PRODUCTION OF BILAL AHMED

2017-CH-80

BIOFUEL FROM
ALGAE
Contents
1.1. Introduction 2

1.2. Renewable Fuels 2

1.3. Green Fuels 3
1.4. Biofuels 3
1.5. Algae 3
1.6. Why Algae Biofuel? 3
1.7. What Type of Algae? 4
1.8. Experiment 4
1.8.1. Process Overview 4
1.8.2. Algae Growth 5
1.8.3. Algae Cultivation 5
1.8.3.1. Open Pond 5
1.8.3.2. Closed Pond System 5
1.8.4. How to Harvest Algae 5
1.8.4.1. Bulk Harvesting 5
1.8.4.2. Thickening 6
1.8.4.3. Dewatering 6
1.8.4.4. Drying by External Heat 6
1.8.5. Method of Extraction of oil 6
1.8.5.1. Oil Press 6
1.8.5.2. Solvent Extraction Method 7
1.8.5.3. Supercritical Fluid Method 10
1.8.5.4. Ultrasonic Assisted extraction 11
1.8.6. Fatty Acid Analysis 11
1.8.7. Advantages and Disadvantages of the Process 11
1.8.7.1. Advantages 11
1.8.7.2. Disadvantages 12
1.8.8. Future Aspects 12
1.8.9. Conclusion 12

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Abstract
Algae are a filamentous waste plant growing in any type of water such as fresh, sea water
etc. Normally algae are regarded as a menace in water bodies. Algae oil is an interesting
sustainable feedstock for biodiesel manufacturing. There are various methods for extracting
the oil from algae, such as mechanical pressing, hexane solvent extraction etc. The paper
discusses experimental method developed for the extraction of oil from algae which is obtained
from open pond system. It is observed that the solvent extraction method recovers almost all
the oil and leaves behind only 0.5% to 0.7% residual oil in the raw material. Because of the
high percentage of recovered oil, solvent extraction is found to be an effective method for
extraction of oils and fats, but is having disadvantage of being costly as compared to expeller
method. An experimental investigation shows that expeller pressing method can recover 75%
of the oil from algae. Even though expeller pressing method is an economical method than the
hexane solvent extraction method, further to make this method more effective, some
modifications in the design of expeller are required which will increase the recovery of oil.

1.1. Introduction

Extraction refers to an operation in which one or more components of a liquid or a solid

phase are transferred to another liquid phase. Extraction utilizes the differences in the
solubilities of components. In liquid-liquid extraction or solvent extraction, a solute in a liquid
solution is removed by contacting with another liquid solvent, which is relatively immiscible
with the solution. The liquid, which is added to solution to bring about the extraction is known
as solvent. This solvent layer is called extract and the other layer, the raffinate. Leaching
involves treating a finely divided solid with a liquid that dissolves and removes a solute
contained in the solid. Ex. oilseed extraction.

This paper discusses the extraction of oil by solvent extraction method and mechanical
pressing method, respectively. The solvent extraction method recovers almost all the oils and
leaves behind only 0.5% to 0.7% residual oil in the raw material. The solvent extraction method
can be applied to any low oil content materials. It can also be used for pre-pressed oil cakes
obtained from high oil content materials. Because of the high percentage of recovered oil,
solvent extraction has become most popular method of extraction of oils and fats. Mechanical
pressing methods include the expeller method, hydraulic presses etc.

1.2. Renewable Fuels

Renewable resources are natural resources that can be regenerated or replaced by

ecological processes on a relevant timescale. They include biological resources such as
biomass, plants, and animals. They also include freshwater, fresh air, soil fertility, and elements
like carbon and nitrogen. Renewable resources also include inexhaustible solar energy.

Though there are a number of popular technologies that generate renewable energy such
as solar and wind power, there are also simple everyday resources that are considered
renewables. In a sense, the concept of renewable generation is often solely tied to images of
solar panels and wind turbines when in reality renewables span far beyond these two products.
One can think of renewable energy in terms of the various natural occurring events that create

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it as well as common beneficial outputs (renewable commodities) that exist only because of
renewables.

