A sustainable distributed energy system using methanol

for energy storage

SHASHANK NAGARAJA
GRADUATE STUDENT
CLEAN FOSSIL AND ALTERNATIVE FUELS ENERGY
KIC INNOENERGY

DIVYA HARIRAMANI
GRADUATE STUDENT
RENEWABLE ENERGY
KIC INNOENERGY

A sustainable distributed energy system using methanol for energy storage

Contents
1 Introduction

2 Hydrogen Economy and its limitation

3 Methane and Methanol

3.1 Production of Renewable
3.2 Storage and Transport .
3.2.1 Methane Storage
3.2.2 Methanol Storage
3.3 Process Chain . . . . . .

Methane and Renewable

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Methanol
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4 Methanol Economy
5 Methanol Production
5.1 Production of hydrogen from renewable resources . . . . .
5.1.1 Electrochemical . . . . . . . . . . . . . . . . . . . .
5.1.2 Photochemical . . . . . . . . . . . . . . . . . . . . .
5.1.3 Thermochemical . . . . . . . . . . . . . . . . . . .
5.1.4 Biological . . . . . . . . . . . . . . . . . . . . . . .
5.2 CO2 Separation . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Production of Renewable Methanol . . . . . . . . . . . . .
5.3.1 The Lurgi Process . . . . . . . . . . . . . . . . . .
5.3.2 CAMERE process . . . . . . . . . . . . . . . . . . .
5.3.3 MITSUI process . . . . . . . . . . . . . . . . . . . .
5.3.4 Methanol production using Nickel Gallium catalyst
5.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . .

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6 Utilization of Methanol
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6.1 Micro-Turbines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
6.2 Internal Combustion Engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
7 Conclusion and Scope for future work

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A sustainable distributed energy system using methanol for energy storage

List of Figures
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Classification of EES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Schematic diagram of the proposed concept . . . . . . . . . . . . . . . . . . . .
Energy density of different fuels on volumetric basis . . . . . . . . . . . . . . . .
Storage capacities and discharge time of different technologies . . . . . . . . . .
Methanex Ocean Tanker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Process chain for power storage systems of methane and methanol . . . . . . . .
Methanol derivatives and their uses . . . . . . . . . . . . . . . . . . . . . . . . .
Methanol Economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
AEL apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
PEMEL apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
HTEL apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Photochemical Splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Setup for methanol synthesis based on CO2 and H2 . . . . . . . . . . . . . . . . .
CAMERE process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Percentage of WTT Energy spent in each process of methanol production . . . .
Life cycle CO2 emissions for production of 1 kg of MeOH using different production paths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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A sustainable distributed energy system using methanol for energy storage

Introduction

Solar, wind and other renewables are booming as never before. On the face of it, theres
nothing to stop them becoming the dominant source of our electricity sometime during the
course of this century. However, solar energy is inherently only available during daylight hours.
Wind-generated power is a variable resource, and the amount of electricity produced at any
given point in time by a given plant will depend on wind speeds, air density, and turbine
characteristics. These challenges posed by the intermittent nature of renewable sources can be
tackled by having efficient energy storage medium. To date, no technology has proven cheap
or practical enough to provide this on the (massive) scale required. Electrical energy storage
(EES) solutions can also alleviate the problem of peak demand. EES systems are classified
into mechanical, electrochemical, chemical, electrical and thermal energy storage systems. The
broad classification is shown in Figure 1 [1].

Figure 1: Classification of EES

The present report emphasizes on energy storage using chemicals. The focus is on use of
methanol as an energy storage medium. This approach appears to provide solution not only
to the energy storage quandary but also to the gargantuan problem of carbon dioxide (CO2 )
emissions.
Carbon dioxide, a significant greenhouse gas, is considered a harmful pollutant of our atmosphere and a major source for human-caused global warming. So far, however, besides the
proposed collection and sequestration of excess CO2 , a costly and only temporary solution,
which in seismically active areas could cause devastating releases of CO2 in case of earthquakes
4

