Value Creation Options from CO2- A Potential

Route Map

Presented by
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Introduction
• These days ,on average, a person is causing 5 tpy CO2 emission. The
range varies from 15 tpy in developed nations to less than 2 tpy in India.
However the lower number is no solace to us, as the impact of climate
change, unfortunately affects countries like India most.
• The efforts and technological development added with a strong
commitment from the Government enables us to leapfrog into
technologies of tomorrow to tackle the situation.
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The need for CO2 to Chemicals

• During the last 5 years atmospheric CO2 has irreversibly crossed 400
ppm level. The changes have begun and perhaps non-stoppable.
• However, there is an effort to arrest the increase in concentration, and a
vast and still developing subject-climate science experts believe that
with concentrated efforts CO2 levels can be brought down to beginning
of the century levels.
• Treating CO2 as something to build upon rather than a waste product
that needs to be disposed is the key principle in all CO2 conversion
processes.
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CO2 Generation and Use Pathways

• IEA report gives a concise picture that
explains all
• Some of the conversion processes are
merely a way to store one form of
energy into another as any fuel will
eventually release back CO2.
• Building materials capture the CO2 at
surface levels.
• Fertilizer sends back the CO2 into
biomass.
Source :IEA 2019
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Pathways Detail
Researchers identify 10
main pathways for CO2
utilization

Source : Nature Nov 2019

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CO2 Pathways characterization

• 10 pathways can be
characterized by means of the
processes and combination
steps of conversion, sourcing,
storage etc.

The focus of the present discussion is on

Transformation Pathways (L)

Source : Nature Nov 2019

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Methanol
• One of the starting point of chemical conversion of
CO2 to fuels and chemicals.
• Methanol is an important chemical NOT manufactured
in India. Global production is 80 Million Tons/yr. (2018)
• Today 65% of the production starts with Natural Gas
• There are technologies emerging to convert CO2 to
Methanol using alternative energy.
• Several catalysts have been developed for direct
hydrogenation of CO2 to methanol.
• The cost of this technology presently is not
competitive with the cost of methanol synthesis from
syngas.
• The Technology Readiness Levels are varying from 4 to
7. Source: www.methanol.org
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Technology Landscape for Renewable Methanol

• Methanol production involves upto 95%
conversion of CO2.
• Biomass/MSW pathway has been established
already.
• Heterogenous catalysts have been developed
(ZnO, ZrO2, Rare Earths ) for the conversion
process.
• There are processes using electrochemical
reduction of CO2 into methanol.
• The research area is very active.
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Methanol Downstream products

A wide range of
industrial
chemicals can
be produced,
leading to the
concept of a
bio refinery.
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Methanol to Olefins
• Methanol
cracking into
olefins opens
more economic
value addition Methanol

• Commercial
level technology
available for the
conversion
Source : Methanex 2019
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Methanol Use
Almost 2/3rd of Methanol
produced is used for chemical
applications – keeping the CO2
loop closed out from emissions.
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Methanol Potential in India

• Present demand is about 2 million ton per year and is expected to grow
at CAGR of 7.5% to about 5 million ton per year by 2030. Virtually all of
this is imported.
• A methanol economy concept has been already taken by GOI and NITI
Ayog is leading the activities in this regard. Considerable development
has been done regarding policy formulation and road map.
• Methanol /DME fuel blending policies and standards already in place.
• Renewable Methanol fits into the scheme and bears an incentive of
being carbon neutral.
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Di Methyl Carbonate(DMC)
• DMC is a carbonate ester of methanol. It has usage already in chemical
synthesis as methylation agent and as a solvent.
• Novel applications include usage as an electrolyte in Li-ion cells
• From CO2 perspective, DMC can contain three times CO2 as methanol.
• DMC is also used as an intermediate to produce polycarbonate,
polyurethane and specialty chemicals.
• DMC can be considered as a drop-in component for Petrol due to high
RON and safe handling nature.
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Production of DMC
• Traditional DMC route involves phosgene and being abandoned due the
very reason.
• Novel technologies without using phosgene are matured
▫ ENI Chem Italy: oxidative carbonylation of methanol catalyzed by copper catalysts 
▫ Ube Industry, Japan: methanol oxidative carbonylation by methyl nitrate over Pd catalysts
▫ Asahi Industry, Japan: transesterification of cyclic carbonate starting with ethylene oxide
(EO). CO2 and EO form ethylene carbonate (EC), then EC is converted to DMC by
transesterification with methanol
▫ National Institute of Materials & Chemical Research (NIMCR; Tsukuba, Japan -Dimethyl
carbonate is made from Acetal and Supercritical Carbon dioxide in a new process

