Transitional technology for renewable methanol
Adapted from: Transitional technology for renewable methanol - Energy Magazine
(November 8, 2024)
Colin A. Scholes, University of Melbourne Department of Chemical Engineering
In the quest to transition to sustainable energy through hydrogen, methanol has
emerged as a promising solution to the issue of hydrogen storage and transportation.
The versatility of methanol as a hydrogen-carrier and valuable chemical feedstock for a
variety of industries will make methanol a key component in reducing greenhouse gas
emissions and achieving a circular chemical economy.
The methanol economy
The potential for methanol is significant, especially outside of the energy sector.
Methanol will play a crucial role in the global chemical industry as it can serve as a
precursor to a variety of chemicals across numerous sectors, including adhesives and
resins, paints and coatings, plastics, pharmaceuticals, and in solvents and cleaning
products.
This represents the concept of the ‘methanol economy’, whereby methanol is the basis
of the global chemical industry rather than petroleum hydrocarbons. This will enable
carbon intensive industries that are vital to the modern economy to become carbon
neutral. The importance of methanol is recognised by these sectors, and significantly,
renewable methanol production is set to evolve over the next decade, driven largely by
technology innovation.
Making methanol via natural gas
Traditionally, methanol is produced via a two-step process:
Step 1: Steam Reforming of Methane
CH₄ + H₂O → CO + 3H₂ ΔH = positive
*Some CO is further converted into CO₂*
CO + H₂O ⇌ CO₂ + H₂ ΔH = negative
Step 2: Synthesis of Methanol
CO + 2H₂ ⇌ CH₃OH ΔH = negative
This process is mature and widely used with existing large-scale infrastructure, it
converts methane to methanol with relatively high yields, it is cost effective and
large-scale production is possible. However; this process also uses the fossil fuel of
natural gas (CH4) as a feedstock, it releases CO₂ during production, it is highly
energy-intensive requiring extreme heat and pressure and the methanol produced is
also mixed with other unreacted gases.
Making methanol via CO2 hydrogenation
Methanol can also be produced via the CO₂ hydrogenation process, which involves
captured carbon dioxide (CO₂) from the atmosphere being directly reacted with
hydrogen (H2) according to the following equation:
CO2 + 3H2 ⇌ CH3OH + H2O ΔH = negative
Methanol is a liquid at room temperature, so it's easy to transport using existing fuel
infrastructure. Once at the desired destination, it can be reconverted into hydrogen
on-site via steam reforming according to the following equation:
CH3OH + H2O ⇌ CO2 + 3H2 ΔH = positive
Although CO2 is produced, this is not new CO2 as it was originally captured from the
atmosphere. This CO2 can then be used again to create more methanol, creating a
closed carbon loop. If green hydrogen is obtained via electrolysis of water and
combined with captured CO2 from the atmosphere, the methanol produced can be
considered ‘green’.
Using CO2 hydrogenation to produce methanol presents several challenges when
compared to the conventional method through natural gas (CH4):
● CO2 hydrogenation requires an additional molecule of hydrogen than the
conventional route, leading to a higher hydrogen consumption.
● The thermodynamics of CO2 hydrogenation are less favourable than those of
the conventional process, which results in lower methanol yields.
● Competing reactions during CO2 hydrogenation can generate carbon monoxide
(CO), which further reduces methanol production.
Currently, methanol yield from CO2 hydrogenation is less than 40 % due to these
limitations, and the process struggles to compete against the conventional natural gas
route as a result. To improve yield, multi-stage reactors with methanol separators and
selective absorption to recycle unreacted reagents are used; this increases the
operating costs of renewable methanol creation which is economically unfavourable.
Membrane reactors
As previously stated, the goal of CO2 hydrogenation is to turn
CO₂ and H₂ into methanol. But this chemical reaction doesn’t
easily go all the way; it reaches equilibrium before all the CO₂
and H₂ turn into methanol. This limits the yield of methanol
as only a certain percentage of reactants turn into product;
therefore, chemical engineers need to make changes to the
system to push the reaction forward.