A sustainable distributed energy system using methanol for energy storage

or other earth movements, no new technology emerged for its disposal. Deep ocean storage is no
longer considered feasible because it greatly increases the problem of ocean acidification. In the
recent years, extensive work has been carried out at Loker Hydrocarbon Research Institute on
chemical recycling of CO2 to methanol (MeOH) [2]. This practical, feasible approach, not only
offers a solution to the environmental problem of carbon dioxide increase in our atmosphere and
associated global warming, but also renders our fuels renewable and environmentally carbon
neutral.
Carbon Recycling International Inc. (CRI) incorporated in 2006, began operation of first
commercial scale plant, the George Olah Plant in 2011 based on this technology [3]. CRIs
Emission to Liquid (ETL) technology enables cost-effective conversion of renewable energy to
liquid fuel on small scale. ETL consists of a system of electrolytic cracking and catalytic synthesis, leading to a low pressure and low temperature electrochemical production process.
Added to this, scientists from Stanford University, SLAC National Accelerator Laboratory
and the Technical University of Denmark combined theory and experimentation to identify
a new nickel-gallium catalyst that converts hydrogen and carbon dioxide into methanol with
fewer side-products than the conventional catalyst [4].
All these discoveries have created a conducive atmosphere for production of methanol.
It is a well known fact that MeOH is a good fuel for an IC engine (ICE) with very high
octane number. Engines provide a relatively efficient way for energy conversion. The low quality exhaust heat of an engine can be used for central heating or can be converted to electricity
using organic rankine cycle (ORC) depending on the demand. ICEs can be considered as a
point source for capturing CO2 and utilizing it to produce methanol, creating a carbon neutral
cycle.
Integrating these concepts, we can have a solution for our problems. It would be possible
to electrolyze water to produce hydrogen using excess renewable electricity. This hydrogen can
be used to produce methanol using the ETL approach. MeOH fuels the engine whenever there
is demand, creating a sustainable, carbon neutral distributed energy system for small scale
applications. The above concept is described schematically in Figure 2.

A sustainable distributed energy system using methanol for energy storage

Figure 2: Schematic diagram of the proposed concept

In the next section, hydrogen and its limitation as energy storage medium is illustrated.

A sustainable distributed energy system using methanol for energy storage

Hydrogen Economy and its limitation

A typical hydrogen storage system consists of an electrolyzer, a hydrogen storage tank and a
fuel cell. An electrolyzer is an electrochemical converter which splits water with the help of
electricity into hydrogen and oxygen. It is an endothermal process, i.e. heat is required during
the reaction. To generate electricity, both gases flow into the fuel cell where an electrochemical
reaction of hydrogen and oxygen react to produce water, releasing heat and generating electricity. For economic and practical reasons, oxygen is not stored but vented to the atmosphere
on electrolysis, and oxygen from the air is taken for the power generation. In addition to fuel
cells, combustion engines , gas turbines and combined cycles of gas and steam turbines are in
discussion for power generation.
Producing hydrogen is only the first step in the envisioned Hydrogen Economy. The next
challenge is the storage of the generated hydrogen in a form that should be economical, practical, safe and user friendly. Because hydrogen is a very light gas, it contains much less energy
per unit volume than conventional liquid fuels under the same pressure. Under normal conditions, hydrogen requires about 3000 times more space than gasoline for an equivalent amount
of energy. Thus, hydrogen must be compressed, liquefied or absorbed on a solid material to be
of any practical use for energy storage.
Current hydrogen storage technologies involve either physical or chemical storage. Physical
storage is effected in insulated or high-pressure containers in which hydrogen is stored as a
liquefied or compressed gas. Chemical storage involves metals and other materials that absorb
or contain hydrogen and can subsequently readily release it for use.
Liquid hydrogen is a compact form of hydrogen, making it in principle an attractive candidate for hydrogen storage, especially in transportation. In fact, it is in this form that hydrogen
is used as a propellant for space vehicles. However, hydrogen (boiling point of -253 o C) is one
of the the most difficult gases to liquefy. Complex and expensive multi-stage cooling systems
are necessary to obtain liquid hydrogen.
To store sufficient amounts of energy in a given space, hydrogen compression is currently the
preferred solution. However, even under extreme conditions of pressure , hydrogen still has a
much lower energy content per volume than gasoline. This fact is clearly illustrated in Figure
3.

A sustainable distributed energy system using methanol for energy storage

Figure 3: Energy density of different fuels on volumetric basis

Another problem associated with hydrogen storage is its safety. Hydrogen is the most
leak-prone gas, owing to its small size and lightness. Hydrogen itself is non-toxic, but it is
explosive and flammable. Moreover, being colorless, odorless and tasteless, it is difficult to
detect leaks. In the case of natural gas, which is also odorless, colorless and tasteless, volatile
sulfur compounds are added to make leaks readily detectable, but the addition of such odorants
is impractical in the case of hydrogen.
Added to this, there is no large scale existing infrastructure for transport of hydrogen. To
overcome the problems associated with hydrogen storage and distribution, many approaches
are being pursued to use liquids that are rich in hydrogen, like methanol, as a hydrogen source.
Methanol has a higher energy content per volume than even liquid hydrogen. Excess methanol
produced can be distributed through the existing infrastructure like gasoline with minor modifications. Hence, this study provides an insight into production of hydrogen using renewable
resources and its storage in the form of methanol.
In the succeeding section, we look into the comparison between methane and methanol.

A sustainable distributed energy system using methanol for energy storage

Methane and Methanol

Due to the increasing investment on renewable power and phasing out of nuclear power in
Europe, it is inevitable to find the solutions to the dilemma of energy storage. After briefly
understanding the drawbacks associated with hydrogen storage, it is beneficial to have an
insight into other tangible solutions. The two most discussed approaches are production of
methane and methanol from hydrogen. In Germany alone, a storage capacity of 20 TWh would
be required in 2040 [5]. Figure 4 shows the potential of energy storage of different technologies
[6].

