HYDROGASIFICATION OF BIOMASS FOR COGENERATION OF ELECTRICITY AND SYNTHETIC NATURAL GAS

S.P. Cicconardi1, R. Cozzolino1, M. Minutillo2, A. Perna1, G. Spazzafumo1

1 Department of of Civil and Mechanic Engineering, University of Cassino and Southern Lazio
2 Department of Technologies, University of Naples “Parthenope”

spazzafumo@unicas.it
Abstract
The infrastructure for transport and distribution of hydrogen, the fuel of choice for fuel cells, is currently lacking. In a short to medium term, efficient production of hydrogen from reforming of fuels that have existing infrastructure (e.g.
natural gas, gasoline or LPG) would remove a major drawback to use fuel cells for distributed power generation (energy conversion systems with power up to about 1 MW operating close to the final users).
In such a scenario, the use of renewable hydrogen, generated from renewable sources, to produce synthetic fuels can play an important role to overcome the disadvantages of renewable sources (i. e. dissimilarities between energy
availability and energy demand) and to achieve a satisfactory reduction and control of CO2 emissions.
In this paper we analysed the chemical section of an integrated system based on renewable hydrogen production and biomass hydrogasification process. The main product of the process is a substitute of natural gas. In order to define
the optimal operating conditions we carried out a sensitivity analysis by varying the sensible working parameters of the hydrogasification/methanation island such as hydrogen to biomass ratio, pressure, biomass humidity. The HHV of the
dry gas produced is around 88% of the total energy input (biomass+hydrogen).

Intr oduction
Dry syngas composition Dry SNG composition
Carbon dioxide emissions could be reduced either by improving the efficiency of the final use of energy or replacing
fossil fuels with renewable energy sources (RES). A problem of this second opportunity is that the current 100% 100%
technologies to convert RES mainly generate electric energy and the existing grids are not suitable to accept an
irregular power like that obtainable from RES. Moreover the final energy users requires more fuel than electric 80% 80%
energy. 60% 60%
Biomasses are more suitable to generate fuel, but they are not suitable to replace the current fuel need.
Hydrogen is a fuel and could be easily produced from electric energy generated from RES. For such a reason 40% 40%
hydrogen is considered the ideal solution. The bottleneck is hydrogen storage and distribution. So the exploitation of 20% 20%
RES will be limited until these issues will be solved.
A bridge solution to speed-up the utilisation of hydrogen from RES could be its conversion in other fuels, more 0% 0%
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
similar to the current used ones. That is to generate hydrocarbons. It requires carbon, not only hydrogen. And carbon
could be supplied by biomasses or fossil fuels. Using biomasses the resulting fuel would be renewable and carbon- biomass humidity [%] biomass humidity [%]
neutral. CH4 H2 CO2 CO CH4 H2 CO2 CO
The hydrocarbon produced could be liquid (e.g. methanol) or gaseous (e.g: methane). Methane is the main
component of natural gas which is normally distributed and used in most of buildings. Moreover the number of
vehicle using natural gas is gradually increasing. And different blends of methane and hydrogen could be distributed
utilising the existing natural gas pipelines and could be efficiently utilised in internal combustion engines. 3.0 800
Depending on the kind of biomass, a gasification process or a fermentation process can be used to generate a 700
gaseuous fuel. In any case the gas generated will contain mainly hydrogen and carbon oxides which could be 2.5
600
converted to water and methane by means of a methanation process.

temperature [°C]
2.0

heat flow [MW]

500
Concept 1.5 400
In this work we have analysed a particular gasification 300
process: hydrogasification, that is gasification using water 1.0
200
hydrogen as a gasifying mean: 0.5 Syngas Methanator & SNG
100
Methanator Syngas SNG
y exceeding 0
( )
0.0
C x H y O z + 2x− + z H 2 → x CH 4 + z H 2 O energy 0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
2
Electrolysis oxygen biomass humidity [%] biomass humidity [%]

