A STUDY INTO T HE C ULTIVATION OF ALGAE

FOR C ARBON D IOXIDE SEQUESTRATION FROM A

POWER P LANT AND IT’S USE AS A BIO F UEL.

Adam A Marsh
0404304
15 th December 2008
Cardiff University
 A STUDY INTO THE CULTIVATION OF ALGAE

FOR CARBON DIOXIDE SEQUESTRATION FROM A POWER PLANT

AND IT’S USE AS A BIO FUEL .

ADAM A MARSH

0404304

15T H DECEMBER 2008

MSC SUSTAINABLE ENERGY AND ENVIRONMENT

CARDIFF SCHOOL OF ENGINEERING

CARDIFF UNIVERSITY
ABSTRACT

This review explores the possibilities of using algae to remove carbon dioxide
from power plant flue gas by photosynthesis through review of literature.
Different species of algae, algal products and factors affecting the photosynthetic
and carbon dioxide fixation rates were explored. The principle was applied to a
1500MWe coal fired power station whilst addressing the possibilities for using the
produced biomass as a fuel.

It is shown that the algal species Chlorella sorokiniana can be grown from the
flue gas emissions of a coal fired power plant in the South West ern regions of
the United Kingdom. The entire carbon dioxide emissions from a 1500MWe coal
fired power plant can be absorbed in a 2x2km field of Chlorella sorokiniana with
a starting algal concentration of 5x107 cells.ml-1, producing biomass at an
average rate of 14.2 kg.s -1. Directly burning this biomass when dry will provide
5% of the fuel demand whilst anaerobic digestion will provide 7.3%. It has been
determined that the most useful product from such a product is to be biodiesel
from hydrocarbon produci ng algal species.
DECLARATION
CONTENTS

LIST OF FIGURES 3

LIST OF TABLES 6

1. I NTRODUCTION 7

2. P HOTO- BIOREACTORS 10

3. A LGAE 13

3.1 Chlorella vulgaris 14

3.2 Chlorella sorokiniana 15
3.3 Botryococcus braunii 15
3.4 Chlamydomonas reinhardtii 16

4. P HOTOSYNTHESIS 20

4.1 Light 21
4.1.1 Light Intensity 23
4.1.2 Photoperiod 26
4.1.3 Photo-Limitation 27
4.1.4 Local Conditions 35
4.2 Carbon Dioxide 38
4.2.1 Concentration 38
4.2.2 Fixation Rate 40
4.3 Temperature 43
4.4 Nutrients 44

5. CARBON DIOXIDE SEQUESTRATION 46

1
6. A LGAE BIOFUEL 49

6.1 Biomass 49
6.2 Anaerobic Digestion 50
6.3 Biodiesel 52

7. CARBON STORAGE 55

8. HARVESTING 56

9. C ONCLUSIONS 57

R EFERENCES 59

A PPENDIX

2
LIST OF FIGURES

Figure Description Page

1.1 2006 UK Electricity Generation Mix

2.1 (A) Arial view of a raceway pond

(B) A tubular photobioreactor with horizontal tubes

3.1 The changes in dissolved O 2, pH and volume of the H2

produced during the cultivation of sulphur deprived
algae under photoautotrophic conditions.

4.1 Chlorophyll light absorption spectra

4.2 The growth rates of four species of algae at 25oC
under different intensities of continuous light.
4.3 The impact of light intensity on Botryococcus Braunii
algal growth at 23 oC, 12h light, 12h dark.
(A) Low light range (W.m-2); (B) High light range (W.m -2)
4.4 Relative total lipid content (rTLC) of Botryococcus
braunii under various light intensities.
4.5 The mean relative lipid content of three Botryococcus
braunii strains at different irradiance, 25 oC
4.6 Impact of different photoperiods on algal growth of
Botryococcus braunii at 25 oC and 30Wm-2
4.7 Light intensity change with depth at different algal
concentrations.
4.8 Effect of cell concentration on illuminated volume
fraction of a cubical photo-bioreactor.

3
 A= Single side illumination at 325µmol.m -2.s-1
B= Two side illumination at 162.5µmol.m -2.s-1
4.9 Schematic representation of a cuboidal reactor,
illuminated exteriorly from above.
4.10 Changes in light distribution coefficient with increasing
depth of a cuboidal photobioreactor.
4.11 Schematic representation of a cylindrical reactor,
illuminated exteriorly.
4.12 Changes in light distribution coefficient with increasing
diameter of an externally illuminated photobioreactor.
4.13 Schematic representation of a cylindrical reactor,
illuminated interiorly.
4.14 Changes in light distribution coefficient with increasing
diameter of an internally illuminated photobioreactor.
4.15 Yearly total global horizontal irradiation
(a) Europe, (b) UK and Ireland
4.16 Monthly variation of Solar Irradiance in Cardiff
4.17 Effects of different concentrations of CO2 aeration
of the growth of Chlorella sp.
4.18 Effect of CO2 concentration on the growth of Chlorella
sorokiniana H-84 at 40oC
4.19 Effect of gas flow rate on CO2 fixation and O 2 evolution,
4.20 Effect of luminous intensity on CO2 fixation and O2
evolution by Chlorella vulgaris,
4.21 Comparisons of the total amount and efficiency of CO2
` reduction in the single and the six-parallel
photobioreactor of semicontinuous Chlorella sp. Under
2%, 5%, 10% and 15% CO 2 aeration.
4.22 Temperature effects on photosynthetic activity
4.23 Impact of temperature effects on growth over time,

4
 (a) Botryococcus braunii
(b) Chlorella sorokiniana

5.1 Input and output characteristics of a coal fired power

station
5.2 Photobioreactor design dimensions

6.1 Relationship of optical density to algae cell number and

dry weight biomass.
6.2 Process flow schematic for bio-diesel production

5
LIST OF TABLES

Table Description Page

2.1 Comparison of the properties of different large-scale

algal culture systems

3.1 Chemical composition of C. sorokiniana H-84 grown in

air containing 10% CO2 at 35oC.