Figure 4: Storage capacities and discharge time of different technologies

It is clear from the above figure that Synthetic Natural Gas (SNG), which is mainly composed of methane and methanol are the two feasible alternatives in the TWh range. In this
section, a comparison between these alternatives is illustrated.

A sustainable distributed energy system using methanol for energy storage

3.1

Production of Renewable Methane and Renewable Methanol

The reaction of H2 and CO2 to methane was discovered at the beginning of the 20th century
by Sabatier and Senderens (the Sabatier process). A pilot plant for the production of synthetic
natural gas (SNG: 90 % CH4 , 5 % H2 , 5 % CO2 ) with H2 from electrolysis and CO2 from the air
was put into operation in late 2012 in Stuttgart, Germany, with a power-to-methane-to-power
(pmp) efficiency of 16 % [7]. The first semi-commercial was erected in 2013 in Werlte, Germany
by Audi AG with a pmp efficiency of up to 21 %. The Audi e-gas (SNG) plant produces roughly
1,000 metric tons of e-gas per year [8].
Methanol is a liquid under ambient conditions, which can easily be stored, transported, and
dispensed, similar to gasoline and diesel fuel. It can also be converted into fuel substitutes
such as dimethyl ether (DME), a diesel substitute with a cetane number of 55. Alternatively,
methanol can be converted into gasoline via the methanol-to-gasoline process or into diesel via
the methanol-to diesel process, for instance. For these reasons, the term Methanol Economy
was suggested by Prof. George Olah [9], with the aim of characterising a future economy in
which methanol replaces fossil fuels as a means of energy storage, ground transportation fuel,
and chemical base material. The process for methanol production is similar to methane production. Both the reactions are shown in (1) and (2).

CO2 + 3H2 CH3 OH + H2 O

(1)

CO2 + 4H2 CH4 + 2H2 O

(2)

In Iceland, the first commercial methanol production plant was built in 2011 with a production
rate of 1.7 million liters of methanol per year [10]. Canadian Blue Fuel Energy plans to produce
renewable methanol via green electricity from water power and CO2 separated from NG. The
resulting carbon footprint is substantially lower than that of ethanol from corn [11].

3.2

Storage and Transport

The ability to store and transport the energy carriers methane and methanol, respectively, is
the core topic in the overall process. The differences in physical state and volumetric energy
density necessitate different requirements. For the distribution of methane and methanol, a
well-developed NG and gasoline infrastructure is at hand. The first one consists mainly of
pipelines distributing gas to the consumer. Methanol is mostly transported via trucks and tank
wagons. Methanex, one of the proponents of Methanol Economy is supported by a fleet of 19
methanol ocean tankers for inter-continental transport of methanol. One of their ocean tankers
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A sustainable distributed energy system using methanol for energy storage

is shown in Figure 5 [12].

Figure 5: Methanex Ocean Tanker

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A sustainable distributed energy system using methanol for energy storage

3.2.1

Methane Storage

Methane cannot be stored as a fluid under atmospheric pressure at room temperature. Instead,
it is stored under a pressure of 100-200 bar in salt caverns, for instance. Once injected, only
50-75 % of the gas can be withdrawn again and not more than 75 % of gas is recoverable. In
addition, one has to invest power for gas compression, which consumes approximately 4 % of
the HHV of methane. Furthermore, energy has to be invested for cooling, while in the course
of methane withdrawal the gas requires heating. In sum, these latter two processes consume
another 15 % of the HHV, thus resulting in an overall efficiency of = 77 % for storage, withdrawal, and transport over a distance of 500 km [13]. Added to this, there are pressure losses
in the pipeline.

3.2.2

Methanol Storage

Methanol storage is simple. Because of the higher volumetric energy density compared to
methane, less volume has to be stored and transported for the same amount of energy. Transportation via trucks and tank wagons requires 0.2?-0.4 % per 100 km of the stored energy
content. It has to be noted in this context that methanol, like methane, can easily be transported via pipeline grids, thus rendering it a useful medium to store and transport energy over
long distances [13].

3.3

Process Chain

Dr. Ludolf Plass, another proponent of renewable methanol developed a process chain to
compare power storage systems of methane and methanol [14]. The process chain is shown
in Figure 6. It is evident from this figure that the losses in transportation affect the process
chain of methane significantly. Even though methanol has better overall efficiency, methane
benefits from the well developed natural gas infrastructure. However, in the current scenario,
the scope of the project is long term storage of energy in local applications and hence, the
possibility of surplus fuel is not significant. The benefit of easily storing methanol outweighs
the advantage of existent infrastructure of gas. Added to this, the surplus methanol can be
blended with gasoline or can be sold to chemical industry. This versatility was the main reason
why methanol was given prominence over methane for the present study.

