
monoxide is decreasing. Coming to the second graph we can see that oxygen generation is suddenly increasing at a higher temperature (after
3800˚C), where as hydrogen generation is increasing and getting to a equilibrium out put molar flowrate at around 2400˚C. coming to the
consumption of carbon at a lower temperature it is increasing significantly till the temperature reaches around 1200˚C and after hat the
production of carbon is happening, and after attaining a temperature of 2200˚C it’s getting to a steady sate formation rate.
19. From here we can say that the consumption of methane, carbon dioxide and water is increasing rapidly with increasing
in temperature and the generation of carbon monoxide is increasing with it. from the following graphs we can
understand much better about the product feed formation while increasing the temperature.
S-1 - Results Summary
VARY 1B5 PARAM TEMP C
KMOL/HR
800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000
0
20
40
60
80
100
120
140
CH4 KMOL/HR
CO KMOL/HR
CO2 KMOL/HR
H2O KMOL/HR
S-1 - Results Summary
VARY 1B5 PARAM TEMP C
KMOL/HR
800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000
0
20
40
60
80
100
120
140
C KMOL/HR
H2 KMOL/HR
O2 KMOL/HR
N2 KMOL/HR
Fig – output stream while varying the temperature
20. VARYING PRESSURE:
In this case we made the pressure variable from 1 bar to 50 bar with an increment of 1.
S-1 - Results Summary
VARY 1B3 PARAM PRES BAR
H2OIN-H2
O
CO
IN-C
O
CO
2IN-CO
2
CH4IN-C
H
4
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50
-0.60
-0.55
-0.50
-0.45
-0.40
-0.35
-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
-51.30
-51.25
-51.20
-51.15
-51.10
-51.05
-51.00
-50.95
-50.90
-50.85
-50.80
-50.75
-50.70
-50.65
-50.60
-50.55
-0.065
-0.060
-0.055
-0.050
-0.045
-0.040
-0.035
-0.030
-0.025
-0.020
-0.015
-0.010
-0.005
0.000
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
CH4IN-CH 4
CO2IN-CO2
COIN-CO
H2OIN-H2 O
S-1 - Results Summary
VARY 1B3 PARAM PRES BAR
N2IN-N
2
O2IN-O
2
H2IN
-H2
CIN-C
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
23.0
23.5
24.0
24.5
25.0
25.5
26.0
26.5
27.0
27.5
28.0
28.5
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
2.75
3.00
3.25
3.50
51.30
51.35
51.40
51.45
51.50
51.55
51.60
51.65
51.70
51.75
51.80
51.85
51.90
51.95
52.00
52.05
52.10
CIN-C
H2IN-H2
O2IN-O2
N2IN-N2
Fig- net change in production while changing the pressure
So, as we can see from the two graphs plotted above using ASPEN PLUS sensitivity analysis varying the pressure, the
change is quite linear with respect to change in pressure. Net change is decreasing for methane, carbon dioxide and
water linearly, while the change is increasing linearly for hydrogen, carbon and carbon monoxide. For oxygen and
nitrogen, the graph is showing linear values.
From here we can say that the formation of methane, carbon dioxide and water is increasing, while for hydrogen, carbon
monoxide and carbon formation is decreasing. For nitrogen and oxygen, we can say that it is getting fully used for the
reactions to form other compounds mentioned as per the graph.
22. STEAM METHANE REFORMING:
“Steam Methane Reforming” (S.M.R.) is the most widely used process in the production of
hydrogen.
S.M.R. is a process in which methane of natural gas heated with steam in presence of catalyst to
produce a mixture of carbon monoxide and hydrogen with relatively small amount of carbon
dioxide.
The reaction takes place under a pressure of 8-35 bar.
It is an endothermic process which means heat is provided during the reaction.
“Water Gas Shift reaction” is done in which the produced carbon monoxide and steam are reacted in
presence of catalyst to produce more hydrogen and carbon dioxide.
Last step is “absorption” in which carbon dioxide and other impurities are removed and pure
hydrogen is obtained.
Advantages of S.M.R.:
- It is a cost-effective process of hydrogen production.
- It is energy efficient.
- High levels of purity of hydrogen can be achieved by using pressure swing absorption purification technology.
- It produces green hydrogen which is good for environment as greenhouse gas emission is negligible.