1.3. Green Fuels

Green fuel, also known as bio fuel, is a type of fuel distilled from plants and animal
materials, believed by some to be more environmentally friendly than the widely-
used fossil fuels that power most of the world. In the desperate search for alternative
energy sources, green fuel has evolved as a possible fueling option as the world drains its fossil
fuel resources..

In creating basic forms of bio fuel, crops are broken down into two types: sugar
producing and oil producing. Sugar and starch producing crops, such as sugar cane or corn, are
put through a fermentation process to create ethanol. Oil producing plants, like those used in
vegetable oils, can be used much like fossil sources of oil; they create diesel that can be burned
by cars or further processed to become biodiesel.

1.4. Biofuels

They are the green alternative derived form biological materials through biomass
conversion. They are renewable resource. Their production requires more effort and resources
and can significantly reduce greenhouse gas emissions and release CO2 when burning.

1.5. Algae

A simple, non-flowering, and typically aquatic plant of a large assemblage that includes
the seaweeds and many single-celled forms. Algae contain chlorophyll but lack true stems,
roots, leaves, and vascular tissue. Algae are simple plants that range from microalgae to large
seaweeds, such as giant kelp. Algae can be grown using brackish-, sea-, and wastewater
unsuitable for cultivating agricultural crops. Most microalgae grow through photosynthesis by
converting sunlight, CO2, and a few nutrients, including nitrogen and phosphorous, into
biomass. Other algae can grow in the dark using sugar or starch.

Examples:

▪ Prokaryotic microorganisms: Cyanobacteria (Cyanophyceae)

▪ Eukaryotic microalgae: Green algae (chlorophyta) and diatoms (Bacillariophyta)

1.6. Why Algae Biofuel?

Algae can be used as biofuel because it can be grown on marginal lands useless for
ordinary crops. It high yield per acre – have a harvesting cycle of 1–10 days, can be grown
with minimal impact on fresh water resources, Can be grown using flue gas from power plants
as a CO2 source and can convert a much higher fraction of biomass to oil than conventional
crops, e.g. 60% versus 2-3% for soybean

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 Fig. 1.1: Algae

1.7. What Type of Algae ?

Botryococcus braunii – Converts 61% of its biomass into oil – 86% of it is long chain
hydrocarbons – Drops to only 31% oil under stress – Grows best between 22- 25o C (71-77
o
F).
1.8. Experiment

1.8.1. Process Overview

First algae is grown then it is followed by harvesting and extraction by different

techniques like supercritical fluid extraction and then extracted oil can be converted to biofuel
by using transesterification method.

Fig. 1.2: Process Overview

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1.8.2. Algae growth
Reproduce very quickly and need only sunlight (or other forms of energy like sugar,
water, carbon dioxide and a few inorganic nutrients) to grow.

1.8.3. Algae Cultivation

Algae can grow 20 to 30 times faster than food crops. It takes only1-10 days.
Main sources of algae are:
1.8.3.1. Open pond
▪ Open-pond systems is a method for the cultivation of algae with high-oil content.
▪ Some open sewage ponds trial production has been done in Marlborough, New Zealand
1.8.3.2. Closed loop system
▪ Closed system require cheap source of CO2 as this is not exposed toopenair.
▪ That’s why experts are thinking it would be more economical if the plant is situated next to the power
plant.

Fig. 1.3: Algae Cultivation

1.8.4. How to Harvest Algae ?

Separating algae from its medium is known as harvesting. Generally it involves two main
processes:

1.8.4.1. Bulk harvesting:-

This method aims to separate the algae biomass from the growing solution. This usually
begins with flocculation; adding chemicals to clump the suspended algae particles within the
growing solution into bigger clusters (see figure 1). Various chemicals can be used for
flocculation. The type of flocculant used will depend on the type of algae being produced the
processs used to grow and convert the algae to a biofuel.

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 Fig. 1.4: Harvesting
Flocculation is followed by collecteing the clumped algae. This can be done by one of three
methods:-

▪ Filtration - using filters to capture and remove the clumped algae.