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A sustainable distributed energy system using methanol for energy storage

Figure 6: Process chain for power storage systems of methane and methanol
In the next section, the idea of methanol economy will be discussed in brief.

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A sustainable distributed energy system using methanol for energy storage

Methanol Economy

Oil and natural gas are not only our major energy sources and fuels but also the raw materials
for a great variety of derived hydrocarbon materials and products. When looking for alternatives to supplant fossil fuels, we should also consider this aspect. Indeed, the great majority of
established petrochemical products are achievable using both crude oil and methanol as a raw
material base.
A series of chemical synthesis can be operated on the basis of methanol instead of classic
petrochemicals. The different C1 products derived from methanol and their uses are shown in
Figure 7 [15].

Figure 7: Methanol derivatives and their uses

Methanol is an excellent fuel for IC Engines with an octane number of 100. Only minor
modifications are needed in the engine. Methanol can also be efficiently used to generate electricity in fuel cells. This was initially achieved by first catalytically reforming methanol into
H2 and CO. H2 , after separation from CO, is then fed into a hydrogen fuel cell. However,
methanol can also react directly with air in the direct methanol fuel cell (DMFC), without
the need for reforming. Dimethyl Ether (DME), readily produced from methanol, is itself an
excellent substitute for diesel fuel as well as household gas for cooking and heating. Natural
gas can be transformed into methanol for its ready and safe transportation. Hence, methanol
has potential of superseding Liquified Natural Gas (LNG).
The ready conversion of methanol into synthetic hydrocarbons and their products will ensure
that future generations will have unlimited and inexhaustible access to the essential synthetic
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A sustainable distributed energy system using methanol for energy storage

products and materials that today form an integral part of our life. At the same time, utilization of CO2 for production of methanol will mitigate the problem of global warming. Methanol
Economy suggested by Prof. Olah is shown in Figure 8 [2].

Figure 8: Methanol Economy

The current section provided an overview on methanol economy. The idea of methanol
economy becomes relevant to the scheme of the present project because when there are large
number of distributed energy systems with polygeneration of electricity and methanol, there is
a possibility of excess methanol available and creating a methanol based economy will not only
help in utilization of excess methanol but also reduce the dependence on non-renewable fossil
fuels.
The first few sections provided an understanding about the energy storage medium in consideration and its relative advantages. The next section will concentrate on its production
using renewable hydrogen and CO2 .

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A sustainable distributed energy system using methanol for energy storage

Methanol Production

Methanol can be generated from a wide range of carbon and hydrogen sources. Currently,
large-scale production is dominated by the conversion of fossil resources, mainly natural gas
and coal, to carbon monoxide and hydrogen (synthesis gas) as the intermediate for catalytic
methanol synthesis. With the aim of reducing the dependence on fossil fuels, methanol economy is suggested. Renewable methanol is produced via three pathways: Wastes, biomass and
CO2 [16]. The first two pathways rely on gasification and catalytic conversion technology to
produce renewable methanol, while the third pathway produces methanol from CO2 , water,
and renewable electricity. In the present study, the third pathway is considered.
Methanol synthesis by CO2 hydrogenation is one of the most promising steps toward a future based on sustainability and responsible use of fossil materials. Shortages of fossil fuels
and decreasing crude oil qualities will be great challenges in the coming decades. Methanol
production from CO2 and H2 provides a possible solution for both problems at the same time.
The production of methanol from CO2 will be divided into two subsections. The first subsection
will discuss the production of hydrogen from renewable resources and the second subsection
will provide an overview of different processes used for production of renewable methanol.

5.1

Production of hydrogen from renewable resources

Hydrogen is, besides carbon dioxide, the basic resource for methanol production in the carbon
capture and utilisation (CCU) process and therefore needs to be produced at a competitive
cost. Today, hydrogen is mainly obtained by dehydrogenating fossil resources or producing
synthesis gas from the latter. The simplest available resource for hydrogen is water, which can
be split into hydrogen and oxygen as shown in (3):

2H2 O 2H2 + O2

R H = 572kJ/mol

(3)

The energy required to split water can come from any energy source, focusing on the usage
of renewable energy, various technologies of water splitting can be applied, which are summarized in Table 1 below.

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A sustainable distributed energy system using methanol for energy storage

Table 1: Technologies available for water splitting and type of renewable energy used

There are three main routes to produce hydrogen from renewable energies:
Electrolysis - splitting water into hydrogen and oxygen using electricity from one of the
many renewable sources.
Solar conversion - by either thermolysis, using solar-generated heat for high temperature chemical cycle hydrogen production or photolysis, in which solar photons are used
in biological or electrochemical systems to produce hydrogen directly.
Biomass conversion - via either thermochemical or biochemical conversion to intermediate products that can then be separated or reformed to hydrogen; or fermentation
techniques that produce hydrogen directly.
In the next part, we will describe a number of established as well as state of the art processes
of water-splitting technologies achieved with renewable energies.

