Biological Carbon CH443 (OPEN

ELECTIVE)
Sequestration
11/16/2023 CHEMICAL ENGINEERING, NIT WARANGAL 1
Biological Sequestration
 Biomimetic Sequestration
⮚ Major contributor to green house gas (GHG) effect is CO2
because of emission rate and significant effect on the climate change.
⮚ Atmospheric concentration is increased from 280 to 420 ppm from
pre- industrial revolution to now..
⮚ Fossil fuels will be major source of energy in next few decades.
⮚ Physical means of CO2 storage
⮚ Geological sequestration - cost and leakage problem
⮚ Ocean storage - mechanism unknown
⮚ Biological storage
⮚ Biological reaction capture
⮚ Photosynthesis and soil carbon storage
⮚ Heterotrophic bacteria - enzymes
⮚ Reliable and viable solution to reduce the CO2 emissions with high rate and
low cost.
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 Bio Sequestration - Photosynthesis
⮚ Forests are one of the natural sinks of CO2.
⮚ Tress convert the CO2 into biomass by photosynthesis and releases
same
CO2 to environment through respiration and decomposition.

⮚ By avoiding deforestation in tropical forests – 2.8 billion tonnes of CO2

per
year can be reduced.
⮚ Usage of bio-energy crops which provide carbon neutral energy.
⮚ Sugarcane, oil crops, cereals, maize and wheat – largest
contributors of ethanol. 4
 Bio Sequestration – Capture by
⮚ Soil containsSoil
three times carbon than in living forms.
⮚ Carbon from aboveground mass enters as soil organic/inorganic carbon pool.
⮚ Development of photoliths or biochar – increases the soil sequestration.
⮚ Photolith – rigid microscopic structures of silica which stores carbon
for several thousand years permanently.
⮚ Biochar – Charcoal created after the pyrolysis of biomass.
⮚ Ceratain types of grass increases the soil carbon by reducing the CO2 from
2
– 4.7 tonnes/yr/acre.

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 Bio Sequestration – Microbes in Carbon
⮚ Fixation
Microbes are tiny living things that are found in the water, soil, air.
⮚ The microbes are able to recycle the essential elements of cell makeup
which directly effect the environment.
⮚ Photosynhtetic microbes – algae and autotrophic bacteria play important
role in fixing CO2.
⮚ Cyanobacteria – produces oxygen during photosynthesis.
⮚ Autotrophs – producers in natural cycles. They make organic
matter by
consuming inorganic matter and with the help of sunlight.

https://biologydictionary.net
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 Algal Sequestration of CO2
⮚ Microalgae carry out photosynthesis using free CO2 and bicarbonate ions.
⮚ Microalgae produce rapidly and in all kinds of environment –
attractive to power plant exhaust CO2 capture.
⮚ Lomentaria articulata– gain of 52% carbon gain and 314% wet
biomasss production rate when CO2 concentration is doubled.
⮚ Algal biomass produced - biofuels, food supplements,
pharmaceuticals,
enzymes, and animal feed.
⮚ The biomass can be converted into electricity by combustion or to
methane by anaerobic digestion.

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 Heterotrophic Bacteria in CO2 Sequestration
⮚ Conversion of CO2 to CH4 is an attractive method for CO2
sequestration using hydrogenotrophic methanogens .
⮚ Methanogens live in anaerobic conditions, CO2 and acetate presence,
at a
temperatures between 9 – 100 °C.
⮚ Advantages of bioconversion of CO2 to CH4
1. Requires less energy for reduction of CO2.
2. Burning CH4 is carbon neutral – only liberates CO2 which is reduced in
first stage to methane.
3. CH4 from microbes is more ecofriendly than a corn ethanol.
4. Does not compete with food production.
5. No need of agricultural resources such as land, irrigation and fertilizers.
⮚ In reactors at suitable conditions, methanogens can produce methane from
carbon dioxide with 100 % conversion rate in 4 hours retention time.
⮚ Methanogens can reproduce natural gas deposit reservoirs 8
 Enzymatic Carbon Capture – Carbonic
⮚ Anhydrase
Carbonic anhydrase (CA) enzyme that can capture carbon
emissions in energy efficient manner.