Source: K. Takeuchi 2012

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DMC In India
• RIL has developed mixed oxide stable catalyst for high yield &
selective direct DMC synthesis process.
• The main usage of DMC in India is envisaged to be in Electric
Mobility ( Li ion cell electrolyte) and as a fuel additive.
• With 25% EV penetration , DMC requirement by 2030 exceeds 150
kT/yr

Source: Reliance Industries Ltd., 2019

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FT Synthesis
• CO2 to Chemicals – an old way is FT synthesis
• It is again to be considered as an energy storage option as FT synthesis
consumes energy. Using conventional fuels for FT is not CO2 neutral
process.
• The advancement of FT synthesis with increased CO2 consumption is
feasible with alternative energy
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Urea
• Urea is the largest-scale chemical utilization pathway for CO2 fixing. 140 Mt CO2/ yr is
utilized to produce 200 Mt/yr of urea.
• Those days Urea was considered as a chemical fertilizer. Now Urea is also a polymer
important chemical.
• CO2 fixation naturally happens in Urea when used for non-fertilizer applications
• Other than on purpose production of NH3 in fertilizer units, Refineries do generate
economically relevant amount of NH3 due to clean fuel manufacturing and this NH3
can be used to capture CO2 into urea.
• A new development is the production of urea from carbon dioxide and nitrogen in the
flue gas of the power plants
• Breakeven costs per ton of CO2, calculated, for urea (around −$100) indicates viability
and maturity of technology
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Gas Phase Fermentation

• Novel process involving conversion of a mixture of CO2, CO and H2 into
Ethanol and higher alcohols.
• MRPL is in the process of implementing a 60 KLPD plant using agri
wastes.
• Similar technology is also adopted for converting blast furnace gases,
coke oven gases and purge gas from steam methane reformer-PSA units
into value added chemicals while fixing CO2.
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Climate change vs Economic Considerations

• CO2 can be transformed efficiently into a range of chemicals, but only a
few of the technologies are economically viable and scalable.
• Some are commercialized, such as the production of Methanol, DMC,
Urea and polycarbonate polyols.
• The estimated utilization potential for CO2 in chemicals is around 0.3 to
0.6 Gt CO2 yr−1 in 2050.

Source :Hepburn 2019

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Conclusion
• CO2 to be used as a starting material is the best strategy.
• CO2 fixing can be handled effectively with the available technologies to
impart a starting momentum to the change.
• Industries can achieve the objective of economic advantage while
adopting latest CO2 conversion processes
• Methanol and Methanol derivatives, DMC, FT chemicals using
alternative energy are good candidates.
• Further research is needed and happening in India as well.
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Ultimate CO2 Converter

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End of Presentation
• Q&A
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References
1. Putting CO2 to Use- Technology Report IEA Sep 2019
2. Hepburn, C., Adlen, E., Beddington, J. et al. The technological and
economic prospects for CO2 utilization and removal. Nature 575, 87–
97 (2019). https://doi.org/10.1038/s41586-019-1681-6
3. Gaseous Carbon Waste Streams Utilization: Status and Research
Needs (2019- National Academic Press.
4. Renewable Methanol Report. Jan 2019, www.methanol.org
5. K. Takeuchi, in Polymer Science: A Comprehensive Reference, 2012
THANK YOU

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