1.

Microstructured methanation unit for thermal integration 'Power-to-Gas'

converter
1.1 Initial position :
Power-to-Gas process chain was first proposed in Japan . In the 1980s - 1990s by
Hashimotoetal. Proposed, reused seawater and built a pilot plant in 2003. Power-to-
Gas (PtG) technology is the process linking the grid to the gas grid by means of
surplus capacity conversion into a grid compatible gas , through two steps: Producing
H2 by electrolysis of water and converting H 2 with an external CO or CO2 source into
CH4 through methanation

Progress The conversion of carbon monoxide and carbon dioxide are both highly
exothermic and have equilibrium limits also with temperature High will limit the
conversion of carbon dioxide. On the other hand, then the certainty is advanced allow
transfer higher conversion rate and prevent soot formation. In addition, the resulting
CH4, known as alternative natural gas (SNG), can be injected into existing gas
distribution grids or gas depots, used as CNG engine fuel, and it has a can easily be
used in all natural gas facilities , To feed synthetic natural gas (SNG) to the gas grid,
the goal of carbon dioxide conversion is high , typically 98–99%. Furthermore, a large
amount of heat must be removed during methanation, typically in the range of 2 MW
per m3 of catalyst volume . Eastern time equally important is the need to recover and
utilize the reaction heat. However, the main limitation of Power-to-Gas is its
relatively low performance and cost high .
 1.2 Integrated 'Power-to-Gas' Conversion Process