⮚ Human isozyme - human carbonic anhydrase isozyme (HCAII) - This

can hydrate 1.4*10^6 molecules of CO2 per second.
⮚ Other physiological processes – respiration, bicarbonate transfer, ion transfer,
acid-base regulation and bio mineralization.
11/17/2020 CH-416 & 443 – CO2 Capture, Sequestration & Utilization naresht@nitw.ac.in 9
 Enzymatic Carbon Capture – Carbonic
Anhydrase
⮚ A bio-reactor within which
CA is immobilized on a
matrix can separate the CO2
from flue gas.
⮚ Cost is when
reduced
compared to
capture
other methods.
carbon
⮚ The bicarbonate solution is
utilized to capture the CO2
and separate, store the CO2.
⮚ The same solution can be
used to produce the limestone
and other mineral based
carbonates.

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 Enzymatic Carbon Capture – Carbonic
Anhydrase

⮚ A three phase reactor

with HCAII enzyme
immobilized onto a
silica coated porous
steel. Water is sprayed
along the column
which
causes dissolution of
CO2.

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 Enzymatic Carbon Capture – Carbonic
Anhydrase
⮚ NASA model – to purify air in confined space environments. The core of
liquid membrane consists of thin layer (330 µm) enzymatic solution.
⮚ CO2 is captured in liquid membrane and diffuses to other side in vaccum
or to a carrier gas.

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 Enzymatic Carbon Capture – Carbonic
Anhydrase
⮚ Carbozyme Inc. model – It is based
on hollow microporous propylene
microfiber, separated by control
separators which are made of thin
oxide powders..
⮚ Water vapour is used as a
sweeping
gas under moderate vaccum
condition.
⮚ The sweeping gas has reached to
95% for a flue gas with 15% CO2.
⮚ This is particularly effective for flue
gas carrying 0.05 – 40 % CO2
between 15 to 85 °C.
⮚ Harsh conditions – CA activity ⮚ 0.6 g/l enzyme can extract 99%
need to be taken care. of CO2 in flue gas.
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 Bio-mineralization using Carbon Anhydrase
⮚ Natural mineralization of CO2 – Calcite, aragonite, dolomite etc. The process
involves the reaction of CO2 with metal oxides.
⮚ Natural process of forming insoluble carbonates is known as
silicate
weathering.
⮚ Weathering can occur in both fresh water or sea water having dissolved CO2
in equilibrium with HCO3 - and CO3 -2.

⮚ Conversion of CO2 to H2CO3

is the slowest reaction which
⮚ is
CArate
having
limiting step.
= 1015-17
/s
can kmake
cat the reaction
very fast.

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 Bio-mineralization using Carbon Anhydrase
⮚ Advantages of mineralization
 Carbonates formed are safe and stable.
 They are fixed permanently over geological time scales.
 No issue of further leakage.
 Raw materials for CO2 fixing are abundant.
 No need of transportation of CO2
 Thermodynamically favourable process – carbonates
represent lower energy state than CO2.
 Carbonates can be utilized – cement, lime stone (creates revenue)
 Carbonates are used in the purification of iron in blast furnace.
 Economically viable solution
 The enzyme based mix to build the walls of buildings
 Enzyme based mineralized sealing to the saline aquifers/ coal mines

