CO2 TO PRODUCTS

a feasibility analysis

Team Tamil Nadu

Spring 2021

 CO2 to Products
a desk top study

Abstract
Over at least two decades, scientific communities in various institutions are actively
pursuing to hasten the carbon cycle done by nature to convert Carbon dioxide
(CO2), a green house gas attributed to global warming, into useful organic
compounds. There is huge urgency to get the process of conversion of CO2 looking
erratic weather, extreme climates, cloud outbursts, severe drought, etc. leading both
economic chaos and life threatening incidents. Report of sea rising and vanishing
coastal area is like a time bomb
awaiting to destroy earth unless
we find a lasting solution and aid
the conversion of CO2 into
products - it can be as simple as
methanol, ethanol, dimethyl
ether, formic acid or as complex
as poly carbonates. The
challenge is to make the process
viable from all aspects of
reaction kinetics, economic scale
of commercial size, environmental friendly and above all safely too. CO2 being a
highly stable product, the conversion is too slow for adoption of conventional
processes. Past experiments like algae to oil in CO2 ambience did not give
encouraging outcome despite initial promises glorified with tall claims. Well, the
approach followed by “Team Tamil Nadu” is that of process intensification. Pros
and cons of different pathways are evaluated in arriving at the most plausible
solution (s). Next will be to carry out proof of concept in a research institute. As
such availability of pure CO2 is not an issue as one can get thousands of tonnes of
CO2 from refinery sources specially from hydrogen producing units.

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Setting Premises
Being a vast domain, it would be apt to set boundary conditions so as to derive
solutions within and converge on selection of candidate hypothesis for next level of
carrying out proof of concept in any reputed research institute. The following
assumptions are made to study the options in conversion of CO2 into useful
products that have large commercial value.

i) CO2 of desired purity shall be made available in ample quantity from any
hydrogen manufacturing plant at crude oil refineries. Typically a reasonable size
refinery of say 100,000 Bbls per day will need hydrogen any where from 0.7 to
2%wt on crude intake. Hence, the amount of pure CO2 availability will be
above 500 tonnes per day from one refinery, which is sizable for a commercial
activity. With ~ 600 refineries in the world processing crude over 82 mmbpsd
CO2 availability will be minimum 0.5 mmtpa from hydrogen plants alone.
ii) It will be of great interest if any of the refinery streams / products, sold below
crude oil delivered cost, are used while making CO2 based end products. These
streams include:- a) Disulphide oil which is typically a blend of organic sulphur
compounds such as dimethyl disulphide, methyl ethyl disulphide, diethyl
disulphide, etc; b) Clarified slurry oil; c) Fuel Oil; d) Petcoke; e) Elemental
Sulphur; f) Acid Soluble Oil; g) Refinery slop and tank sludges h) Refinery sour
water which contains H2S, NH3, COS, etc. either as such and or post stripping;
i) Refinery off gases from vacuum columns and j) Hy residue like Vacuum unit
bottoms, asphalts, bitumen, Extra heavy Coker gas oil, etc.. Methane available
in refinery can still be considered as long as its need is restricted to say one
hundredth of CO2 converted into valuable product.
iii) Use of CO2 either as such in any solvent extraction unit within the unit or as a
co-solvent can be considered, if such option is feasible. Also, CO2 catalyst can
be considered too when any such requirement foreseen.
iv) Any end product utilizing CO2 should ideally be of immediate value with ready
market which will help to shrink the time to market.
v) Use of CO2 in food chain products even as inerting medium needs a careful
approach as it would involve various statutory approval process
vi) Bio processes being slow and unwieldy on commercial scale are not considered.

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Size of Pie
Globally, 36 Giga tonnes of CO2 per annum (approx. 100 MMTPD), get emitted
to atmosphere. Oil sector contributes to over 45 % of this. India’s share is about
7%, though one of the lowest on per capita basis. Incidentally, India stands 3rd in
the world with over 2.6 Giga tonnes of CO2 emission to the atmosphere after
China and United States of America. The issue is serious to be addressed. As such,
the GenNext in the last world economic forum have accused the nations of robbing
their future which shows up in nature giving back with fury now across the globe.