4.1 Optimum temperatures for four species of algae

4.2 Typical Nutrient Supplementation

6.1 Chemical composition of biomass

6.2 Range of biochemical methane potential data from

biomass or waste feedstock.

6.3 Comparison of some sources of Bio-diesel

6.4 Comparison between Extract and Cass-C Heavy Oil

8.1 Biomass recovery options

6
1. INTRODUCTION

Recent technologies have made it possible to take accurate measurements of

many of the processes at work in the atmosphere. Phenomenon such as global
warming, increased carbon dioxide levels and the correlations between the two
have been strongly researched and heavily debated in recent years. Human
industrial activities and energy production through the burning of fossil fuels are
currently regarded as the major causes of this increase in carbon dioxide and
average global temperature. Immediate drastic reductions in carbon dioxide
emissions are needed to quench the related environmental effects.

In the UK, approximately 90% of energy requirements are provided by oil, gas
and coal.1 Figure 1.1 shows the UK electricity generation mix for the year 2006,
where 76% is supplied by fossil fuels. Fossil fuel reserves remain plentiful,
especially coal, and are predicted to remain the predominant sources of energy
in 2020. The British Government do however, aim to reduce carbon dioxide
emissions from 1990 levels by 60% by 2050 lead by benchmark reductions of
26-32% by 2020 and 12% by 2012, the latter of which is a legally bound
agreement through the Kyoto Protocol. Outside of the UK, coal remains a rapidly
growing fuel. In 2006, China built 105GW of new coal-fired power stations whilst
the rapidly growing country of India will remain heavily reliant on coal for
decades to come. Both China and India are also signed to the Kyoto Protocol.

7
 Figure 1.1; 2006 UK Electricity Generation Mix

Carbon sequestration or carbon capture and storage is the process of removing

carbon dioxide from the flue gasses produced by combustion, preventing them
from reaching the atmosphere. As coal is a very carbon intensive fuel, this
technology is required to reduce the environmental impacts of burning coal.
Carbon capture and storage is however in its infancy without suitable
commercial-scale projects in use. 2 The addition of capture systems to a power
plant increases the cost of generated electricity and dramatically reduces the
efficiency of a power station. Having removed the carbon dioxide, the issue of
storage, never allowing it to reach the atmosphere remains. Current ideas lead to
burial in un-minable coal beds, depleted oil reserves and North Sea saline
reservoirs. The deep ocean is also a possibility, however far more research into
ecological effects must be addressed before this is a possibility.

The use of plants to absorb man made carbon dioxide is not a new idea. Trees
and forests are consistently planted for carbon offsetting, however the success of
such schemes for their intended use is doubtful due to the slow rates of carbon
capture and international location. 3 Recently however, the use of fast growing
plants such as algae has been noted for their efficiencies of fixating carbon

8
dioxide from combustion systems, and the products that can be obtained from
them. It is actually the latter that has lead to the development of the former,
through research into the production of biofuels from algae. Algae have featured
in much press as the new saviour of the world’s energy and pollution crisis;
“Algae can grow from ambient (0.04%) to 100% carbon dioxide
concentrations”,4 “1kg of algae will ‘eat’ 3 kg of carbon dioxide”,5 they “can
produce copious amounts of hydrogen”6 and “algal oils could be made into a
kerosene-like fuel”7.

This study investigates these claims and aims to determine the practical
possibilities for the use of algae in power plant carbon capture, storage and
energy production.

9
2. P HOTO -BIOREACTORS

A photo -bioreactor is the term given to a construct used to grow biological

material with the medium of light. There exists a large range of commercial sized
photo-bioreactor style and table 2.1 compares a wide selection. They can
primarily be split into two groups, open or closed system. An open system has
contact with the surrounding environment and is therefore subject to similar
conditions such as temperature. A physical barrier separates a closed system
from the local environment allowing independent control of the conditions within,
but increasing cost. Open systems are generally ponds although there are a
number of variations of the simple system. Figure 2.1A shows the plan view of a
raceway pond. A pond will typically be very shallow, around 0.3m deep and
require a pump to cause a flow of culture around the pond. New culture will be
fed after the pump, whilst harvest of the grown culture will occur just before.8
Culture passing through a pump may well cause damage that must be avoided.
Because ponds are open to the atmosphere, they are easily contaminated by
bacteria and do not perform to a high carbon dioxide efficiency as much which is
added, is lost. Their main uses are to grow algae for food, utilising ambient
carbon dioxide from the surrounding atmosphere.

Figure 2.1; (A) Arial view of a raceway pond. (B) A tubular photobioreactor with horizontal tubes.

10
Table 2.1; Comparison of the properties of different large-scale algal culture systems

A tubular reactor, figure 2.1B, is typically constructed from glass or plastic, with
diameters of around 0.1m. The tubes can be arranged horizontally, orientated
North to South, or stacked vertically, needing less ground area, but reducing the
light levels incident upon the lower tubes. A pump is again required and
turbulence should be encouraged to allow mixing of gas, algae and supplying a
constant rotation of algae to the edges of the reactor. Tubular reactors are
subject to heavy shading of the interior areas in high algal concentrations,
resulting in small diameters being required.

Tubular photo-bioreactors are generally more effective at producing high yields

of algal biomass in a shorter period of time than ponds and have are more
efficient use of carbon dioxide. They are however more expensive, using more
materials and care must be taken to prevent clogging of the tubes by biomass,
an occurrence more likely in grouping, glutinous species. For carbon dioxide
fixation and biofuel production, closed system reactors are the only viable option

11
as any contamination from, and leaking of carbon dioxide to, the surrounding
environm ent cannot be tolerated.9

In experiment, small-scale tubular bioreactors are most commonly used, typically

under 4L in volume. They are illuminated from all directions by artificial lighting
or internally, using fibre optics. The results from such experim ents therefore are
not true representations of natural conditions and some of the designs used are
simply not suitable for large-scale commercial applications.

