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ALGAE CONVERSION

Algae
• Plant-like organisms
• Photosynthetic and aquatic
• Have simple reproductive structures.
• Distributed worldwide in the sea, in freshwater and in wastewater
Types
Microalgae Macroalgae
microscopic organisms, unicellular multiple cells which organize to
or filamentous, Size: 0.5-100µm structures resembling roots,
stems, and leaves of higher
plants, e.g kelps
Size: mm – m scale

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Macroalgae
• Mainly consists of carbohydrates which are good candidates for biofuel production such as
biogas, bioethanol and bio-oils
• Can be harvested more easily
• Classified into three major groups based on their photosynthetic pigmentation variations: red
(Rhodophyta), brown (Phaeophyta) and green (Chlorophyta)
• Is cultivated at present for food production, fertilizers and hydrocolloid extraction in Asia with
China, Korea, Philippines and Japan accounting for about 72% of global annual production.
• The productivity for macroalgae ranges from 150 to 600 t per hectare per year fresh weight and
the total worldwide production reaches 12 million tonnes dry matter/year
• Seasonal nature of growth and culture; thus methods of storage or preservation must be
developed to enable its use in year-round fuels manufacturing processes
Microalgae (They’re Awesome!)
• The fastest growing plants in the world
• The most important classes are: green algae (Chlorophyta), red algae (Rhodophyta) and diatoms
(Bacillariophyta).
• Autotrophic algae require only inorganic compounds such as CO2, salts and a light energy source for
growth
• Heterotrophic algae are nonphotosynthetic; therefore require an external source of organic
compounds (e.g.glucose) to stimulate growth and as an energy source
• Mixotrophic algae have the ability to both perform photosynthesis and acquire exogenous organic
nutrients
• Can inhabit diverse ecological habitats ranging from freshwater, brackish water, or seawater
• Equipped to thrive in various extreme temperatures and pH conditions
• Can fix CO2 from three different sources, namely: CO2 from the atmosphere; CO2 in discharge gases
from heavy industry, and; CO2 from soluble carbonates
Composition
Composition
Starch content in Microalgae
Why ALGAE?
• Does not compete with agriculture
• High yield per acre
• Contains no sulphur therefore no SO2 emissions
• Non toxic and highly biodegradable
• Does not require soil for growth
• Adaptable anywhere even at great distances from water
• Abatement of CO2 – carbon neutral
Why ALGAE?
• Have simple growth requirement, tolerate wide range of pH and temperature, can grow to high
densities, and use light, carbon dioxide, and other inorganic nutrients efficiently
• Have higher photon conversion efficiency
• Can synthesize & accumulate large quantities of carbohydrate biomass
• Microalgae easily grown in various aquatic environments i.e. fresh water, saline water or
municipal waste water, thus reduces the use of freshwater use for agriculture purposes.
• Microalgae can tolerate and utilize substantially higher levels of CO2
• Grows much faster than crop
• Yields >10x those for land plants so much less land is needed

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Microalgae Cultivation Factors
• Temperature
o influences algal growth rate, cell size, biochemical composition and nutrient requirements
o range of temperatures (from 15 to 40 °C), depending upon strain, region, and season
o Below optimal growth temperatures, growth rate (μ) increases with increasing temperature but declines
markedly above the species- or strain- specific optimum
o Temperature is also reported to impact starch & lipid content in the algal cell
• Light
◦ is the energy source during photoautotrophic growth phase and organisms use light energy to convert carbon
dioxide to organic compounds—especially, sugars
◦ range of light intensity varies from 1500 to 8500 W⋅h/m2/day with strong regional and seasonal dependence
◦ Light intensity effects growth of algae through its impact on photosynthesis
◦ The growth rate of algae is maximal at saturation intensity and decreases with both increase or decrease in
light intensity
◦ Light intensity also affects the cellular composition of algae ,Dunaliela tertiolecta exhibits a decrease in
protein content and an increase in the lipid fraction with increasing light intensities up to saturation
Microalgae Cultivation Factors
• pH
◦ determines the solubility and availability of CO2 and essential nutrients, and because it can have a
significant impact on algal metabolism
◦ Maximum algal growth occurs around neutral pH,
◦ acidic conditions can alter nutrient uptake or induce metal toxicity and thus affect algal growth
◦ Alkaline conditions limits the availability of carbon from CO2, which, in turn, suppresses algal growth