We supposed to have an excess of electrical energy which

could not be supplied to the grid and we supposed to produce Increasing the hydrogen/biomass ratio results in an increasing content of hydrogen in the syngas, but has a positive
hydrogen (and oxygen) by means of electrolysis. Oxygen effect on the SNG composition: even with a unique isothermic methanator, the conversion of carbon into methane
could be sold. Hydrogen is stored into metal hydrides which can be considered complete when the hydrogen/biomass ratio reaches the value of 0.155. For higher values of such a
hydrogen ratio the content of hydrogen grows rapidly as there is no more carbon or oxygen to react with.
are suitable for a stationary storage. When required it is
supplied to the hydrogasifier to react with biomass and the
Dry syngas composition Dry SNG composition
result is a syngas with a comparative high methane content.
The reaction is not complete and some of the carbon 100% 100%
generates carbon oxides depending on the operating Hydro 80% 80%
parameters. biomass
gasification 60% 60%
To complete the conversion of carbon to methane the
hydrogasification process is followed by a methanation 40% 40%
process: 20% 20%
0% 0%
syngas
CO+3 H 2 →CH 4 + H 2 O 0.125 0.135 0.145
0.125 0.135 0.145
0.155 0.155
CO 2 +4 H 2 →CH 4 +2 H 2 O 0.165 0.175 0.165 0.175
hydrogen/biomass ratio hydrogen/biomass ratio
Methanation is an exothermic process but the reaction is heat
favoured by low temperature. In general it is carried out in two CH4 H2 CO2 CO CH4 H2 CO2 CO
or three reactors with the last one isothermic with an
operating temperature of 300-400 °C. In this analysis we The hydrogen/biomass ratio has a small effect on HHV (which varies in the range 88-88.7% of the energy input) and
supposed to have only an isothermic methanator. Depending has not a significant impact on the syngas temperature on the heat flow from syngas cooler and methanator, while
on the operating parameters the gas obtained could consist heat the heat content of SNG increases with hydrogen/biomass ratio.
only of methane and hydrogen and has properties similar to
Methanation
natural gas. For such a reason it could be referred as
3.0 800
substitute of natural gas (SNG).
Hydrogasification is an exothermic process too. The syngas is 2.5 700
released at a temperature of 600-800 °C which is too high for 600
heat flow [MW]

heat 2.0
temperature [°C]

methanation reactions. For such a reason it is necessary to 500

cool the syngas before feeding it to the methanator. 1.5 400
Therefore it is possible to recover heat from the methanator,
from the syngas cooler and from the SNG cooler. Such a heat 1.0 300
could be used into a bottoming cycle to generate electric SNG 200
energy. 0.5 Syngas Methanator & SNG
Methanator Syngas SNG 100
0.0 0
Method and r esults 0.125 0.135 0.145 0.155 0.165 0.175 0.125 0.135 0.145 0.155 0.165 0.175
The analysis was limited to the subsystem formed by the hydrogasifier, the methanator and the heat exchangers. The hydrogen/biomass ratio hydrogen/biomass ratio
integration with the electrolyser and with the bottoming cycle will be next step of this research.
A base case was considered:
● operating pressure, 30 bar Increasing pressure the content of methane into the syngas grows consuming hydrogen due to the fact that
● hydrogen/biomass ratio to the hydrogasifier, 0.16 pressure favours the reduction of the numbers of molecules. When considering the dry SNG composition the
● biomass composition (weight): influence of pressure is significant only at relatively low values: at 12 bar the content of methane is over 99% of its
➢ carbon 48.8% content at 100 bar.
➢ hydrogen 5.5% Dry syngas composition Dry SNG composition
➢ oxygen 37.4%
100% 100%
➢ nitrogen 0.2%
➢ ash 0.1% 80% 80%
➢ humidity 10% 60% 60%
The dry syngas is at 50% methane with a 40% of hydrogen and 10% of carbon oxides. The high hydrogen content is 40% 40%
due to the high temperature (696 °C). In the methanator almost all carbon is converted to methane and the dry SNG is
20% 20%
a blend of methane (87.2%) and hydrogen (12.6%). Its higher heating value (HHV) is 88% of the HHV of the biomass
and hydrogen supplied to the hydrogasifier. 0% 0%
1 4.3 1 4.3
7.6 10.9 7.6 10.9
14.2 17.5 14.2 17.5
Hydrogasifier output (dry syngas) Methanator output (dry SNG) 20.8 24.1 20.8 24.1
27.4 30.7 27.4 30.7

pressure [bar] pressure [bar]

CH4 H2 CO2 CO CH4 H2 CO2 CO

Low pressure is favourable to HHV of dry SNG which is 88.9% of the energy input for atmospheric conditions, while
high pressure is favourable to heat recovery as the temperature of the syngas and the heat flow from syngas cooler
increase.

2.5 800
700
2
600
CH4 H2 CO2 CO CH4 H2 CO2 CO
temperature [°C]
heat flow [MW]

1.5 500
400
A sensitivity analysis was carried out by varying the following parameters:
1 300
• biomass humidity;
• hydrogen/biomass ratio to the hydrogasifier; 200
0.5 Syngas Methanator & SNG
• operating pressure; Methanator Syngas SNG 100
• oxygen content of the biomass (leaving constant the C/H ratio). 0 0
The main effect of humidity is to decrease the amount of the other components of the biomass and the result is that a 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
lower amount of carbon is available to produce methane and carbon oxides. For such a reason the content of carbon pressure [bar] pressure [bar]
oxides in SNG decreases by a factor of 10 when humidity increases from 0% to 10%.
Humidity has a small influence on HHV of the dry gas which varies from 88% to 88.6% of the energy input, while
affects the heat recoverable increasing the heat available into the SNG and decreasing the heat available from syngas A variation of the oxygen content in the range ±5% did not show any significant change.
cooler and methanator. Also the temperature of the syngas decreases. Therefore we can say that humidity has a
negative effect on the heat recovery. Conclusion
We can conclude that the process has a very high chemical efficiency which shows small variations when varying
values of the operating parameters. This means that these values could be selected to optimise the operations of the
electrolyser and of the heat recovery section.