5.1.1

Electrochemical

Electrolysis
Water splitting by electrolysis is the most common technology for hydrogen generation from
water and is the only one operating on an industrial scale. In 2009, 4 % of the worldwide
production of hydrogen was realised by water electrolysis [14] . By means of electric power,
water is split into the elements hydrogen and oxygen, which are deposited at the cathode and
anode, respectively. The reactions are shown in (4) and (5).
Cathode:
2H2 O + 2e H2 + 2OH

(4)
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A sustainable distributed energy system using methanol for energy storage

Anode:
2H2 O O2 + 4H + + 4e

(5)

Currently, there are three types of electrolysers for hydrogen production, namely Alkaline,
PEM (Polymer Electrolyte Membrane) and SOEs (Solid Oxide Electrolysers). Alkaline is the
most mature technique, suitable for large scale, but it needs a constant input of electricity,
which poses a potential problem when the facility is directly coupled to an intermittent renewable electricity supply. PEM electrolysers are in their demonstration stages and are capable of
processing a fluctuating input, thereby making them the best option for small scale commercial
hydrogen production. SOEs are still in the R & D stage and they are based on high temperature
electrolysis [17].
Electrolyser units only require raw water at ambient temperature and electricity as an input. Additional research with the aim of decreasing electric power uptake for water splitting
has been undertaken in combination with photo-electrochemically active electrodes. Under the
influence of sunlight, they build up an electrochemical potential to another electrode, which can
be standard equipment. Another possibility is the conversion of waste kinetic or thermal energy
into power by piezo electrochemical and pyro electrochemical active substances to produce an
additional amount of hydrogen by electrolysis [13].
A brief overview of types of electrolysis is provided below.
Alkaline Electrolysis
Alkaline Electrolysis (AEL) is the oldest known electrolysis technology and is usually conducted in an aqueous solution of 30 % KOH at 80-90 o C. During the process, hydroxide
ions migrate through the diaphragm from cathode to anode. The reactions are shown in
(6) and (7).
Cathode:
2H2 O + 2e H2 + 2OH

(6)

4OH O2 + 2H2 O + 4e

(7)

Anode:

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A sustainable distributed energy system using methanol for energy storage

The electrodes are usually nickel based due to its resistance to corrosion in this environment. Thus, neither expensive special alloys nor noble metals have to be used. The
electrolysis cell itself has low investment costs and a long lifetime. The setup is shown in
Figure 9. 1, 2 and 3 represents the electrode, diaphragm and gas-fluid separator respectively.

Figure 9: AEL apparatus

Disadvantages arise from the liquid electrolyte, which is very corrosive and the concentration of the electrolyte has to be controlled and adjusted constantly, hence requiring a
more complex plant setup. The major drawback for its use with fluctuating renewable
energy, such as wind power, is the poor partial load properties and the lag time for startup and shutdown of the electrolysis plant.
Recent developments in the field of advanced AEL include an increase of the active electrode surfaces by using porous electrodes, better catalyst systems that support the redox
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A sustainable distributed energy system using methanol for energy storage

reactions at the electrodes and higher process temperatures to decrease the decomposition
voltage. In order to decrease the investment costs, less complex plants are being designed
and anion exchange membranes are being used instead of liquid electrolyte solutions.

Proton-Exchange Membrane Electrolysis

On the other side of the spectrum we also have acidic electrolysis. This requires a proton
exchange membrane, allowing for protons to migrate from anode to cathode. The reactions of PE is shown in (8) and (9) respectively.
Cathode:
4H + + 4e 2H2

(8)

2H2 O O2 + 4H + + 4e

(9)

Anode:

The advantages of Proton-Exchange Membrane Electrolysis (PEMEL) compared to AEL

include the compact setup, higher power efficiency and density, which result in higher
production rates for hydrogen per cell. Moreover, the partial load properties are better,
so the plant is suitable for fluctuating power from renewable resources. However, the applied membranes are expensive and therefore imply higher investment costs and limited
long-term stability. The PEMEL setup is shown in Figure 10.

Figure 10: PEMEL apparatus

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A sustainable distributed energy system using methanol for energy storage

This process proves to be the most relevant technology to integrate excess renewable energy in small communities for methanol production, hence an in-depth analysis will be
provided in the following section.