• Salinity
◦ refers to sodium chloride concentration unless otherwise specified
◦ Is the factor that alters the biochemical composition of algal cells
◦ Exposing algae to lower or higher salinity levels than their natural (or adapted) levels can change growth
rate and alter composition
◦ higher salinity increases the algae lipid content
Microalgae Cultivation Factors
• Nutrients
◦ Nitrogen and phosphate are two important macronutrients for growth and metabolism of algal cells
◦ Nitrogen is a fundamental element for the formation of proteins and nucleic acids
◦ Major effects of nitrogen deficiency in algal culture results in a higher lipid/protein ratio at the expense
of growth rate
◦ Phosphate is also a part of the backbone of DNA , RNA & phospholipids
◦ Limitation of these key nutrients shifts the metabolic pathway of the organism –e.g. increases the total
lipid content of green algae
◦ Carbon, hydrogen, and oxygen are three essential non-mineral nutrients
◦ Carbon is essential for photosynthesis and hence algal growth and reproduction
◦ Trace metals are metals present in algal cells in extremely small quantities (<4 ppm)
◦ Iron (Fe), manganese (Mn), cobalt (Co), zinc (Zn), copper (Cu) and nickel (Ni) are the six most important
trace metals required by algae for various metabolic functions
Microalgae Cultivation Factors
• Mixing
◦ It homogenizes the cells distribution, heat, metabolites, and facilitates transfer of gases
◦ A certain degree of turbulence, especially in large-scale production, is desirable in order to promote the
fast circulation of microalgae cells from the dark to the light zone of the reactor
◦ high liquid velocities and degrees of turbulence (due to mechanical mixing or air bubbles mixing) can
damage microalgae due to shear stress
◦ The optimum level of turbulence (above which cell death occurs) is strain dependent and should be
investigated in order to avoid decline in productivity
Summary of factors
Summary of factors
Microalgae Cultivation System
• Culture system must have as many of the following characteristics as possible
1. high area productivity
2. high volumetric productivity
3. inexpensiveness (both in terms of investment and maintenance costs)
4. easiness of control of the culture parameters (temperature, pH, O2, turbulence)
5. reliability
Microalgae Cultivation System-Open-Air
systems
• It is simply growing algae in natural waters, lakes, lagoons, ponds) and artificial ponds or
containers.
• The ponds have to be shallow and wide as this maximizes the sunlight taken in by the algae
• Nutrients can be provided through runoff water from nearby land areas or by channeling the
water from sewage/water treatment plants.
• Advantages: simplicity and convenience, easier to construct and operate, resulting in low
production and operating costs.
• Disadvantages: uneven light intensity and distribution within the pond would have negative
effects on the algae's growth.
Microalgae Cultivation System-Open-air
systems
• Raceway pond
◦ They are typically made of a closed loop, oval shaped recirculation channels, generally between 0.2 and
0.5 m deep
◦ The pond is designed in a raceway configuration, in which a paddlewheel circulates and mixes the algal
cells and nutrients.
◦ The raceway are typically made from poured concrete or they are simply dug into the earth and line
with a plastic liner to prevent the ground from soaking up the liquid.
◦ Baffles in the channel guide the flow around the bends in order to minimize space.
◦ The system is often operated in a continuous mode, i.e the algae broth and nutrients is added in front of
the paddlewheel , and algal broth is harvested behind the paddlewheel after it has circulated through
the loop.
Microalgae Cultivation System-Close
pond system
• An alternative to open ponds are closed ponds.
• Closed ponds are just variations of the open pond system, where one simply closes the open pond
off with a greenhouse.
• Closed ponds allow better control over the environment than that for the open ponds.
• Cost more than the open ponds, and considerably less than photobioreactors for similar areas of
operation
• Usually closed ponds are used in Spirulina cultivation
• Advantages of closed pond over many of the problems associated with an open system :
◦ Allows more species to be grown
◦ Allows the species that are being grown to stay dominant
◦ Extends the growing season and if heated it can produce algae year round
◦ Possible to increase the amount of carbon dioxide, further increasing growth of algae
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Microalgae Cultivation System-
Photobioreactor
• Is a piece of equipment that provides a controlled environment to cultivate algae.
• Parameters such as carbon dioxide, water, temperature, exposure to light, mixing regime, etc can be
controlled very accurately.
• These systems receive sunlight either directly through the transparent container walls or via light
fibres or tubes that channel it from sunlight collectors
• The cost of cultivation using photobioreactors is very high, preventing the photobioreactor from
being used as much.
• Advantages : reduced contamination risk, no CO2 losses, reproducible cultivation conditions,
controllable hydrodynamics and temperature, and flexible technical design
• Many different designs have been developed, but the main categories include:
• tubular (e.g. Helical, manifold, and α-shaped);
• flat (e.g. Alveolar panels and glass plates);
• column (e.g. Bubble columns and airlift).
Microalgae Cultivation System-
Photobioreactor
Tubular photobioreactors
◦ It can be horizontal, near horizontal, vertical, inclined and conical-shaped
◦ Consists of an array of straight transparent tubes that are usually made of plastic or glass with 0.1 m or
less in diameter
◦ Microalgal broth is circulated by a pump from a reservoir to the solar collector and back to the reservoir.
◦ Systems are relatively cheap, have a large illumination surface area and have fairly good biomass
productivities
◦ Tube diameter is limited because light does not penetrate too deeply in the dense culture broth that is
necessary for ensuring a high biomass productivity of the photobioreactor.
◦ Difficult to control culture temperatures in most tubular photobioreactors. Although they can be
equipped with thermostat to maintain the desired culture temperature, this could be very expensive
and difficult to implement.
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Microalgae Cultivation System-
Photobioreactor
Flat-plate photobioreactors
◦ Made of transparent materials for maximum utilization of solar light energy
◦ A thin layer of very dense culture is mixed or flown across a flat transparent panel, which allows
radiation absorbance in the first few millimetres thickness.
◦ Suitable for mass cultures of microalgae due to the low accumulation of dissolved oxygen and the high
photosynthetic efficiency achieved when compared to tubular designs
◦ Usually, the panels are illuminated mainly on one side by direct sunlight and have the added advantage
that they can be positioned vertically or inclined at an optimum angle facing the sun permitting a better
efficiency in terms of energy absorbed from incident sunlight.
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Microalgae Cultivation System-
Photobioreactor
Column photobioreactors
◦ Occasionally stirred tank reactors but more often bubble columns or airlifts
◦ The columns are placed vertically, aerated from the bottom, and illuminated through transparent walls
or internally.
◦ Column bioreactors offer the most efficient mixing, the highest volumetric gas transfer rates, and the
best controllable growth conditions
◦ They are low-cost, compact and easy to operate
◦ Their performance (i.e. final biomass concentration and specific growth rate) compares favorably with
the values typically reported for tubular PBRs.
◦ These reactor designs have a low surface/volume, but substantially greater gas hold-ups than horizontal
reactors and a much more chaotic gas–liquid flow
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MIT rooftop,1950
Recovery of microalgae biomass