Figure 1: Integrated 'Power-to-Gas' Conversion Process Diagram

1.2.1 Production of H 2 by electrolysis of water.
*Basic principles:
Electrolysis of water to produce H2 and O2 is a reaction electrochemistry can be
divided into 2 steps, When the cathode is negatively charged, the reduction reaction
takes place ( 2 ) , while the oxidation reaction takes place at the positive charge
Anode (3)
H 2 O (l) = H 2 (g) + O 2 ( g ) H= 285.58 ( kJ / mol) (1)
H 2O + 2 e -= H 2+ O 2- ( 2 )
O 2 - = 1/2 O 2 + 2 e - (3)
1.2.1. 1 Electrolysis of water
The excess electrolytic energy can be used to produce H 2 through electrolysis of
water. There are 3 different ways to electrolyze in the PtG chain:
+ Alkaline electrolysis (AEL)
+ Polymer electrolytic membrane (PEM)
+ Solid Oxide Electrolysis (SOEC)
1. Alkaline Electrolysis (AEL)
One of the three types of electrolysis technology in the PtG chain, which is alkaline
electrolysis, is The most advanced and production technology (available on the
market for decades). In AEL, an alkaline solution in water (KOH or NaOH) is used as
the electrolyte. AEL operates in the atmosphere, under high pressure. Alkaline
electrolysis machine have lower efficiency and produce a lower purity product than
atmospheric AEL. The top advantage of a pressurized AEL over an atmospheric AEL
is that it generates hydrogen (either for grid injection or further use) with less energy
input .
One of the results of this fact is that the decrease in electrolytic efficiency of
electrolysis when increasing the pressure is lower than the energy required to
compress the hydrogen to produce pro.
According to the manufacturers, AEL electrolyzers can be operated from 20 to 100%
of design capacity, and up to 150% of operating capacity. It is this that makes AEL a
good choice for systems in PtG and is associated with oscillating and intermittent
power supplies. One issue to consider is that it takes 30 - 60 minutes to restart the
system after an outage [27]. The biggest disadvantage of AEL is the use of highly
corrosive electrolytes, thus requiring high maintenance costs. However, in recent
years, AEL have been optimized, especially in terms of efficiency and total
investment.
1.2 Polymer electrolytic membrane ( PEM )
Compared to AEL, PEM is a relatively new technology, with the first commercially
available PEM electrolyzer available for purchase in 1978 . This technology is based
on solid polymeric membranes. The main advantages of PEM include faster cold
starting, greater flexibility and better matching with dynamic and system interruption.
Furthermore, the purity of the H2 produced is very high. However, this technology is
currently more expensive than the AEL system (due to the cost of the membrane and
the use of catalyst metal), and the limited lifespan is also a disadvantage.
1.3 Solid Oxide Electrolysis (SOEC)
Solid oxide electrolysis (also known as high temperature electrolysis) is the most
recently developed electrolysis technology and is still at the laboratory stage. In
SOEC, ZrO2 doped 8 mol% and Y2O3 are used as electrolyte, at high temperature the
high temperature conducts oxygen ions (charge carriers). However, high temperature
can reduce the equilibrium cell voltage and hence the demand for electron-tricity
demand . However, the demand for heat also increases with the increase in increased
temperature. The low power demand is a significant advantage of the SOEC system.
Theoretically, over 100% efficiency (endothermic mode) can be achieved. In
particular, the combination with exothermic reactions in the PtG and PtL Process
Chains leads to higher overall efficiency.. Due to the low power usage, the energy
storage requires low investment. The biggest challenges for the SOEC system are that
the material degrades quickly and the long-term stability is limited, because both are
due to high temperature operation. Furthermore, the SOEC System is not stable
against power fluctuations and discontinuities.
1.2.3 Cacbon converts H2 with an external CO or CO2 source into CH 4 through
methanation
* Fundamentals
Methanation can be performed both in biological media and catalyzed methanation
reactors. To compare the methanation technology, different parameters were selected:
- Achieved air quality of product gas
- Reactor volume required to achieve required gas quality and volume flow
- The complexity of the setup process
The characteristics of the NG produced in the PtG chain should be similar to those of
the natural gas distributed in the gas network. Typically, natural gas contains more
than 80% CH4 . Even more important are the higher order hydrocarbons. Examples are
ethane, propane and butane. On the other hand, inert components such as CO 2 or N2
can also be found in natural gas. Normally, the CO2 methanation on a nickel catalyst
has almost 100% selectivity.
3.2. Catalytic methanation
Catalyzed methanation has been known since 1900. Since the oil crisis of the 1970s,
there has been an increasing demand for methanate for CIS production from syngas.
The process of methanation of CO2 to produce CIS has also been studied for many
decades. Some concepts about reactors for large-scale coal-to-gas plants has been
develop . However, the PtG chain requires new concepts that are optimized for
smaller plant sizes. Catalytic methane reactors are typically operated at temperatures
between 200oC and 550oC and at pressures between 1 and 100 bar. Some metals such
as Ni, Ru, Rh and Co can be used as a catalyst for the methanol reaction. However,
often Ni is considered as the optimal catalyst choice due to its relatively high activity,
good CH selectivity and low cost raw material. However, nickel-based catalysts require
high purity.
The methane reaction is exothermic. Therefore, an important issue in methanation
reactors is to implement temperature control inside the reactor to prevent
thermodynamic and catalyst limitation is essential. To meet this essential goal, several
steady-state reactor concepts have been developed, namely fixed bed, fluidized, three-
phase and structured reactors. For adiabatic fixed-stage reactors, the conventional
approach relies on a series of adiabatic reactors, typically 2 - 5, with refrigeration and
sometimes gas recirculation. Due to the adiabatic mode of operation, the catalyst must
be able to withstand the temperature range (250 - 700 C). Typically, a reactor contains
bundles of cooling tubes; one more possibility is Use cooling pads. Due to cooling,
the setup process is simple, however, the reactor itself is more expensive. In a
fluidized bed reactor, the mixing of solids leads to quasi-isothermal conditions in the
reactor that facilitate control of the behavior of the substances. Providing more
efficient heat rejection is the main advantage of this concept. In addition, the fluidized
bed reactor is limited by the gas velocity inside the reactor: it must not be too low to
Ensure that the curing conditions are minimal and not too high in order to avoid
catalyst elution. Other concepts are based on the use of three-phase reactors for
methanation.
In general, a reactor is filled with a liquid phase, in which the fine catalyst particles
are suspended by gas flow. The presence of a liquid phase with a high heat capacity
reduces it to low, for efficient and precise temperature control: the heat of the reaction
can be completely eliminated and the reactor can operate almost isothermally. ,
resulting in a simple process design.
3.3. Biological Methanation
Biological Methanation (BM) is another alternative to the PtG process chain.
Therefore, methanogenic microorganisms act as biological catalysts. In a biogas
project, it is shown that there are steps, the first step is the hydrolysis from organic
substrates (biomass) to simple monomers (mono saccharides, amino acids and fatty
acids). Then the monomers are converted to acetate, carbon dioxide and hydrogen
(acidogenesis, acetogenesis). Finally, methane is produced by aceticlastic methanol
generation (acetate depletion) and metrophic hydrogen generation (CO2 reduction with

H2 ) . The direct production of methane from CO 2 and H 2 is carried out by

microorganisms (cell type: archea), which obtain energy for growth by anaerobic
metabolism of hydrogen and carbon dioxide. In BM , methane is generated through
hydrogenotrophic methane generation from CO and H2 .
One advantage that can be mentioned is that the process conditions and Reactor
design can be tailored to the requirements of the hydrogenotrophic methanogens. In
situ biomethane process. Part or all of the CO produced by aceticlastic methagonese is
then converted in situ to CH 4 resulting in biogas with higher methane content and
heat. The rate of methane formation of biomethane is limited by the rate of CO2
occurrence during biogas generation.
In summary, compared with a conventional process diagram using a low-
temperature electrolysis system, alkaline or proton exchange membrane (PEM)
technology, the efficiency of the integrated process in Figure 1 for electricity and
carbon dioxide conversion into CIS is expected to increase due to the reduced energy
demand for hydrogen production , from the evaporative state of water. efficiency can
increase from 61% up to 88% . However, process integration also presents major
challenges specific to the methanation unit. In addition, the presence of carbon
monoxide in the feed increases the likelihood of carbon black coke formation through
the Boudouard reaction .