12
3. ALGAE

Algae are the most basic form of plant life. There are tens of thousands of
different species ranging from single celled organisms to the most complex
marine seaweeds. Forming about 1.5 billion years ago, algae are a key cause in
the earth’s evolution of a hospitable atmosphere, reducing carbon dioxide and
increasing oxygen levels.

The more developed an organism, the more complex and less efficient the
energy harvesting process is, mainly due to the difficulty of distributing a carbon
dioxide supply around large organisms with many cell walls. Algae therefore,
being very basic in structure and often single cellular, have an extremely high
efficiency of solar energy use per unit of growth and are swift to adapt to new
environments. The high algal photosynthetic efficiencies lead to the incredibly
rapid growth rates causing algal blooms. Historically this rapid growth has
dominated life forms in rivers, lakes and shallow coasts when artificial
eutrophication by fertilisers has taken place. This has classed algae as a pollutant
in some cases, with vast numbers of papers written on the subject and how to
reduce the growth of rapid growth algae.10

A true alga is a eukaryotic organism with a nucleus and organelles such as

chloroplasts. Having evolved from prokaryotic organisms (organisms lacking
membrane bound organelles, such as a nucleus), cyanobacteria, or blue-green
algae is no longer classed as algae, but bacteria. Therefore, outside the algae
family and plant kingdom, many more organisms exist that obtain energy
through photosynthesis and therefore may also be eligible for use as is
suggested in this study.

13
Through literature review, four key species of algae emerge for they have much
written about them on products of growth or carbon dioxide sequestration. They
are Chlamydomonas reinhardtii, Botryococcus braunii and two from the genus
Chlorella, Chlorella vulgaris and Chlorella sorokiniana. These species are
discussed for their products and suitability for carbon dioxide sequestration
below.

3.1 C HLORELLA VULGARIS

Chlorella species have much literature as their nutritional value was noted early
in the 1940’s and hence batches for experimentation have long existed. It is
unicellular and easily cultured resulting in many photosynthesis related studies
having been carried out with this species before any other. This is the situation
we find ourselves in when it comes to determining rates of carbon dioxide
sequestration. The majority of algal behaviour discussed later in this study is
based on studies upon Chlorella species, so only brief descriptions are given
here.

Chlorella vulgaris can be found in lakes and ponds all over the world. It is
relatively fast growing with doubling times of under a day.11 Current studies
using Chlorella vulgaris for biological fixation of carbon dioxide have shown it to
be easy to utilise in engineering systems keeping high reproduction rates and
photosynthetic capacity. 12

14
3.2 C HLORELLA SOROKINIANIA

Chlorella sorokiniania is very successful in high temperatures and high

concentrations of carbon dioxide,13 being found in hot springs. Under optimum
conditions, doubling times of 2.5 hours have been achieved, producing large
amounts of biomass.

Studies into the structure of Chlorella sorokiniana revealed its chemical

composition, shown in table 3.1.

Table 3.1; chemical composition of C. sorokiniana H-84 grown in air containing 10% CO2 at 35 o C.

3.3 BOTRYOCOCCUS BRAUNII

Botryococcus braunii naturally produces hydrocarbons in the form of lipids.14,15

Although normally a green algae, during algal blooms the cells produce a huge
amount of carotenoids turning them yellow or orange. In this state, the lipid
composition can reach 80% of the cell’s dry weight. These lipids are formed
outside of the cell and embed single cells into a gelatinous mass.

15
The majority of hydrocarbons produced range from C27H 52 to C34H 58.15,16 Using
the Milne formula for calculating the calorific value of a fuel, given as equation
3.1, individually these hydrocarbons have high heating values of around 33.8
MJ.kg-1, a higher value than coal. In experiment, hydrocarbon contents of 50%
are regularly achieved. Assuming the remaining relative composition of the algal
cell is similar to that of Chlorella sorokiniana given previously, the dry high
heating value remains higher than 33 MJ.kg-1. If the hydrocarbon content
increases to 80%, then the calorific value increases to over 42 MJ.kg -1. If the
hydrocarbons are separated from the algal mass, they can be cracked into more
conventional fuels such as gasoline. 17

HHVmilne = 0.341 C + 1.322 H - 0.12 O – 012 N + 0.0686 S – 0.0153 Ash (3.1)

Botryococcus is found all over the world and has the advantage of being able to
grow in brackish (slightly saline) waters. It does however have a rather slow
growth rate of a few days. Due to the grouping nature of Botryococcus, biofilms
may form in narrow spaces, blocking fluid flow. These prove a major problem in
the medical field with needle thin tubes, but may not prove to be more than a
cleaning inconvenience in larger diameter photo-bioreactors.

3.4 C HLAMYDOMONAS REINHARDTII

Chlamydomonas reinhardtii, when deprived of sulphur, can sustain the

production of hydrogen.18,19 The sulphur deprivation partially deactivates the
photosynthetic oxygen evolution complex, causing a transition to anaerobic
conditions,20 activating a hydrogenase enzyme that carries out the reversible
reduction of H+ ions with an electrons, shown by equation 3.2. Activation of the

16
hydrogenase enzyme occurs after several hours of anaerobic induction in the
dark. Under continuous light, this increased to a few days.