Pathways, Enablers and Barriers

Product / Co Feed Pathway / Enablers / Barriers Market
1. Ethanol Atomically dispersed copper on a carbon-powder 47 MMTPA
support to conduct electrochemical conversion of with 5 to 6%
CO2 and H2O
carbon dioxide- to- ethanol process. growth
rate.
Ethanol to ethylene is another opportunity to make
integrated petrochemicals in same site @ 2$/gal it
is about
Need renewable source for generating electricity.
670$/tonne
Competition from production sources like grain based
ethanol which is 70% of total make today.
2. Di Methyl Ether Chemical looping CO 2 /H 2 O splitting (CL) unit Nearly $8B
producing syngas (CO and H2) for the DME synthesis with ~ 17%
CO2, CH4 and H2O or
using the exhaust gases of an oxyfuel power cycle. growth
Simply CO2 and H2 rate.
Alt. produce methanol from CO2 hydrogenation and
(hydrogen from
then convert MeOH into DME. H2 should be from Price is
electrolysis of water)
electrolysis process using renewable power. about $500/
tonne
Worth exploring process to make DME & H2 from CH4
in existing steam reforming units at refineries which
produce H2 and CO2. As such DME can be blended into
LPG or used as alternative fuel to diesel IC engines.
Overall CH4 use per mole of CO2 consumed is 2.
3. Acetic Acid A temperature programmed reaction for acetic acid ~ $9 B with
from CO2 & CH4 on 5% Pt/Alumina at ~400 °C. Another 5% growth.
CO2 and CH4
involves Cu-modulated zeolites catalyst & its structure 2023 demand
Methane use is 0.36T/ of both active copper species and zeolite pore channels.. is 22mmtpa
tonne of CO2. As such
An ideal option when excess gas exists in refinery. Also, Price is
both are responsible for
good to leverage coal bed methane. $620 / tonne
greenhouse effect.
C–H bonds dissociation, C–C bond coupling,
See Note 1 also.
protonation of acetate, & desorption of acetic acid
control reactions

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Product / Co Feed Pathway / Enablers / Barriers Market
4. Poly Propylene Fixation CO2 into polymer is a feasible proposal to Globally
Carbonate (PPC) & construct high value-added biodegradable plastic. C2= & C3=
Poly Ethylene Direct copolymerization of CO2 with different epoxides make are
Carbonate (PEC) viz. isobutylene oxide (BO), cyclohexane oxide (CHO), 192 & 125
propylene oxide (PO), or ethylene oxide (EO) to produce MMTPA
CO2 and Propylene
respectively
oxide / Ethylene Oxide aliphatic polycarbonates & poly (carbonate-ether)s.
while CO2
Biodegradable polymer is good for environment. PPC being let is
has huge prospect in packaging industry. 100 million
1.23 tonnes of Propylene Oxide needed per tonne CO2. tonnes per
Improvements on thermal & mechanical performances day.
of PPC needed by physical & chemical modifications.
5. Methanol It is a pyroelectric process using bismuth tungstate Global need
CO2 and H2O nanoplates that converts heat energy generated from is Methanol
temperature variation of day & night into electrical ~80mmtpa.
The production of energy which in turn converts CO2 to methanol.
methanol can lead to
several other derivatives This catalyst could generate methanol over 20 thermal
like olefins, ether, cycles with temperatures varying between 15°C & 70°C
formaldehyde. etc. at atm. pressure. Truly a disruptive technology. Still in
proof of concept stage.
6. CO2 as supercritical Research on supercritical CO2 offers new opportunitiesScope is
fluid solvent..(scCO2) in - i) microelectronics; ii) caffeine extraction; iii) dry
large and
cleaning; iv) biological processing; v) nano technology;
no dearth
CO2 with suitable
vi) organic synthesis and vii) enhanced oil recovery.
of market
surfactants.
opportunity
Another promising area awaiting breakthrough.
when seen
scCO2 is a very uncooperative solvent incompatible in totality.
with vast solutes & surfactants. To dissolve high mol.
wt. or polar compounds in scCO2 additives / surfactants
needed to produce nanometer sized domains in scCO2
by forming micelles or micro emulsions. Cost is high.
7. Acetal including Blending of acetal with bio jet (in Jet A1 grade) is The global
acetal based bio Jet. acceptable as acetal has excellent stability. Acetal is growth is
derived by the condensation reaction between carbonyl 7-9 % CAGR
CO2 and CH4
compound and alcohol.
Acetal market looks promising with opportunities in
automotive, healthcare, and electronics. The major
drivers are increasing applications in food & packaging,
and in resistance to weather changes.
Acetal-based bio-jet fuel produced under milder & less
energy intensive conditions, 1,1 - di methoxy nonane
(acetal derived from nonanal), is comparable to Jet A-1
quality and didn’t significantly affect at 10 % blend.
The higher acidity level attributed to presence of excess
nonanal can be handled in purification step.