Technology innovation in CO2 hydrogenation is focused on an
alternative reaction approach to produce methanol through a
membrane reactor, which integrates the reaction and
separation processes into a single process unit; it allows methanol escape as soon as it
is made and keeps CO₂ and H₂ inside until they react.
CO₂ and H₂ go into the reactor and start reacting to form methanol. The membrane is a
filter-like material that blocks the reactants (CO₂ and H₂) and allows only the methanol
to pass through. As methanol is removed immediately, the position of equilibrium
shifts.
An innovative new technology
The University of Melbourne has developed catalyst membrane reactor technology
that can effectively produce purified methanol at a rate that is over 300 % higher than
conventional approaches. This technology is based on two core achievements;
development of a catalyst ideal for CO2 hydrogenation, and utilising high temperature
performance polymeric membranes.
The catalyst is vital to the overall process as it is used to speed up the CO2
hydrogenation reaction, without which CO2 and H2 would not convert to methanol in a
meaningful timescale. They are using a combination of copper and zinc oxide as the
catalyst; copper helps the reaction work well at low temperatures and pressures, and
zinc oxide improves how well the catalyst performs. The catalyst is made of tiny
particles (nanoparticles) that are spread out loosely on the surface of the membrane.
Therefore there is more surface area and better access to reactants, and reaction
efficiency is improved by letting gases diffuse easily and reach the catalyst. The
positioning of the catalyst directly upon the membrane surface ensures that the
produced methanol is removed directly from the catalyst reaction zone upon
formation, meaning high conversion efficiencies are achieved.
The membrane is like a filter that lets methanol pass
through but keeps CO₂ and H₂ in the reaction area;
this helps achieve a higher product purity. This is
tricky because methanol is a larger molecule than
CO₂ and H₂, and usually membranes let small
molecules through more easily; hence, the design
behind the material must be different to other
membrane processes. To solve this, the University of
Melbourne is using special polymers that are strong
enough to work at high temperatures (up to 400°C)
and let methanol pass through based on solubility in
the membrane material, not just size. Methanol
sticks to the membrane material and passes through. CO₂ and H₂ don’t stick, so they
stay behind. Water, which is also made in the reaction, also passes through and is
removed, which further helps the position of equilibrium shift.
This combination of catalyst and high temperature membranes enables the University
of Melbourne’s membrane reactor technology to successfully produce methanol
between 100°C to 200°C, significantly lower than the 300°C required through a
conventional reactor.
This is possible because:
● The active removal of methanol and water from the reaction shifts the position
of equilibrium.
● The catalyst enables the reaction to take place at lower temperatures, while
sustaining a reasonable reaction rate.
● The membrane’s high selectivity ensures the methanol is separated so it is of
high purity, with almost no CO2 or H2 present.
These are extremely innovative ways of improving efficiency without needing higher
temperature or pressure.
Looking to the future
The next step for this new methanol technology is to test it on a much larger scale, in a
plant that can make large amounts of methanol. Currently, there aren’t any large
factories in the world that make methanol using carbon dioxide and hydrogen like this,
so the University of Melbourne has a chance to be a global leader in this area. The
membrane and catalyst materials may be expensive or difficult to manufacture on a
large scale; early-stage technologies often face high capital costs before they can
compete with well-established industrial methods.
The demonstration plant will make methanol as a starting material to create other
useful chemicals like dimethyl ether and liquid fuels, which can be used as greener
alternatives to petrol. This will help show how methanol can be part of a cleaner
energy future, especially while the world is still preparing to use hydrogen more widely.
CO2 hydrogenation to methanol is a promising approach that offers a way to recycle
carbon dioxide and produce a valuable chemical. By utilising advanced catalysts and
integrating membranes, optimal membrane reactor technology has been developed,
which will contribute to a more sustainable future.
Whilst there are challenges remaining, the key research and development has been
achieved, and viable technology is ready for demonstration that will fully unlock the
full benefits of CO2 hydrogenation to methanol.