(3.2)

Most laboratory experiments on this process have required the addition of

acetate, a salt or ester of ethanoic acid, into the culture solution. This is
consumed during aerobic stages of growth, but not during hydrogen production.
Excluding the addition of acetate would dramatically reduce the cost of growing
Chlamydomonas reinhardtii on large scale operations. Under strict light pH
control and CO 2 supplementation during sulphur deprivation, hydrogen
production can be sustained with the addition of carbon dioxide gas instead of
acetate under photoautotrophic (synthesising food using light as the energy
source) conditions. If using flue gas from an electrical power plant, any sulphates
must be removed before entering the algal culture. The presence of oxygen will
prevent the anaerobic process and hence the formation of hydrogen as aerobic
processes can resume. 21

The culture conditions must be strictly regimented to produce hydrogen and pre
stages of growth are required, as can be seen in figure 3.1. The first stage is
regular, aerobic photosynthesis forming oxygen, starch and inducing cell growth.
The carbon dioxide supply is then removed, starting the second phase and
forcing energy to be converted from stored starch whilst the previously created
oxygen is consumed. When there is no longer oxygen available in the growth
medium, anaerobic conditions form, initiating a delayed hydrogen production,
and stunting growth. Sustaining hydrogen production for a prolonged duration of
time will eventually cause the algae cell to die as the starch is consumed, so
aerobic photosynthesis must be reintroduced before this point if it is desired to
continue using the same cells.

17
Figure 3.1; The changes in dissolved O2 , pH and volume of the H2 produced during the cultivation of
sulphur deprived algae under photoautotrophic conditions.

It is claimed that a maximum H2 production rate of 56.4 mL.L -1 can be achieved

under photoautotrophic conditions if the culture is supplied with carbon dioxide
for the first 24 hours of sulphur deprivation, exposed to high light intensities
(110-120 µ.E.m -2.s-1) during the oxygen producing stage and finally exposed to
low light intensities (20-25 µ.E.m-2.s-1) during the oxygen consumption and
hydrogen production stages.

18
Under aerobic growth conditions, a specific growth rate of 0.27h-1 can be
achieved. 22 This is an equivalent doubling time of 3.7 hours under linear growth
conditions.

Papers were not found on the rates of carbon dioxide sequestration for the
hydrogen producing species, Chlamydomonas reinhardtii, however the hydrogen
production rate of 56.4 mL per L of culture for an average cell density of 15x10-3
kg.m -3 can be utilised to determine what mass of cells are needed to produce
required quantities of hydrogen. If hydrogen can be produced cleanly and
reliably by this species of algae, the possibilities for fuel can expand into a new
era. If bio-hydrogen were to be used in a power plant, the algae would require a
new source of carbon dioxide, as it is no longer a by-product of combustion.
There are also many channels for hydrogen use in the transport sector, car
manufacturers have invested heavily in hydrogen fuel cell powered cars.23

The rates of carbon dioxide sequestration by Chlamydomonas reinhardtii need to

be determined before this alga can be considered appropriate for removing flue
gas carbon dioxide. A less regimented process of light levels for the production is
also required if natural sunlight is to be harnessed.

19
4. P HOTOSYNTHESIS

Organisms of the plant kingdom and some bacteria create their own energy
supply by utilizing that of the sun. This process is known as photosynthesis, the
generic form of which is given as equation 4.1. Conditions allowing
photosynthesis are referred to as autotrophic. Carbon dioxide and water are
required in the process whilst oxygen is released. The carbon is effectively stored
as organic substances with the only external energy source being the sun, which
by human time scales, is inexhaustible.

(4.1)

If the carbon dioxide from flue gasses can be supplied effectively to a culture of
photosynthetic organisms, then these emissions after passing will be reduced
and organic structures produced, in other words, growth. This forms the basis of
this study.

This section discusses the factors that influence the rate of photosynthesis and
hence growth, explaining how they can be optimised for an algal culture.

20
4.1 LIGHT

Light drives photosynthesis by supplying the energy for two key systems; the
transfer of electrons from water to NADPH (nicotinamaide adenine dinucleotide
phosphate) and the generation of ATP (andenosine triphospate). The range of
electromagnetic radiation enabling photosynthesis is referred to as the
photosynthetically active radiation range, wav elengths between 400nm and
800nm.24 Chlorophyll typically absorbs light at around 450nm and 650nm,
perceived by the human eye as blue and red respectively, shown in figure 4.1. It
is therefore these wavelengths that need to be present for photosynthesis to
take place. Naturally, this light is sourced from the day’s sunlight but provided
the correct wavelengths are present, photosynthesis will take place under
artificial light also, with the added advantage of control. It should be noted that
almost all laboratory experiments are carried out under artificial light.

Figure 4.1; Chlorophyll light absorption spectra

There are three further light variables that will influence the process of
photosynthesis, and hence algal growth. The first is light intensity; how much
light energy enters the culture. Enough suitably energised photons must be
captured by chlorophyll pigments to initiate the chain of reactions that is

21
photosynthesis, but if too much energy is presented cell damage will occur,
inhibiting growth. Excess light stunting growth is referred to as photo-inhibition.

The second variable is photoperiod; the ratio of light and dark, typically
measured over a 24 hour period. If NADPH and ATP compounds are available,
the remaining processes of photosynthesis can take place without the necessity
of light. These reactions are referred to as ‘dark reactions’, 25 although naturally
they take place in both light and dark conditions. It may be hypothesised that
the fasted growth will take place under continuous light, however, algae has
evolved in systems with light and dark periods, therefore excess light may not be
utilised. This is an important factor when considering algae for large scale
production; will the energy used illuminating a culture overnight be recovered by
the extra levels of growth?

The third factor to be considered in large scale algal farms is photo-limitation or

light shading. By the nature of photosynthesis, photons captured by chlorophyll
cannot penetrate further into the culture. This results in an optimum depth of
algal culture where any deeper cells would not receive photons of suitable
wavelength, similar to the effect of the tree canopy in a forest.

For algae to be a renewable fuel source natural light must be utilised so local
solar irradiance, weather patterns and seasonal changes for suitability of algal
growth are also discussed.

22
4.1.1 LIGHT I NTENSITY

Sorokin shows that the optimum light intensity for algal growth lies between 400
and 3000 foot candles 26 (6.30 and 47.28 W.m-2),27 figure 4.2. Each light intensity
curve starts with a light dependant region where growth rate increases with light
intensity, followed by a light independent plateau, finalising with a second light
dependant region where growth declines with higher light intensities. It can also
be seen that different species have distinguishable characteristics, although the
same tri-region curve fits all considered, with a similar plateau light intensity
range.