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 Product / Co Feed Pathway / Enablers / Barriers Market
8. Sodium Carbonate & NaHCO3 and or Na2CO3 can be made using Solvay Na2CO3
Bicarbonate process and reacting NaCl with CO2, NH3 and H2O. A price $ 230 -
US patent describes making Na2CO3 from NaOH & CO2. 260 / Ton.
CO2 and NaOH
Bicarbonate
In 2020, the global Sodium Carbonate market size was
market is 5
US$ 15040 million and it is expected to reach US$ 16650
MMTPA.
million by the end of 2027. This is about 45 MMTPA of
Soda ash world over. Use of Soda ash range from
container glass (28 %); flat glass (16 %); chemicals (18 %);
soaps & detergents (10 %); metals & mining (3 %); pulp &
paper (2 %); others (23 %)
Requirements are too small to leverage and solve CO2
problem.
9. Ammonium Absorption of CO2 in aqueous ammonia results in Global need
Bicarbonate ammonium bicarbonate formation. 198 mmtpa
now grows
CO2, NH3 and H2O. Ammonium bicarbonate used in Food, Pharmaceutical,
at a CAGR
Beverage, Health & Personal care products, Agriculture/
of 4%. The
Animal Feed / Poultry and in manufacturing of plastics
current
& rubbers as a fire retardant. Also used as raising agent
price 200$/T
in flat baked goods viz. cookies, crackers and similar
applications in food industry where it is preferred as it
does not affect the taste of flat baked goods.
Ideal option for refineries to produce ammonium
bicarbonate instead of destroying NH3 in Sulphur unit.
Ammonium bicarbonate decomposes above 36 °C into
NH3, CO2, and H2O in an endothermic process. In other
words, it has poor thermal stability.
Note: - 1. The binuclear copper-oxo cluster ([CuOCu]2+) in the three-dimensional BEA and MFI zeolites and tri-nuclear copper-oxo cluster ([Cu3(μ-O)3]2+) in the
one-dimensional MOR and TON zeolites are catalytically active in the direct conversion of CO2 and CH4 to acetic acid. The MOR zeolite carrying [Cu3(μ-O)3]2+
clusters ([Cu3(μ-O)3]-MOR) exhibits superior catalytic activity to make acetic acid with a low apparent activation energy (57 kJ mol−1).

It will be worth pursuing all these nine ideas to next level of proof of concept after looking at the
energy need and reaction kinetics closely. The most appealing ones are: - a) Making Ethanol or
Methanol; b) Acetic acid; c) Acetal of different grades and d) Use of CO2 and solvent.

Road Ahead
1. Note of CO2 to Products shall be circulated within the team members for
their review. Based on assessment, the most promising ideas (at least 3 to 4)
shall be offered to science students pursuing masters / doctoral programme.

2. It is expected that students can either collaborate with other institutes and or
engage their own research facilities to explore the various pathways in
converting CO2 to Products and develop most promising hypothesis with

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 adequate reasoning. The team shall review the approach suggested and take
up the workable ideas to next phase, which is setting up “Proof of
Concept” (POC) in consultation with the heads of institutes.

3. In the meanwhile additional ‘prior art search’ shall be conducted by the

team and facilitate needed IP protection and control thereof.

4. Also, the team will explore the market opportunity for any new products
which may be an outcome of in-depth study by the science students.

5. The POC done on lab scale will then be pursued on pilot scale taking
assistance from any CSIR labs and or at R&D set up with oil refiners in
India under exclusivity arrangement and Non Disclosure Arrangements.

6. At pilot stage, the team shall review the process variables that could impact
the overall conversion and quality of end products targeted apart from
evaluation of cost of production to ensure economic feasibility.

7. Post successful trial of pilot, the chosen pathway will be patented and
canvassed for suitable commercial adoption with leading oil refiners. Any
coordination work in this regard will be done by the team.

Funding will be discussed separately.

References: -
A. https://polymer-additives.specialchem.com/_/media/news/polymer-additives/neo-import/
2021/01/co2-utilization-as-an-alternative-renewable-chemical-feedstock-for-virgin-
polymers.jpg?la=en
B. https://www.sciencedirect.com/science/article/abs/pii/S2452223618301202
C. https://www.thehindubusinessline.com/news/lt-evaluating-tech-for-co2-to-methanol-plant/
article32545296.ece
D. https://www.thehindubusinessline.com/news/lt-evaluating-tech-for-co2-to-methanol-plant/
article32545296.ece

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