24. METHODOLOGY:
A simple hydrogen plant which works on S.M.R. is explained below. The natural gas is first mixed with steam in the mixture
and is entered in the conversion reactor where steam methane reforming reaction takes place. The heat required is
provided for the reaction as it is an endothermic reaction. The vapour output I then cooled in a cooler and then is passed
to an equilibrium reactor where water shift reaction takes place. The vapour output is found to contain less amount of
hydrogen so to maximise the hydrogen production and to make the hydrogen pure we need to remove the carbon dioxide
and carbon monoxide. So, the vapour outlet is again cooled and passed in an equilibrium reactor to perform shift reaction
and the same process is done another time. Final step is absorption where the impurities are removed and pure hydrogen
is obtained. Here we have used water as an absorbent. Carbon dioxide comes out with the water as bottom product and
the distillate mostly contains pure hydrogen with negligible amount of carbon monoxide and water vapour. We have found
that we can get about 99% pure hydrogen by this process. The HYSYS simulation is attached below.
26. VARYING NATURAL GAS MASS FLOW AND
STEAM MOLAR FLOW:
Here in the above case studies, we have taken natural gas mass flow and steam molar flow rate as an independent variable
to get an idea about how purity of hydrogen produced depends on them. We have varied steam molar flowrate int the
range o 500kg-mol/hr to 6000 kg-mol/hr at a step size of 100 and we have varied the natural gas mass flowrate from 1000
kg/hr to 20000 kg/hr at step size of 500. So, from here we can understand that there is a relation between natural gas
mass-flowrate and steam molar-flowrate in the purity of hydrogen produced. so natural gas needs a specific amount of
steam molar flowrate to generate much more pure hydrogen around 99.9% if we provide less steam flowrate the purity of
hydrogen will be less for a specific amount of natural gas mass flow rate, but if we provide excess water then the purity
will not change further.
27. PURITY OF HYDROGEN:
From the case study mentioned above we have tried to relate the purity of hydrogen with the ratio of
mass flow of natural gas and steam molar flowrate.
82
84
86
88
90
92
94
96
98
100
1 2 3 4 5
Purity
of
Hydrogen
Decreasing Ratio
Purity of Hydrogen vs Ratio of mass flow of Natural
Gas and steam molar-flowrate
From the graph we can conclude that the purity of hydrogen increases with decrease in the ratio of mass flow of
natural gas and steam molar flowrate. This is because methane requires a significant amount of water for conversion
and we also require a significant amount of water for the shift reaction so as to maximise the amount of hydrogen
produced. For this reason, we need to maintain the ratio of feed gas and steam to get much more pure hydrogen.
28. VARYING NATURAL GAS MASS FLOWRATE
AND NATURAL GAS TEMPERATURE:
Here, we have taken natural gas mass flow and natural gas temperature to be independent variable to get an idea about
how purity of hydrogen produced depends on them and we have kept the steam molar flow rate constant. We have
varied the temperature from 30˚C to 300˚C at a step size of 5 and the mass flow rate from 1000kg/hr to 20000kg/hr at a
step size of 1000. From the graph we can conclude that the temperature has no effect on the purity of hydrogen
produced but we can see that the purity of hydrogen decreases drastically after a certain natural gas mass flow rate. this
happens because we have kept the steam flow rate constant so as the natural gas flow rate exceeds a specific value the
purity of hydrogen decreases drastically.
29. FURTHER IMPROVEMENT
For COAL GASIFICATION, there is much carbon footprint which can be reduced by channelling the
product feed obtained from the process to SMR, as it helps to produce much pure hydrogen with
negligible carbon footprint. We are attaching the simulation result below –
0
100
200
300
400
500
600
700
800
methane CO2 CO H2O H2 N2
coal-gasification product feed SMR Product
Fig – comparison of composition after passing coal gasification product feed through SMR
So, as we can see from the above-mentioned result that there is significant improvement in
reducing the carbon footprint as well as production of hydrogen.
30. CONCLUSION:
For coal gasification, there is another way to reduce carbon footprints in hydrogen by doing plasma
gasification of coal. Plasma is generally referred to as the “fourth state matter” which is a highly
ionised gas having high temperature capable of conducting electricity. It is formed by passing an
electric arc through a stream of air or oxygen. It dissociates the gas into ions which has a
successively high temperature at around 6000˚C. But its main drawback is the excess demand of
energy which makes it too much costly. If we could somehow fulfil the huge demand of energy with
the help of renewable energy such as solar energy, windmill energy, hydro-energy etc. then plasma
gasification can be done.
In the gasification process, we can maximise the hydrogen production if we can decrease the
residence time of the gasifier. Here we have used fluidised bed gasifier which is operated at 600-
900˚C but takes tens of minutes to gasify coals and biomass and if we use entrained bed gasifier the
time taken to gasify will be 2-3 sec but it requires high temperature in the range of 1400-1700˚C.
But all these problems can be solved if we can use transport gasifier which operates at around 800-
1000˚C and takes around 10 to 30 sec to gasify.