Stage 1 (harvesting/primary concentration): increases the biomass concentration by a concentration factor of 10–20. The
material retains its fluid like consistency.
Stage II (thickening): thickens the primary concentrate by an additional concentration factor of 10 and generates a
material with slurry-like consistency.
Stage III (dewatering): dewaters the thickened biomass to approximately 15–25% solids and generates a wet paste.
Stage IV (drying): removes unbound and possibly bound water, generating a dry solid and may increase stability by
minimise spoilage.
Recovery of microalgae biomass
• Properties of microalgae which influence their recovery include:
1. particle shape ( filamentous, rods, spheres, or chains),
2. particle size (generally between 2 and 20 mm)
3. specific weight (generally between 1.05 and 1.1)
4. charge (usually negative)

• These properties depend on the microalgae, the growth conditions and the age of the culture.
Recovery of microalgae biomass
• The recovery of microalgal biomass requires one or more solid–liquid separation steps is a
challenging phase of the algal biomass production process
• Accounts for 20–30% of the total costs of production according to one source
• The processes involved include flocculation, filtration, flotation, and centrifugal sedimentation;
some of which are highly energy intensive
• Low cell densities (typically in the range of 0.3–5 g /l)when there is limited light penetration,
and the small size of some algal cells (typically in the range of 2–40 mm), make the recovery of
biomass difficult
• Factor in selection of harvesting technology include strain selection, which are much easier to
harvest and desired product concentration
Common industrial solid-liquid separation techniques
Recovery of microalgae -Flocculation
• First stage in the bulk harvesting process that is intended to aggregate the microalgal cells in order to increase
the effective ‘‘particle’’ size
• Flocculation is a preparatory step prior to other harvesting methods such as filtration, flotation or gravity
sedimentation
• Since microalgae cells carry a negative charge that prevents natural aggregation of cells in suspension, addition
of flocculants such as multivalent cations and cationic polymers neutralises or reduces the negative charge
• Multivalent metal salts like ferric chloride (FeCl3), aluminium sulphate (Al2(SO4)3) and ferric sulphate
(Fe2(SO4)3) are suitable flocculants, Magnafloc LT-25, adjustment of the algae culture pH using NaOH, Chitosan
• Flocculation efficiencies of >80%.
• The main disadvantage of this separation method is the additional chemicals are difficult to remove from the
separated algae
• Use of flocculant is often too expensive for large operations
• Interrupting the carbon dioxide supply to an algal system can cause algae to flocculate on its own, which is
called "autoflocculation"
Recovery of microalgae -Ultrasonic
aggregation
Ultrasound gentle, acoustically induced aggregation followed by enhanced sedimentation
Achieved 92% separation efficiency and a concentration factor of 20 times (the factor by which
the original liquid mixture has been concentrated).
The main advantages of ultrasonic harvesting are that it can be operated continuously without
inducing shear stress on the biomass, which could destroy potentially valuable metabolites, and
it is a non-fouling technique
Recovery of microalgae -Floatation
Dissolved air floatation
◦ Flotation methods are based on the trapping of algae cells using dispersed micro-air bubbles
◦ It uses alum to flocculate an algae/air mixture, with fine bubbles supplied by an air compressor

Froth Flotation
◦ separating algae from the medium by adjusting pH and bubbling air through a column to create a froth
of algae that accumulates above liquid level
◦ The algae collects in a froth above the liquid level, and may be removed by suction.
◦ The pH required depends on algal species

Froth flotation and drying are currently considered too expensive for commercial use.
Recovery of microalgae - Centrifugation
• Is preferred for harvesting of high value metabolites and extended shelf-life concentrates
• The process is rapid and energy intensive