Figure 4.2; the growth rates of four species of algae at 25 o C

under different intensities of continuous light.

A similar experiment by Qin on the algal species Botryococcus braunii showed

similar results,28 figure 4.3. The highest growth rates were produced under light
intensities of 30 and 60 Wm-2, with doubling periods of 2.61 and 2.51 days
respectively. The trend line gradients of intensities either side of 30 and 60W.m-2

23
indicate a very similar effect to that seen above with limited growth at intensities
above 100 W.m -2 and below 20 W.m -2.

Figure 4.3; The impact of light intensity on Botryococcus Braunii algal growth at 23o C,

12h light, 12h dark. (A) Low light range (W.m-2 ); (B) High light range (W.m-2)27

Some algal behavioural observations were also noted in this second experiment.
Under 20 W.m-2, the cells agglutinated together after stirring rather than
spreading to an even distribution as noticed between 30 and 60 W.m -2. A similar
effect was observed over 150 W.m-2 and at 300 W.m-2, most algal cells died.

Although the optimum light intensities are shown here to be over 30 W.m -2,
photosynthesis will occur at lower light intensities. The lowest value of
illumination to allow for photosynthesis is called the critical illumination, denoted
Ic. When looking at individual reactions, experiments have determined the
energy needed for each molecule of oxygen to be produced. Pirt describes the
minimum quantum demand to be in the order of 5.3 to 8.6 hv.O 2-1,29 where h =
plank’s constant (6.62x10-34 J.s) and v is the frequency (Hz, s-1). The minimum
quantum yield is therefore the equivalent of 5.3 to 8.6 joules. This energy can be
summated by the capture of lesser energy photons as the potential produced by
a single interaction can be stored for a brief amount of time in chlorophyll
antenna, reducing the lowest light intensities for photosynthesis further.

24
The optimum light intensity for growth was proven to also be the optimum for
hydrocarbon production for Botryococcus braunii, 27 as shown on figure 4.4. The
highest constituency was over 80%, but lowered dramatically under light
intensities of over 60 Wm-2.

Figure 4.4; Relative total lipid content (rTLC) of Botryococcus braunii under various light
intensities.

Further study comparing three different Botryococcus strains showed that a UK

strain (UK 807-2) contained the highest relative lipid content at 60 Wm -2 with a
comparable 75%,30 figure 4.5. It also indicates a drop off in productivity over 60
Wm-2.

Figure 4.5; the mean relative lipid content of three Botryococcus braunii strains at different
irradiance, 25 o C.

25
4.1.2 PHOTOPERIOD

Qin also shows that higher growth rates take place under longer photoperiods,27
shown in figure 4.6. Algal growths are severely inhibited with only 4 hours of
sunlight a day and slow with 8 hours of light a day. It can also be seen that
there is a limited difference between 12 hours and 24 hours of light over a 24-
hour period, although continuous light does show a slight advantage at greater
optical densities.

Figure 4.6; Impact of different photoperiods on algal growth of

Botryococcus braunii at 25 o C and 30Wm-2

This indicates that there will be no recoverable advantage illuminating an algal

culture over an entire 24 hours, but mechanical light may well prove a worthy
investment to ensure 12 hours of illumination during seasonal short days. This
will unfortunately increase costs, reducing profits the further away from the
equator the photobioreactor is based, unless the extra light received during
summer months can be utilised.

26
This artificial light does not have to be continuous however. The maximum
growth rate of a Chlorella species was shown by Pirt to be maintained if each cell
is exposed to 20 W.m-2 for 0.5s followed by a 9s dark period.31 If this finding can
realistically be put into practice, an hour’s growth can be produced with the
equivalent of 3.2 minutes of illumination.

4.1.3 PHOTO-L IMITATION

Light entering a dense algal culture is rapidly dispersed, forming many various
irradiances and light gradients amongst the culture whilst self-shading of cells
will occur.32 If the light is dispersed or captured too rapidly, only the outer edges
of a tubular reactor or the top surface of an algal pond will have high enough
illumination to support photosynthesis. These effects can be overcome by
lowering the cell density, increasing the dilution rate, increasing the irradiance
(remaining below a level to cause photo-inhibition), reducing the diameter of a
photobioreactor, reducing the depth of an algal pond or creating currents to
ensure individual cells pass through all irradiance levels for suitable periods of
time. A precise understanding of each of these variables is required to
understand how many algal cells will be under optimal growth conditions at a
particular time. Photo -bioreactors need to be designed to reduce the effects of
photo-limitation to allow the highest algal densities to cultivate within their
boundaries. There are a number of methods used in literature to determine the
light distribution in a photo-bioreactor.

Anderson et al.33 state that equation 4.2 can be used to determine the light
intensity at a required culture depth at a specific concentration;

I 
ln  o  = k × C × d (4.2)
I 

27
Where;
I = Light intensity at depth of penetration d
Io = Incident light intensity
C = Algae concentration (kg.m-3 or g.L-1)
d = Depth (m)
k = Light extinction coefficient (m 2.kg-1)

The light extinction coefficient can be split up into the factors of each constituent
of the culture. In an algal culture, the constituents of consideration are non-
photosynthetic elements (water and minerals) and chlorophyll a, for which the
concentration (c) must also be considered. 34 This leads to the Bannister linear
equation;

k = k w + kc c (4.3)

A light extinction coefficient value of 200m 2.kg -1 was determined by Ogbonna

and Tanaka for Chlorella sp.35 Using a concentration of 10g.L-1, the light levels at
a depth of 1mm will be 13% of those at the surface and at 2mm, only 2% of the
incident light will have penetrated, indicating how dramatic this phenomenon is,
shown in figure 4.7.