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 Bio-Sequestration of CO2 – Potential &
⮚Challenges
Potentials – Low cost, viable and safe sequestration option.
⮚ Technical Issues: mode of transfer of flue gas to alagal culture medium and
harvest of microalgae.
⮚ Fiscal Issues: Cost of setup of the facility and maintenance cost.
⮚ Terrestrial Sequestration - Trees that can survive at high temperatures are
important
⮚ Ocean Fertilization – phytoplankton are primary producers
that fix
atmospheric CO2 (~ 6–8 % of atmospheric CO2)
⮚ Ferrigation – fertilization of ocean with iron to support
phytoplankton
growth. (disturbing nature)
⮚ Microalgae are aquatic and live in all kinds of environment – fresh,
sea, sewage waters.
⮚ The growth in different environments is different for microalgae.
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 Bio-Sequestration of CO2 – Potential &
⮚Challenges
Microalgae are potential candidates for carbon sequestration
⮚ The regeneration time of microalgae is less than a day under suitable
environmental conditions.
⮚ Photosynthesis rate is higher when compares to plant rate.
⮚ Stomata of land plants alter the photosynthesis due to temperature rise
and transpiration process. Algae has no such mechanism so it can
uptake CO2 continuously even at very high temperatures.
⮚ Algal biomass – production of nutraceuticals which are rich in proteins,
pigments, lipids with omega fatty acids.
⮚ Algae biomass can be utilized as a source of biofuel.
⮚ Microalgae can assimilate CO2 and NOx from the flue gas and tolerate
the SO2 concentration upto 200 ppm

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Microalgae – Important
Products

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Microalgae Cultivation

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 Microalgae Cultivation – Opportunities and
Challenges

⮚ Microalgae cultivation can be done with any water in a shallow, circular

or raceway pond on any type of land.
⮚ Not always possible to setup cultivation plant near to plant for
space
constraints and also effect of dust on alagal bioponds.
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 Microalgae Cultivation – Opportunities and
Challenges

⮚ Flue gas cooling, compression, transport, and supply to algal mass units
costs major share of total production cost.
⮚ Enrich water with flue gas and can be transported to algal cultivation.
⮚ pH of enriched flue gas water should be monitored. Fresh water alagae –
pH
of 6 and marine water alage – pH 8 is required. 21
Microalgae Cultivation – Opportunities and
Challenges

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 Microalgae Cultivation – Opportunities and
Challenges
⮚ Microalgae cultivation has challenges as well
⮚ Some cases the transportation costs might be high
which is also common with other carbon capture technologies.
⮚ Closed systems – photo bioreactors. Fully automated with respect
to temperature, feed, pH etc.
⮚ Photo bioreactors can pose problem of contamination.
Running photo
bioreactor is an energy intensive process.
⮚ Scalability to industrial scales – maximum of 100 m2 area.
This may cost more than the value of algal mass that we produced.
⮚ Open systems – mass systems for cultivation of microalgae. These
are
shallow ponds with 10 – 50 cm deep with concrete/mud walls lining.
⮚ Consistent production depends on the variation of climate,
rain etc. Seed culture/mixotropy is needed for continuous mass
production. 23
 Cyanobacteria – CO2 Utilization
⮚ Cyanobacteria are as the most primitive photosynthetic
considered prokaryotes.
Commonly known as Cyanophyta, Myxophyta,
Cyanochloronta, blue-green algae.
⮚ This bacteria is almost 8% of total bacteria in water bodies.
⮚ The bacteria requires very less nutrients and susceptible to changes in local
physical and chemical alterations, and nutrient conditions.
⮚ Gram negative autotrophic bacteria – oxygenic photosynthesis fixing
atmospheric CO2.
⮚ They are able to compensate the difference between local and
environmental concentration of CO2 by applying carbon concentrating
mechanism (CCM).
⮚ The concentration mechanism improves photosynthetic performance and
subsequently CO2 fixation.