• Recovery depends on the settling characteristics of the cells, slurry residence time in the centrifuge,
and settling depth
• The disadvantages of the process include high energy costs and potentially higher maintenance
requirements due to freely moving parts
• Harvesting efficiency of>95%, and increase in slurry concentration by up to 150 times for 15% total
suspended solids are technically feasible
• Continuous-flow centrifugation with the classical Foerst rotor is widely used method
• Is reasonably efficient, but sensitive algal cells may be damaged by pelleting against the rotor wall
• Is essentially unselective ; all particles with a sedimentation rate above some limiting value will be
collected.
Recovery of microalgae - Gravity
sedimentation
• Gravity sedimentation is the most common harvesting technique for algae biomass in
wastewater treatment because of the large volumes treated and the low value of the biomass
generated.
• However, the method is only suitable for large (ca. >70 mm) microalgae such as Spirulina
• More diluted than centrifugally recovered biomass, which substantially influence the
economics of product recovery further downstream
• Not practical for microalgae since the sinking rate of small micro-algae 4–5 µm in the is
‘insignificantly small’
Recovery of microalgae -Filtration
• A conventional filtration process is most appropriate for harvesting of relatively large (>70 mm)
microalgae such as Coelastrum and Spirulina.
• It cannot be used to harvest algae species approaching bacterial dimensions (<30 mm) like
Scenedesmus, Dunaliella and Chlorella.
• Conventional filtration operates under pressure or suction, filtration aids such as cellulose can
be used to improve efficiency
Recovery of microalgae -Filtration
• For recovery of smaller algae cells (<30 mm), membrane microfiltration and ultra-filtration (a
form of membrane filtration using hydrostatic pressure) are technically viable alternatives to
conventional filtration.
• It is suitable for fragile cells that require low trans-membrane pressure and low cross-flow
velocity conditions. For processing of low broth volumes (<2m3 per day), membrane filtration
can be more cost effective compared to centrifugation.
• Owing to the cost for membrane replacement and pumping in larger scales of production (>20
m3 per day), centrifugation may be a more economic method of harvesting the biomass
Recovery of microalgae -Filtration
Microstrainers
◦ Attractive harvesting method because of their mechanical simplicity and availability in large unit sizes.
◦ The recent availability of very fine mesh polyester screens has revived interest in their use for
microalgae harvesting.
◦ Subsequent studies concluded that it would be necessary to flocculate the cells prior to microstraining.
◦ the original suspension may be faintly green, which could be further concentrated
Microstrainers
Summary
Dehydration process
• The harvested biomass slurry (typical 5–15% dry solid content) is perishable and must be
processed rapidly after harvest
• Methods that have been used include sun drying, low-pressure shelf drying, spray drying,
drum drying, freeze drying
• Sun drying is the cheapest dehydration method; but main disadvantages include long drying
times, the requirement for large drying surfaces, and the risk of material loss
• Spray drying is commonly used for extraction of high value products, but it is relatively
expensive and can cause significant deterioration of some algal pigments
• Freeze drying is equally expensive, especially for large scale operations, but it eases extraction
of oils.
• Intracellular elements such as oils are difficult to extract from wet biomass with solvents
without cell disruption, but are extracted more easily from freeze dried biomass
Oil Extraction for Biofuel-Mechanical
Method
Expression/Expeller press:
Algae is dried it retains its oil content, which then can be "pressed" out with an oil press.
Since different strains of algae vary widely in their physical attributes, various press configurations
(screw, expeller, piston, etc) work better for specific algae types.
Drying temperature during lipid extraction affects both the lipid composition and the lipid yield from
the algal biomass