High-temperature Electrolysis using Solid Oxide Electrolysis Cells

Under high temperatures, decomposition voltage of water and overvoltage at the electrodes decrease while ion conductivity increases, which has made High Temperature
Electrolysis (HTEL) the focus of current research. The cathode and anode reactions
are given by (10) and (11).
Cathode:
2H2 O + 4e 2H2 + 2O2

(10)

2O2 O2 + 4e

(11)

Anode:

To generate heat and electricity for Solid Oxide Electrolysis Cells (SOECs) from renewable resources, concentrated sunlight could be used. Sunlight is concentrated by reflectors
and is guided through a ray separator, which reflects heat radiation and allows visible
light to pass. The heat radiation is concentrated in a steam generator for a SOEC, while
the electricity is provided from photovoltaic (PV) cells, which can be located behind the
separator and convert the visible light. With this technology, conversion rates up to 40
% for solar-to-hydrogen appear within reach in the near-term future. The apparatus for
HTEL is shown in Figure 11.

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A sustainable distributed energy system using methanol for energy storage

Figure 11: HTEL apparatus

5.1.2

Photochemical

As an alternative to the electrochemical methods seen, it is possible to split water with sunlight only. In solar photonic processes, the solar photons are absorbed directly into an absorber,
without complete conversion to heat. The absorber may convert part of the photon energy to
electricity (as in a photovoltaic cell) or store part as chemical energy in an endergonic chemical
reaction. The advantage is a direct use of sunlight without the electrolysis process. However,
supporting reagents are required to supply the electrons generated by photons for H+ reduction
as well as to absorb electrons from O2 oxidation.
Nevertheless, hydrogen and oxygen are not produced separately and conversion rates range
below 1 %. The process of photochemical splitting is shown in Figure 12.

Figure 12: Photochemical Splitting

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A sustainable distributed energy system using methanol for energy storage

5.1.3

Thermochemical

Thermal water splitting into its elements could be realised with geothermal heat ( < 600 o C)
and solar thermal heat ( < 3000 o C) with different technologies.
Direct thermal water splitting is not practicable due to the required temperatures of > 2,500 o C
and simultaneous generation of hydrogen and oxygen. Therefore, more than 300 thermochemical and hybrid electrochemical-thermochemical processes via supporting reagents have been
developed up to now. In the centre of interest are:
1) the hybrid Cu-Cl cycle process for geothermal plants [18],
2) the S-I cycle process
3) The hybrid sulphur cycle (HyS) process for solar thermal plants.
The HyS process generates hydrogen via electrolysis of an aqueous solution of sulphur dioxide (SO2 ). The produced sulphuric acid is decomposed at 800-1,000 o C to give sulphur dioxide,
thus closing the loop [19].
Currently, there is no process that is working on an industrial scale, but promising technologies
are being developed. The main advantage of solar thermal water splitting technologies is their
superior use of solar energy with a conversion rate of up to 45 % in comparison to 16 % for
electrolysis combined with PVs ( = 20 % for PV and 80 % for electrolysis) [19].

5.1.4

Biological

There are three major concepts for producing hydrogen with biological/biochemical methods:
1. Biological WGS reaction with purple bacteria
2. Fermentation with bacteria like Enterobacter aerogenses
3. Photosynthesis with cyanobacteria or green algae.
A disadvantage of bacteria-based technologies is the substrate required for consumption, which
competes with the direct biomass gasification to methanol. Additionally, it is possible to use
bacteria that produce methanol directly. Much work is still needed to optimise the processes
within the organisms, and numerous engineering challenges need to be met to develop hydrogen
generation biological systems.
Biological processes are out of scope for the present review in small communities renewable
energy.

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A sustainable distributed energy system using methanol for energy storage

After getting an overview on production of hydrogen, we look into production of methanol.

Since the focus is on creation of carbon neutral process, the production of methanol involves
separation and capture of CO2 . A brief summary about CO2 separation is provided.

5.2

CO2 Separation

CO2 can be separated using different techniques based on composition, temperature and pressure of CO2 containing streams. Commonly used operations are absorption, adsorption and
membrane.
The absorption process uses amine solutions like triethanolamine (TEA), diethanolamine (DEA),
diisopropanolamine (DIPA), monoethanolamine (MEA) and methyldiethanolamine (MDEA).
The main concerns regarding this method are stability of amines and energy efficiency of the
process [20].
The adsorption process is similar to absorption but using porous solid adsorbents such as
zeolites and activated carbon. There is possibility of reaction between adsorbent and CO2 .
Membrane technology have been developed using both polymers and inorganic materials.
Porous membranes with supporting amine solutions can be very effective.
MEA absorption process is widely studied. MEA reacts with CO2 in the gas stream to form
MEA carbamate. The CO2 -rich MEA solution is then sent to a stripper where it is reheated
to release almost pure CO2 . The MEA solution is then recycled. This process is uneconomical.

5.3

Production of Renewable Methanol

Methanol synthesis by CO2 hydrogenation is one of the most promising steps toward a future
based on sustainability and responsible use of fossil materials. Different processes available now
will be discussed in this section.