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 Cyanobacteria – CO2
Utilization
⮚ The bacteria adapted over billion years of time due to variation of CO2 and
O2 levels in the atmosphere.
⮚ The diffusional resistance to CO2 transfer in liquid initiated the changes
to
sustain with low-efficiency carbon gain and photorespiration.
⮚ The CCM functions to actively transport inorganic carbon species
(HCO 3
-) within the cell.
(Ci, HCO 3-, and CO2) resulting in conditional
⮚ These
accumulationof bicarbonate
changes made the inorganic transport and carbon uptake around the
primary carboxylating enzyme – ribulose bisphosphate carboxylase-
oxygenase (RuBisCO).
⮚ The concentration mechanism improves photosynthetic performance and
subsequently CO2 fixation.
⮚ These inducible, active transport mechanisms enable the cyanobacteria to
accumulate large internal concentrations of inorganic carbon that may be
up to 1000-fold higher than the external concentration.
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 Cyanobacteria – CO2 Utilization

Metabolic pathways of cyanobacteria

11/17/2020 CH-416 & 443 – CO2 Capture, Sequestration & Utilization naresht@nitw.ac.in 26
 Cyanobacteria – CO2 Utilization
⮚ Replacing the fossil fuels with RES can reduce 80% CO2 emissions.
Production of biofuels such as biodiesel, bioethanol or biogas which are
carbon neutral can reduce the additional emissions.
⮚ Biological systems are sustainable, renewable. Photosynthesis in algae can
capture the fossil fuel emissions.
⮚ It also produces betakeratanoids, amino acids, food stuff and pharma
compounds.

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 Cyanobacteria – Extracellular Polymeric
Substances polymeric substances (EPS) are natural
⮚ Extracellular high
polymers of molecular weight secreted by microorganisms
into their environment.
⮚ EPS can remain on the cell surface or can release into the surrounding
environment as released polysaccharides(RPS). Under stress conditions, the
EPS will change its properties which is a boundary between cell and
environment.
⮚ EPS of cyanobacteria – uronic acids and Sulphur groups – which
gives
negative charge and removes positively charged metals.
⮚ Used in aquaculture, waste water treatment, food,
fertilizers,
pharmaceuticals.
⮚ Flow properties of solutions
⮚ Thickening agents
⮚ Rheological properties

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 Cyanobacteria EPS as Bioflocculants and Biosurfactants
⮚ Flocculants – facilitates the formation of flocs and aggregates for fast and
easy separation of solids from liquids.
⮚ At molecular level, the repulsive forces are reduced of the particle
surfaces
which facilitates easy interactions.
⮚ Bioflocculants – environmental friendly, biodegradable, non-toxic. These
contain various organic groups and polysaccharides which are able to bind
the metals.

https://www.wur.nl/en/show/Harvesting-of-microalgae-for-oil-

extraction.htm 29
 Cyanobacteria EPS as Bioflocculants and Biosurfactants
⮚ Surfactants – Which facilitate the reduction of interfacial tension
between two liquids or liquid-solid.
⮚ Biosurfactants – surface tension reduction, emulsion stabilization, foaming
promotion. These are non-toxic and biodegradable but highly expensive.
⮚ Chemically synthesized surfactants are not biodegradable and can be toxic.
⮚ Cosmetics, pharmaceuticals, food preservatives, and detergent industries use
these biosurfactants.
⮚ Advantages
⮚ Lower toxicity
⮚ Effective at high T, pH and salinity
⮚ Enhanced oil recovery
⮚ Metal sequestering (biosorption)
⮚ Gold and platinum seperation
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 Reference
1.
s
Peter Styring, Elsje Alessandra Quadrelli, Katy Armstrong, Carbon dioxide utilization: Closing the
Carbon Cycle, Elsevier, 2015.
2. Goel M, Sudhakar M, Shahi RV, Carbon Capture, Storage and, Utilization: A Possible Climate Change
Solution for Energy Industry, TERI, Energy and Resources Institute, 2015.
3. Amitava Bandyopadhyay, Carbon Capture and Storage, CO2 Management Technologies, CRC Press,
2014. 4.
4. Fennell P, Anthony B, Calcium and Chemical Looping Technology for Power Generation and Carbon
Dioxide (CO2) Capture, Woodhead Publishing Series in Energy: No. 82, 2015.
5. Mercedes Maroto-Valer M, Developments in Innovation in Carbon Dioxide Capture and Storage
Technology: Carbon Dioxide Storage and Utilization, Vol 2, Woodhead Publishing Series in Energy,
2014.

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