28
 Figure 4.7; Light intensity change with depth at different algal concentrations.

This indicates that a photo-bioreactor requires a very high surface area to

volume ratio to absorb enough light for high algal densities, or very low algal
concentration values must be used. Low concentrations will require greater
volume and hence larger land areas. Ogbonna further discusses the need for a
new method of rating a photo-bioreactor, based upon its light distribution
characteristics. 36

Using the same nomenclature as before, where in this case d=depth of reactor,
the average light intensity can be given by equation 4.4.

I av =
(
I o 1 − e( − kCd ) )
(4.4)
kCd

The average light intensity will be under 50% of the incident light intensity in
any pond reactor over 2mm deep with a 10g.L-1 concentration. As explained
previously, there is a very rapid illumination gradient in an algal culture, so the
average light intensity favours shallow reactors, whatever the size or shape,

29
making scaling difficult. Instead it was proposed that the reactor could be divided
into illuminated and non-illuminated volume fractions. The ratio of the volume
receiving sufficient light for photosynthesis against the volume that does not
gives the illuminated volume fraction, denoted VF. V F may be close to unity at
low algal concentrations and will tend towards zero at high concentrations. This
is shown in figure 4.8. It is further proposed that an index of the light
distribution of a reactor be defined as the algal concentration that will reduce the
illuminated volume fraction to 50%. This index is named the light distribution
coefficient and is denoted Kiv .

Figure 4.8; Effect of cell concentration on illuminated volume fraction of a cubical photo-bioreactor.
A= Single side illumination at 325µmol.m-2 .s-1 , B= Two side illumination at 162.5µmol.m-2.s -1

If assuming that the critical light intensity for photosynthesis (Ic) is 7.65µmol.m -
2
.s-1 (1.66W.m -2, from 1µmol=0.2176J), as stated in the paper, and that k
remained 200m2.kg-1, it was found empirically from figure 11 that the Kiv values
were 1.9kg.m -3 and 3.1kg.m-3 for condition A and B respectively. This clearly
informs that design B is a more efficient method, capable of housing a higher
concentration. Calculation of the light distribution coefficient differs for various
reactor shapes and illumination methods. The equations for an externally
illuminated cuboidal reactor, externally illuminated cylindrical reactor and
internally illuminated cylindrical reactor are given as equation 4.5, 4.6 and 4.8

30
respectively with figures 4.9, 4.11 and 4.13 respectively displaying schematics of
each reactor. The variation of the light distribution coefficient with
photobioreactor size for each model are shown as figures 4.10, 4.12 and 4.14
respectively. The following assumptions are applied to each model; Io = 60W.m -
2
; Ic = 2W/m-2; k = 200m2.kg-1

It should be noted that these are greatly simplified models to what will exist in
commercial applications. The true behaviour will be a combination of the effects
existing mainly in pond and exteriorly illuminated conditions.

Figure 4.9; Schematic representation of a cuboidal reactor,

illuminated exteriorly from above.

I 
ln  o 
Kiv =  Ic  (4.5)
0.5 × k × D

Figure 4.10; Changes in light distribution coefficient with increasing depth of a

cuboidal photobioreactor.

31
The depth values for a pond are very small with the largest depth being 10cm
providing a light distribution coefficient of under 4kg/m 3. If ponds are to be used,
they will have to be very shallow, and hence occupying a large surface area
making for control of the culture very difficult.

Figure 4.11; Schematic representation of a cylindrical reactor, illuminated exteriorly.

 I oD 
ln  
 I c (D − 2 LL ) 
Kiv = (4.6)
k × LL

LL can be determined by calculation by equation 4.7, derived from the area

equation of a circle, provided the Kiv value is for 50% photosynthetically active
volume, ignoring effects at either end of the reactor.

1 D 
LL = D−  = 0.1464 D (4.7)
2 2

32
 Figure 4.12; Changes in light distribution coefficient with increasing diameter of an externally
illuminated photobioreactor.

These are particularly low values, and in experiment, far better algal
concentrations have been grown. At smaller tube diameters, the pond effects will
play a larger role, especially as there will be a dominant solar irradiance direction
from above.

Figure 4.13; Schematic representation of a cylindrical reactor, illuminated interiorly.

 Io d 
ln  
 I ( 2L + d )  (4.8)
K iv = c L

k × LL

LL can be determined by calculation by equation 4.9, provided the Kiv value is for
50% photosynthetically active volume, ignoring effects at either end of the
reactor.

33
  D  2  d  2 
− d + d 2 + 2  −   
 2   2  
LL = (4.9)
2

Figure 4.14; Changes in light distribution coefficient with increasing diameter of an internally
illuminated photobioreactor.

Assuming ; d = 0.05m

It appears that an internally illuminated reactor can support relatively high algal
concentration cultures. This suggests that any artificial illumination shoul d
perhaps be utilised in this way.

34
4.1.4 LOCAL C ONDITIONS

As much as possible of the energy needed from light to drive enough

photosynthesis to reduce the carbon dioxide emissions from flue gas should be
harnessed from the natural source of the sun. This will not only reduce costs
when compared to an artificially illuminated system, but will prevent extra
energy use, and hence carbon dioxide emissions directly from the power plant.
The natural solar illumination available will depend on the location from the
equator, local weather patterns and the time of year. The UK and Ireland’s total
annual horizontal solar irradiance is shown as figure 4.15, whilst the monthly
average conditions for Cardiff are shown in figure 4.16.