5.3.1

The Lurgi Process

This process was carried out by Lurgi during 1990s. The key to process was a copper-zinc
oxide catalyst. Commercially available Cu/ZnO/Al2 O3 catalyst showed excellent activity at 60
bar pressure and 260-270 o C. The catalyst showed almost complete conversion of CO2 with a
per-pass conversions in the range of 35-45 %. Apart from water, which is an inevitable byproduct, concentration of other byproducts from parallel reaction was negligible. according to data
provided by Lurgi, overall selectivity for methanol was 99.96 % and the content of byproducts
except water was 390 ppm [13].The setup for methanol synthesis is shown in Figure 13. From
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A sustainable distributed energy system using methanol for energy storage

this process, a water containing product mixture with 63.9 wt % methanol becomes available.

Figure 13: Setup for methanol synthesis based on CO2 and H2 .

5.3.2

CAMERE process

CAMERE stands for carbon dioxide hydrogenation to form methanol via reverse water- gasshift-reaction (RWGS). The research is funded by Korean Government. In the CAMERE
process, CO2 is converted to CO and H2 O through the RWGS reaction. The product obtained
consists of CO, CO2 , H2 and H2 O. The products are dehydrated and fed to methanol reactor.
Fe2 O3 /Cr2 O3 catalyst is used for the process. CAMERE process diagram is shown in Figure
14 [21].

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A sustainable distributed energy system using methanol for energy storage

Figure 14: CAMERE process

5.3.3

MITSUI process

This process was developed by Mitsui chemicals. An oxidised copper, zinc, aluminium, zirconium and silicon catalyst is used. According to their patent, the process comprises of
step (a) of reacting hydrogen and carbon dioxide With each other in a reactor in the presence
of a copper-containing catalyst to produce a reaction mixture containing methanol;
a step (b) of circulating part or all of the reaction mixture to the step (a);
a step (cl) of combusting part of the reaction mixture to produce a combustion product and
energy, and a step (c2) of circulating part or all of the combustion product to the step (a), the
step (cl) and the step (c2) being performed when the reaction mixture contains a compound
(p) containing carbon and hydrogen except methanol at not less than 0.1 mol % (wherein all
components of the reaction mixture excluding methanol and water represent 100 mol %);
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A sustainable distributed energy system using methanol for energy storage

a step (d) of separating a component including methanol from the reaction mixture.
The compound (p) is preferably inert to the copper containing catalyst.
It is preferable that at least part of the compounds (p) be a hydrocarbon, and more preferably
methane. It is particularly preferable that the compound (p) be methane. Preferably, the
reaction mixture contains the compound (p) at 0.1 to 50 mol %. [22]
5.3.4

Methanol production using Nickel Gallium catalyst

The discovery of a Ni-Ga catalyst by a team researchers from SLAC National Laboratory,
Stanford University and Denmark University shows the reducion of CO2 to methanol at ambient
pressure [4]. The catalyst was identified through a descriptor-based analysis of the process
and the use of computational methods to identify Ni-Ga intermetallic compounds as stable
candidates with good activity. A number of catalysts were synthesized and found that Ni5 Ga3 is
particularly active and selective. Comparison with conventional copper based catalysts revealed
the same or better methanol synthesis activity, as well as considerably lower production of CO
due to reduced the RWGS activity in favour of methanol production. There are many hurdles
to cross but this may prove to be the first step in development of small-scale low-pressure
devices for CO2 reduction to methanol for energy storage.

5.4

Summary

The processes to produce methanol from carbon dioxide are existent. Discovery of new catalysts
are aiding the process of decentralized methanol generation for energy storage. However, the
two severe impediments for commercialisation of this technology are :
1. Economical production of hydrogen from renewable resources in a large scale.
2. Feasibility of clean CO2 from waste streams.
The next section discusses about utilization of methanol to produce power.

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A sustainable distributed energy system using methanol for energy storage

Utilization of Methanol

A basic overview on two technologies, namely Micro-turbines and Internal Combustion Engines
will be provided in this section. Another important technology of fuel cells is out of scope for
the present study as the focus is on sustainable distributed poly-generation systems.

6.1

Micro-Turbines

Micro-turbines are versatile technical solutions for the production of electrical and thermal
power. This term is applied to a new group of small gas turbines being used to provide on-site
power and becoming an attractive option to feed the load of small users.
Most microturbines with a power range from 20 kW to 250 kW are based on technologies
that were originally developed for the use in auxiliary power systems, aircrafts or automotive
turbochargers.
The following are the advantages of micro-turbines [23]:
1. Simple, compact systems - directly connected to high-speed turbo generators
2. Low emissions with multi-fuel capability
3. Low investment costs
4. Reduced maintenance costs
Methanol having a carbon to hydrogen ratio of 0.25 compared to 0.47 of diesel can be a potential fuel to such a system. Although in general, all commercially available microturbine systems
have the potential to be operated with liquid fuels, currently only few microturbines exist which
is specified by the producer for the use of liquid fuels. Several research and demonstration units
investigate the technical and emission properties of liquid fuel systems. Two Turbec T100 units
are operated on methanol (produced from natural gas) by the Norwegian oil and gas company
Statoil ASA. This demonstration project is implemented in the framework of the EC co-funded
project Optimised Microturbine Energy Systems - OMES, and its main aim is to introduce
methanol (as innovative energy carrier) to the fuel market for distributed electricity and heat
production [24]. According to the tests, methanol fired microturbines showed comparable results with gas turbines. Hence, it can be concluded that methanol fired microturbines are
competitive in the present day scenario.
In the next subsection, more widely utilized technology of internal combustion engines will
be discussed.
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A sustainable distributed energy system using methanol for energy storage