Ultrasonic-assisted Extraction:
Ultrasonic extraction can greatly accelerate extraction processes.
Ultrasonic waves are used to create cavitation bubbles in a solvent material, when these bubbles
collapse near the cell walls, it creates shock waves and liquid jets that causes those cells walls to
break and release their contents into the solvent.
OriginOil developed a wet extraction process that combines ultrasound and electromagnetic pulse
induction to break the algae cell walls. Carbon dioxide is added to the algae solution, which lowers
the pH, and separates the biomass from the oil
Oil Extraction for Biofuel-Chemical
Method
• Solvent extraction is normally done directly from the lyophilized biomass
• a quick and efficient extraction method that slightly reduces the degradation.
• Several solvents can be used such as hexane, acetone
• Possible to obtain up to 98% quantitative extraction of purified fatty acids
• For extraction of metabolites in microalgae such as astaxanthine, carotenoid etc, the cell undergo
disruption first for release of the metabolites of interest.
• Several methods can be used depending on the microalgae wall and on the product nature to be
obtained
• Can be mechanical action (e.g. cell homogenizers, bead mills, ultrasounds, autoclave, and spray
drying) or non-mechanical action (e.g. freezing, organic solvents and osmotic shock and acid, base
and enzyme reactions).
• Other type of oil extraction is supercritical fluid extraction CO2 liquid
Videos
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References
Huihui Chen, Dong Zhou, Gang Luo, Shicheng Zhang, Jianmin Chen, Macroalgae for biofuels
production: Progress and perspectivesReview Article, Renewable and Sustainable Energy
Reviews, Volume 47, July 2015, Pages 427-437
Liam Brennan, Philip Owende, Biofuels from microalgae—A review of technologies for
production, processing, and extractions of biofuels and co-products, Renewable and Sustainable
Energy Reviews, Volume 14, Issue 2, February 2010, Pages 557-577
Rojan P. John, G.S. Anisha, K. Madhavan Nampoothiri, Ashok Pandey, Micro and macroalgal
biomass: A renewable source for bioethanol, Bioresource Technology, Volume 102, Issue 1,
January 2011, Pages 186-193
http://www.oilgae.com/
http://repositorio.ucp.pt/bitstream/10400.14/6717/5/Microalgal%20Reactors%20A%20Review
%20of%20Enclosed%20System%20Designs%20and%20Performances.PDF

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