SUSTAINABLE PILLARS - DEVELOPMENT OF PROCESS

There are two steps being carried out in methanol manufacturing. Firstly the feedstock natural
gas will be converted into a synthesis gas stream which consist of carbon monoxide, carbon
dioxide, water and hydrogen element. This is usually performed by the catalytic reforming of
feed gas and steam.

The next step is the catalytic synthesis of methanol from the synthesis gas. Each of these steps
can be carried out in some approaches and numerous technologies that offer a spectrum of
possibilities which may be most suitable for any preferred application.

There are various sources to obtain syngas including natural gas, coal, biomass, or virtually any
hydrocarbon feedstock, by the reaction with steam which known as steam reforming, carbon
dioxide as dry reforming or oxygen as partial oxidation. Syngas is an essential intermediate
resource for production of hydrogen, ammonia, methanol, and artificial hydrocarbon fuels.
Population growth and rising economies have a consequence of growing energy demands
associated with depletion of fossil fuel and impacts towards environment. Carbon dioxide,CO2
which is a well known greenhouse gas, is a source of production of fine chemicals and fuels such
as methanol. It appears in abundance because of anthropogenic human activities. Nowadays,
methanol is typically produced from synthesis-gas which requires conventional fossil fuels,
however, the availability of these fuels is restricted. As an alternative, the vent streams of steam
reforming units, which are rich in carbon dioxide and steam, can be used collectively with
methane (natural gas) in a bi-reforming process for methanol synthesis. The vital concept is that
carbon dioxide and water are recycled like in a synthetic photosynthesis process.
There are two relevant sustainability issues that address to the chemical conversion of methanol
from carbon dioxide which are will be economically feasible replacement of fossil raw materials
and avoidance of greenhouse gas emissions However, chemical stability of carbon dioxide is a
challenging impediment to conversion requiring severe reaction conditions at the expense of
increased energy input, therefore adding capital, operation and environmental costs, which could
result in partial or total override of its potential sustainability as feedstock to the chemical and
energy industries
 Step 1 – Production of Syngas (synthesis gas) from natural gas
.
i. Steam Reforming

Steam reforming is the traditional dominating process where methane gas and steam are
mixed at high temperature and pressure and with the help of catalysts forming carbon
monoxide and hydrogen. The gas mixture are typically passed through pipes coated
with catalysts in a shell and tube heat exchanger to provide the necessary heat which
approximate to 850 °C for the reaction to take place. For a natural gas feedstock with
little heavy-hydrocarbon and sulphur impurity in it, a steam-reforming-based plant is the
most cost effective, better reliability and higher energy efficiency

2CH4 + 2H2O ⇌ 2CO + 6H2

The excess hydrogen gas that are produced from steam reforming needs to be eliminate
and is usually burnt to provide heat for the reformation process to occur but can also be
used for many other purposes.

The synthesis gas production is endothermic and requires a lot of thermal energy. The
production of methanol may produce some heat that can be recovered but heat is also
provided by burning some of the natural gas. The production of synthesis gas and
subsequent compression requires large amount of the investment cost in a methanol
production plant and most of the energy need to power the process and represents
majority of the capital cost

ii. Dry reforming

By reacting methane and carbon dioxide synthesis gas is produced in a process called dry
reforming as no steam is used.
CH4 + CO2 ⇌ 2CO + 2H2
The reaction will be more endothermic as compared to steam reforming and a gas is produces
with significant hydrogen deficit for methanol synthesis. While this is a disadvantage for
methanol synthesis of the gas mixture which has the right composition for any other applications.

iii. Bi-Reforming (Single step)

Process of producing methanol can be perfomed by carrying out steam and dry reformation
process separately. The products of reforming in the earlier process are mixed together before
being introduced into the methanol synthesis process. The catalyst is uses for the second
reaction which may help the reaction to combine the single carbon monoxide and the two
hydrogen to form the product of desired methanol. At high pressure which is between 5 to 30
atm and temperatures of 800-950 C°), a catalyst based on nickel oxide, NiO and magnesium
oxide,MgO are activated under hydrogen which are effective for the bi-reforming. In a single
step, the desired value of 2 for methanol and hydrocarbon synthesis can be obtained in just by
easily adjusting the CO2-to-steam ratio in the gas feed, the H(2)/CO ratio in the produced syn-
gas.
3CH4 + 2H2O + CO 4CO + 8H2

Step 2- catalytic synthesis of methanol from the synthesis gas

In the methanol synthesis step, carbon monoxide and carbon dioxide will react with hydrogen
due to the exothermic reactions. Additionally, both reactants are involved in the water gas shift
reaction which strongly influences the reaction mechanism. The generation of methanol is
limited by chemical equilibrium and works best at low temperatures and pressures. However, in
order to obtain significant reaction rates, the synthesis is conducted in the presence of a
Ni/Zn/Al2O3 catalyst at temperatures between 200–300 ◦C and pressures between 50–100 bar,
resulting in a product of 5–14 mole-% methanol at the outlet. The crude product can be easily
separated from the unreacted syngas through flashing near ambient temperature. The unreacted
syngas is recycled to the inlet of the reactor and combined with fresh make-up gas. As the gas
contains impurities in the form of inert gases such as methane, butane, and propane, only a small
fraction has to be purged from the loop.
CO + 2H2 → CH3OH