6.2

Internal Combustion Engines

Internal combustion (IC) engines are the true workhorses of the modern society. They are
simple, efficient and reliable. IC engines are compact in size, making them very versatile. The
starting times of IC engines are lower compared to other alternatives and hence, used extensively in power back-up systems.
Methanol usage in IC engines is well established. The anti-knock properties of alcohols like
methanol allows for most of the increase in power and efficiency compared to gasoline engines.
This also permits for application of optimal values for spark advance, high compression ratios
and opens opportunities for aggressive downsizing without the need for fuel enrichment at high
loads. On the other hand, it makes methanol unsuitable for use in conventional diesel engines
due to higher auto-ignition temperature. Alcohols can be used in conjunction with another fuel
or additive which is more auto-ignitable in diesel engines. In the present study, only gasoline
engines are considered.
Alcohols have higher laminar flame speed and this reduces unburnt hydrocarbon emissions.
The oxygenated nature of alcohols help in reduction of CO emissions. However, low vapour
pressures of alcohols raise concerns about cold start problems.
The properties of different fuels is shown in Table 2.
Table 2 : Properties of different fuels

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A sustainable distributed energy system using methanol for energy storage

Some methanol-specific design measures have to be taken while using such engines and these
specifications are enumerated below.
1. Increased fuel injector flow rates and fuel tank volume to compensate for lower energy
density of methanol compared to gasoline. Since, the present study is on a stationary
application, this factor is not a major challenge.
2. Use of special materials in the engine due to corrosive nature of methanol.
3. Special cold start strategies.
4. Cylinder head adjustments.
All these adjustments do not add a substantial cost and increase in cost is estimated to be less
than 300 USD.
In an experimental study carried out at University of Gent on two flexible-fuel engines confirmed that the potential for relative power and efficiency benefits up to 10 %. Engine-out
CO2 and NOx levels dropped by 10 % and 5-10 g/kWh respectively, while the other harmful
emissions did not change significantly [25].
It is evident from the review studies that benefits from methanol engines outweigh the drawbacks and thus, authors conclude that use of methanol in dedicated spark ignition engines is a
tangible solution for the present study.
In the next section, a summary of the present study will be provided.

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A sustainable distributed energy system using methanol for energy storage

Conclusion and Scope for future work

This report has shown that methanol instead of hydrogen could be an interesting energy storage medium for the future. Methanol can be used in different ways as energy source. Only
applications in micro-turbines and IC engines were considered in the present study. It was clear
that methanol is a clear alternative for energy storage in distributed poly-generation systems
based on renewable energy. A well to tank (WTT) energy analysis prepared is shown in Figure
15 [26]. It was seen that highest energy is consumed in the process of electrolysis. This is
the energy we intend to store. However, a significant amount of energy is consumed in the
compression process, which can be substantially reduced with discovery of new catalysts and
more efficient process.

Figure 15: Percentage of WTT Energy spent in each process of methanol production

Life cycle assessment of CO2 emissions for methanol synthesis performed by Cifre and Badr
is shown in Figure 16 [27]. Obviously, when CO2 is captured from atmosphere, the life cycle
CO2 is significantly lower.This technology is expensive and immature. Hence, production of
hydrogen from biomass can be considered as the next best alternative assuming biogenic carbon
doesnt contribute to GHG emissions. Life cycle CO2 emissions for CO2 capture from flue gases
is higher compared to biomass due to separation processes and transportation. There is a lot
of scope for future research in this domain as the CO2 capture is imperative and technologies
are not completely effective on a large-scale.

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A sustainable distributed energy system using methanol for energy storage

Figure 16: Life cycle CO2 emissions for production of 1 kg of MeOH using different production
paths

It is evident from this graph, that life cycle CO2 emissions for the three processes involving
renewable hydrogen production are clearly superior over the process involving fossil fuels.
Due to unavailability of large areas in developing nations for biomass cultivation and strict
regulations on CO2 emissions in developed nations, it is inevitable to concentrate on improvement of CO2 capture technologies for production of methanol. Methanol is a solution for energy
storage and CO2 recycling as shown by this review study.
Overall, it is observed that methanol is a suitable medium for energy storage and abatement
of CO2 through process of carbon recycling. Methanol appears to be a practical solution for
distributed energy systems.

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A sustainable distributed energy system using methanol for energy storage

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