▪ Flotation - sending air bubbles to bring the algae clumps to the surface.
▪ Gravity sedimentation - using time and gravity to bring the algae clumps to the bottom.
Many variations of each process exist, which involve the addition of chemicals,
pressurized apparatus or combined processes.
1.8.4.2. Thickening:-
Thickening aims to concentrate the biomass after it is separated. This can be
accomplished by using centrifugal forces, addition of chemicals, or using ultrasonic
radiation. In using centrifugal forces, the more dense component moves farther away from the
spinning point, while the less dense component stays closer.
The idea is to continuously collect the algae without disturbing the growing cycle, to
harvest an algae biomass with a low water content and to use the least amount of time, space,
and money.
1.8.4.3. Dewatering:-
Dewatering involves removing the water from the collected algae so that further
processing is possible and efficient. There are two approaches to this concept:
1.8.4.4. Drying by External Heat:-
Currently, drying algae using external heat is not economically feasible because of high
costs. The process requires large amounts of time, space and money and as a result the costs
are larger than any profits that could be earned.[3] A few methods of drying are sun drying,
spray drying, shelf drying, drum drying and freeze drying.

1.8.5. Methods of Extraction of Oil:-

There are various methods for the extraction of oil from algae.

▪ Oil press
▪ Solvent Extraction
▪ Super critical fluid extraction
▪ Ultrasonic assisted extraction

1.8.5.1. Oil Press

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 This method is a mechanical method and we have made use of expeller to press the
algae. Similar methods are screw expeller method, mechanical pressing method (by piston) and
osmotic shock method6,8. In the osmotic shock method the osmotic pressure is suddenly
reduced. We have carried out our work on screw expeller. The raw materials are squeezed
under high pressure in a single step. Expeller presses can recover 75% of the oil from algae.
The alga was obtained from the open pond system. It was dried by exposure to atmosphere. In
an expeller press, as the raw material is pressed, friction causes it to heat up; in some cases, the
temperatures may exceed 120 oF.

The expeller we used was a screw type machine that presses oil seeds through a caged
barrel like cavity. Algae entered the expeller press on one side of the press and products exit
was on other side of the press. The machine used friction and continuous pressure from the
screw drive to compress the filamentous algae. The algae were green in long strands like fiber.
Initially, the algae did not move easily into the screw. Its surface had to be wetted with water
for easy movement through the caged barrel. The oil seeps through small openings that do not
allow the other components to seep through. Afterwards, the pressed algae almost form cake,
was removed from the machine. Pressures involved in expeller pressing create heat in the range
of 140-210oF. Expeller processing cannot remove the last trace of oil from algae. A significant
amount of oil was left in the cake formed. The cake formed was in large quantity. It was not
subjected to solvent extraction, since the quantity of solvent required would have been much
greater.

The disadvantages of this method are:-

▪ High mechanical press, extracts 75% oil.

▪ Low efficiency
▪ Efficient for oil rich sample
▪ Lot of lubrication and power

1.8.5.2. Solvent extraction method

The solvent extraction method recovers almost all the oils and leaves behind only 0.5%
to 0.7% residual oil in the raw material. The solvent extraction method can be applied to any
low oil content materials. It can also be used for pre-pressed oil cakes obtained from high oil
content materials. Because of the high percentage of recovered oil, solvent extraction has
become most popular method of extraction of oils and fats. The materials use are green algae,
it was obtained from the open pond system and hexane. Experimental setup The algae were
obtained from the open pond system. It was dried by exposure to atmosphere. After drying, the
algae were powdered. A 50 g sample of the dried algae was placed in the thimble of the Soxhlet
apparatus. The thimble is made from thick filter paper, which is loaded in the main chamber of
Soxhlet extractor. The Soxhlet extractor is placed onto a flask containing extraction solvent.
The Soxhlet is than equipped with a condenser. The solvent is heated to reflux. The solvent
hexane forms vapors, which travels up a distillation arm, and floods into the chamber housing
the thimble of solid. The condenser ensures that any solvent vapor that cools drips down into
the chamber housing the solid material. The chamber containing the solid material slowly fills
with warm solvent. Some of the desired compound will then dissolve in the warm hexane.
When the Soxhlet chamber is almost full, the chamber is automatically emptied by the siphon

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side arm, with hexane running back to the distillation flask. This cycle was repeated for varying
time.