Figure 4.15; Yearly total global horizontal irradiation, (a) Europe, (b) UK and Ireland

35
 Figure 4.16; Monthly variation of Solar Irradiance in Cardiff

It was shown previously that optimum growing conditions included 12 hours of

illumination at over 30W.m -2 a day. From figure 4.16 it can be seen that Cardiff
actually receives these conditions naturally between the months of April and
September, with substantially longer days in the summer months. The remaining
six months will require artificial lighting in the mornings and evenings. December
will prove to be the most draining of resources requiring six hours of artificial
light a day.
It has not been made clear from previous work if the photoperiod will have the
same effect if the illuminated period is split into different sections. Artificial
illumination over the winter months will coincide with the morning and evening
peak electricity demand periods. Not only will illuminating the culture risk the
possibility of causing too much electrical load during these times, but also the
electricity sold at these hours is at peak rate. If the culture can be illuminated at
night, during times of minimal loads, then the cost of artificial illumination will be
reduced. Issues surrounding light pollution may arise. Such a system should
however be designed for minimum light escaping the cultures, resulting in
maximum efficiency. An internally illuminated photobioreactor may prove to be
the best option under such conditions.

36
South of Cardiff, to the line of the equator, overall solar irradiation levels will
increase with less variation in lengths of day, resulting in steadier, easier to
manage conditions. North of Cardiff the overall illumination will reduce, seen in
figure 18, and the seasonal length of day will increase making for more difficult
conditions to utilise the algal potential. This puts Cardiff, with median conditions,
an excellent place to determine the validity of this study. Required reactor sizes
for an equivalent carbon producer will probably reduce in size in southerly
locations and increase in more northerly locations due to algal density
possibilities.

37
4.2 CARBON DIOXIDE

Carbon dioxide is received by an organism from the medium in which it lives, for
algae, this medium is water.37 In water, the majority of stored carbon dioxide is
in solution. About 1% is stored as carbonic acid, H2CO 3, reducing the pH of the
solution. Increased acidity drives the reaction in the opposite direction, releasing
CO2. Gasses are generally less soluble in warmer solvents and this holds true of
carbon dioxide. The presence of salts and proteins in a solvent also reduces the
solubility of gasses.

The delivery of carbon dioxide to algae must therefore consist of two stages; the
carbon dioxide uptake into water solution and the removal of this carbon dioxide
from solution by algae. Optimum conditions of one may not be the optimum for
the other, but the overall effects can simultaneously be observed by bubbling
carbon dioxide through an algal culture and measuring the rates of carbon
dioxide removal. This is after all, the process that needs to be determined for
removing carbon dioxide from flue gas streams.

This section discusses the variations in concentration and fixation rate in

comparison to growth rates.

4.2.1 CONCENTRATION

Current atmospheric concentrations of carbon dioxide are around 0.038%. This is

a far lower concentration than what can be expected in flue gas, where the
concentrations will be closer to 13%. Figure 4.17 shows that the optimum level
of carbon dioxide for growth of Chlorella vulgaris is at 2%. The growth rate is
actually doubled with this higher concentration in comparison to air but is
severely inhibited at higher concentrations. After increasing the cell density, the

38
algae grew much better at 5% carbon dioxide, suggesting that higher density
cultures can be used with higher carbon dioxide concentrations.

Figure 4.17; Effects of different concentrations of CO2 aeration of the growth of Chlorella sp.
Inoculated at 300 µmol.m-2 s -1 , flow rate of 0.25 vvm, 26 o C, starting density of

(a) 8x10 5 cells.mL-1 , (b) 8x106 cells.mL-1

The huge range of results that exist by using different species of algae can be
seen clearly for Chlorella sorokiniana, shown in figure 4.18. This species appears
to grow very well, and far more rapidly than Chlorella vulgaris in much higher
carbon dioxide concentrations. The growth rate does not reduce until levels of
40% are reached, higher than those produced in power production plant flue gas
composition. For this reason, Chlorella sorokiniana may prove to be the most
suitable species for carbon dioxide sequestration.

Figure 4.18; Effect of CO2 concentration on the growth of

Chlorella sorokiniana H-84 at 40oC

39
4.2.2 FIXATION RATE

The true sizing of an algal carbon dioxide sequestration plant is dependant upon
the rate of carbon dioxide fixation. A faster rate per algal cell will reduce the
number of cells required, reducing the overall volume.

Published experimentation in this field has taken place using very small test
volumes. The rector used to produce the results in figure 4.19 had dimensions of
600mm height and 50mm diameter, providing an effective volume of 1.2 L. It
can be seen that higher gas flow rates reduce the values of carbon dioxide
fixation. This is because of the dramatically reduced retention time. The gas is
simply passing through the culture too fast to dissolve or be utilised by contact
with algae. In small reactor models, the gas flow rate must be reduced to
compensate for this.

Figure 4.19; Effect of gas flow rate on CO2 fixation and O2 evolution,

(T = 25 o C, cell number = 5x107 cells.mL-1 , luminous intensity = 5400 lx)

In larger reactors however, it is the author’s belief that this problem will largely
be overcome, as the retention time will be increased due to the extra lengths of
reactor. It is doubtful also that a commercial reactor will be orientated vertically,
as in experiment, further reducing the speed of gas through the culture and

40
increasing retention time. These factors may allow far higher gas flow rates to be
used. A higher flow rate will aid many other processes of the system. Induced
turbulence will improve fluid mixing and carbon dioxide solubility along with
movement of the algae in eddy currents, allowing each cell time in the higher
light intense regions of the photobioreactor. The true flow rate in a commercial
system is governed by the power output of the power plant at a particular time.
All the gasses that are emitted at the production rate must be accepted into the
culture, determining the flow rate. Requiring low flow rates for each reactor will
increase the overall size of the scrubbing system.

Figure 4.20; Effect of luminous intensity on CO2 fixation and O2 evolution by Chlorella vulgaris,

(T=25oC, cell number=5x107 cells.mL-1, gas flow rate=1.25L.min-1)

Figure 4.20 above has a very similar shape to the photo-dependant regions of
growth curves suggesting that carbon dioxide fixation rate is directly proportional
to growth rate. The optimum growth rate for Chlorella vulgaris was previously
stated to be in carbon dioxide concentrations of 2%. Figure 4.21 below shows
that the optimum efficiency of carbon dioxide reduction is greatest at 2% carbon

41
dioxide concentrations also, with an effective rate of 58%. This indicates the
assumption that the most effective carbon dioxide fixation rate occurs at the
maximum growth rate.