During each cycle, a portion of the oil is dissolved in hexane. After many such cycles,
desired oil was concentrated in the distillation flask. After extraction hexane was removed,
yielding the extracted compound. The insoluble portion of the algae remains in the thimble.
The same process was repeated but this time the open pond algae were 75% moist instead of
complete dry. The same process was repeated but this time, the open pond algae were 50%
moist instead of complete dry.

Fig. 1.5: Soxhlet Apparatus

On industrial scale like the Soxhlet process, the extraction system shown in the diagram
processes a single batch of dried algae at a time. The dried algae is placed inside the Extraction
Chamber and liquid hexane is placed in the Hexane Reservoir. Prior to circulating the hexane
through the dried algae, the system must be evacuated. The hexane is sealed inside the Hexane
Reservoir during evacuation (to prevent hexane loss by evaporation), and the Vacuum Pump
is used to bring the pressure of the system down to approximately 2.5 psia. After vacuum has
been achieved, the entire system will be sealed to maintain it. At this point, the Hexane
Reservoir is opened so that the hexane will drain into the Extraction Chamber and begin
dissolving oil from the algae. Like the Soxhlet setup, the Extraction Chamber will drain when
a siphon is created. The mixture of hexane and oil, called miscella, drains to the Miscella Tank.
A hot-water bath surrounds the Miscella Tank. Because of the low operating pressure of the
system, the boiling point temperature of the hexane is lower (approximately 85°F), which
means that domestic hot water (110120°F) can be used to boil the hexane. The hexane vapor
rises through a tube to the hexane condenser, where the hexane is condensed into liquid. This
hexane condensate drains back to the Hexane Reservoir and then back to the Extraction
Chamber. The hexane is circulated in through the system until adequate oil extraction is
achieved.

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 Fig. 1.6: Solvent Extraction Method

▪ Hexane recovery from miscella

Extracting the oil from the algae is only half of the job of the extraction system. After
extraction, the hexane must be recovered from the miscella and the algae mill. This is done by
using the same heating and cooling system used during the extraction phase. To recover the
hexane from the miscella, the hot water bath is used again to boil the hexane from the Miscella
Tank. However, unlike the extraction phase, the condensed hexane does not flow to the
Extraction Chamber. Instead, a valve at the outlet of the Hexane Reservoir causes the hexane
to collect here. At the end of this recovery process. oil is left in the Miscella Tank, and the
recovered hexane is in the Hexane Reservoir.

▪ Hexane recovery from algae mill

Recovering the hexane from the algae mill is done in a similar way to the recovery from
the miscella tank. A hot-water bath surrounds the Extraction Chamber, and during the hexane
recovery from the mill, hot water enters the bath and heats the chamber. The hexane contained

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in the mill is evaporated, and it flows to the condenser. The hexane condensate then drains to
the Hexane Reservoir, where it is stored for use in the next extraction batch.

1.8.5.3. Super Critical Fluid Method

The supercritical fluids method extracts up to 100 percent of the oil from algae.
Carbon dioxide acts as the supercritical fluid -- when a substance is pressurized and heated to
change its composition into a liquid as well as a gas. At this point, carbon dioxide is mixed
with the algae. When they're combined, the carbon dioxide turns the algae completely into oil.
The additional equipment and work make this method a less popular option.

Once the oil's extracted, it's refined using fatty acid chains in a process
called transesterification. Here, a catalyst such as sodium hydroxide is mixed in with
an alcohol such as methanol. This creates a biodiesel fuel combined with a glycerol. The
mixture is refined to remove the glycerol. The final product is algae biodiesel fuel.

The process of extracting oil from the algae is universal, but companies producing algae
biodiesel are using diverse methods to grow enough algae to produce large amounts of oil.

Carbon dioxide was supplied with a purity of 99.995% from Linde Gases LTDA.
Supercritical carbon dioxide extractions were performed at the temperature range 50 – 85ºC
and pressures range of 200 – 250 bar. These extraction conditions were chosen taking into
account previous work reported for the extraction of lipids from other microalgae.

Fig. 1.7: Supercritical Fluid Method

A schematic diagram of the pilot plant, Bench Scale SFE-500 Separex unit, is given in
Figure 1. Solvent (CO2), from the cylinder, is delivered through a pipe to the condenser. Liquid
CO2 reaches the inlet of the high pressure pump rated up to 200 bar. Compressed fluid is fed
to the heater prior to entering the extraction vessel. The unit contains an extraction container
of 450 ml, closed with stainless steel porous discs. The extractor is heated by a heating jacket

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surrounding the outer surface of the vessel. The extraction pressure was controlled by means
of a back pressure regulator valve, BPR (Tescom 27-1700) where depressurization of CO2
flow stream exiting the extraction vessel took place. The extracted substances were precipitated
and collected into a glass trap, immersed in an ice bath. To ensure a total recovery of
compounds, the gas flow coming out from the first trap passes through a second glass trap. The
extraction pressure is measured at the entrance of the extraction vessel with an accuracy of ±1
bar.

1.8.5.4. Ultrasonic-assisted Extraction

In this ultrasonic waves are used to create cavitation bubbles in a solvent material which 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.

1.8.6. Fatty acid analysis

Lipid extracts were transmethylated with methanol-acethyl chloride, as described by

Lepage and Roy [29], in the presence of an appropriate amount of heptadecanoic acid as an
internal standard. The methyl ester were then analyzed on a 7890 Agilent gas chromatograph
(GC), equipped with a flame ionization detector. Separation was carried out on 0.32 mm x 30
m fused silica capillary column (0.32 μm film thickness) Sulpelcowax 10 (Supelco, Bellafonte
PA, USA) with helium as carrier gas at a flow rate of 3.5 ml/min. The column temperature was
programmed at an initial temperature of 200ºC for 8 min, then increased at 4ºC/min to 240ºC
and held there for 8 min. Injector and detector temperatures were 250 and 280ºC, respectively
and split ratio was 1:50. FAMEs were identified and their response factors calculated by
comparing peak areas of known quantities of authentic standards (Supelco) to the internal
standard, heptadecanoic acid. Averages of duplicate injections were reported.

1.8.7. Advantages and Disadvantages of the Process

1.8.7.1. Advantages

Advantages for production of biofuel from algae are:-

▪ Bio-based fuel with essentially carbon neutral combustion

▪ Drop in replacement for petroleum-based liquid fuels

▪ Inherently renewable

▪ Absorbs carbon dioxide as it grows

▪ Both waste CO2 and wastewater can be used as nutrients

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▪ Higher energy per-acre than other bio-fuels

▪ Can be grown on land unsuitable for other types of agriculture

▪ Scalable: Study found that 17 percent of U.S. oil imports could be met with algae

▪ Investments are being made

▪ Production is presently scaling up (Navy buying 100,000 gallons this year)

▪ Research has been underway for 50 years

1.8.7.2. Disadvantages

Disadvantages for production of biofuel from algae are:-

▪ Need to be grown under controlled temperature conditions

▪ Requires a considerable amount of land and water

▪ Cold flow issues with algal biofuel

▪ Some researchers using genetic engineering to develop optimal algae strains

▪ Requires phosphorus as a fertilizer which is becoming scarce

▪ Fertilizer production is carbon dependent

▪ Relatively high upfront capital costs

▪ Not clear yet what the ultimate cost per gallon will be. Presently too high.

1.8.8. Future Aspects

▪ Biofuel Vehicles “Green” Buildings

▪ More Research & Development

▪ Further Private & Government Investment

▪ Clearer Regulatory & Statutory Guidelines for Algae Businesses

1.8.9. Conclusion

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▪ Algae Biofuel is a very promising candidate to replace fossil fuels

▪ Algae’s cultivation does not require that it compete with food crops •

▪ Ability for algae to be cultivated on non-arable land, using saltwater, greatly reduces
its impact on the environment

▪ Produces over 20 times the oil production of any food crop - an acre of algae can
produce almost 5,000 gallons of biodiesel

▪ Production can reach 60 billion gallons/year that could replace all diesel in the U.S.

▪ However, current economic climate makes development of algal programs quite costly

▪ For algae to be truly competitive, it should receive its own share of the subsidies
currently only allocated to feedstock

▪ A highly feasible way to continue biofuel development while remaining commercially

competitive is to produce algal fuel as a co-product to more lucrative products such as
animal feed and nutraceuticals product

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