Figure 4.21; Comparisons of the total amount and efficiency of CO2 reduction in the single and the
six-parallel photobi oreactor of semicontinuous Chlorella sp. under 2%, 5%, 10% and 15% CO2
aeration.

42
4.3 TEMPERATURE

Temperature affects the rate of photosynthesis by changing the rates of enzyme

reactions involved in systems of the photosynthetic complex. The optimum
growth rate will occur at the optimum temperature, with decreasing rates either
side of the peak, figure 4.22.

Figure 4.22; Temperature effects on photosynthetic activity

The temperature response of different species varies considerably and the

optimum may well lie outside of the regular natural growth conditions. Typical
values fall between 25 oC and 30oC. Table 4.1 indicates the optimum temperature
for a number of species, including Chlorella vulgaris and figure 4.23 shows
growth rates of Botryococcus braunii and Chlorella sorokiniana at different
temperatures.

Table 4.1; Optimum temperatures for four species of algae

43
Figure 4.23; impact of temperature effects on growth over time, (a) Botryococcus
braunii (b) Chlorella sorokiniana

The optimum temperatures for Chlorella vulgaris, Botryococcus braunii and

Chlorella sorokiniana are 30oC, 23oC and 40oC respectively.

44
4.4 NUTRIENTS

Nutrition is required by all plants to photosynthesise effectively. The range of

nutrients required varies on the plant and which processes are active will
determine the required supply rates. 38 Nitrogen is heavily required for production
of proteins, especially light harvesting complexes that constitute almost 50% of
thylakoid membranes. Deficiency of nitrogen will have a wide effect on many
components whilst lesser -used nutrients will have specific effects, such as
electron transport in the case of iron. Phosphate is involved in many functions of
photosynthesis and deficiencies may change the activity of enzymes. Select
supply of nutrients can have favourable effects also, such as sulphur deprivation
in Chlamydomonas reinhardtii producing hydrogen. The highest hydrocarbon
content in Botryococcus braunii required very low levels of nitrates, phosphates
and potassium.39 A table of typical nutrients added to algal cultures in
experimentation is given as table 4.2.

Table 4.2; Typical Nutrient Supplementation

45
5. C ARBON DIOXIDE SEQUESTRATION

Many of the factors that influence the rate of algal growth, and hence carbon
dioxide fixation have been discussed for a selection of different species. It is now
possible to apply these findings to a physical system. As coal is particularly dirty,
has many protesters but is in plentiful supply with respect to other fossil fuels, it
may prove to be the most useful application of algal carbon capture. Here, it is
applied to a medium sized 1500MWe coal burning power plant, figure 5.1.

Figure 5.1; Input and output characteristics of a coal fired power station

A 1500MWe coal -burning power plant with an electrical generation efficiency of

35% will require a thermal input of 4300MW. Using an ultimate analysis of 80%
carbon, 13% oxygen, 6% hydrogen and 1% sulphur, the calorific value of coal is
approximately 30MJ.kg-1. This equates to a fuel demand of 143kg.s -1. The carbon
dioxide producing reaction of burning coal is given as equation 5.1. Carbon has
an atomic mass of 12 whilst oxygen has an atomic mass of 16. Carbon dioxide
therefore has a molecular mass of 44. For each kilogram of carbon burnt as coal,
3.7kg of carbon dioxide is emitted. Running at full capacity, this station is
burning 114.6kg.s-1 of carbon, producing 420kg.s-1 of carbon dioxide.

46
 (5.1)

Typical emissions from a coal plant are 13% carbon dioxide, 82% nitrogen, a
little oxygen and a trace of sulphur dioxide. 420kg of carbon dioxide will occupy
234m3 at 25 oC and 1bar. The total volume of flue gas produced is therefore
1800m 3.s-1 at 13% CO2. The temperature will be higher than 25oC, so these are
conservative volumetric estimates.

It was previously shown that Chlorella sorokiniana has the most rapid growth
rate, thrives in temperatures of 40oC and carbon dioxide concentrations of up to
20%. Chlorella sorokiniana is therefore the most suitable algae for carbon
dioxide sequestration mentioned in this study. Lihai et al suggest that the
optimum gas flow rate for carbon fixation of 1% CO2 through a Chlorella vulgaris
culture was 1.25 L.min-1.12 This was carried out at a lower than optimum light
intensity of 8 W.m-2, and 2% CO2 was earlier shown to be the optimum
concentration levels for vulgaris growth. None the less, with a starting algal
concentration of 5x10 7 cells.ml-1, a carbon dioxide fixation rate of 0.14g.L -1hr-1
was determined. Being from the same genus, we can make the assumption that
at its respective optimum growth conditions, the fixation rate of C. sorokiniana
will be similar to that of C. vulgaris.

Changing each of the figures to S.I. units, we have a carbon dioxide fixation rate
of 0.0023kg.m -3.s-1. Our power station is producing 420kg of carbon dioxide a
second. Assuming a constant fixation rate even though the concentration is
reducing down the reactor, a total reactor volume of 183x103m3 is required. The
experiment was carried out in a tube of diameter 130mm, resulting in a single
tube length of 14,100km. Using the arrangements shown in figure 5.2, allowing
light between adjacent tubes, four tubes can be housed in each metre width.

47
Having done this, a ground surface area of 3.5x106m 2 is required. This can be
housed in a 1.87km square space. Adding a little safety factor by rounding the
numbers up, the carbon dioxide emissions from a 1500Mwe coal fired power
plant can be reduced to zero in a 2km x 2km square algal field.

Figure 5.2; Photobioreactor design using dimensions from lihai et al.

48
6. ALGAE BIOFUEL

6.1 BIOMASS

The flue gas carbon dioxide has been converted into Chlorella sorokiniana algal
biomass with a doubling time of 2.5 hours. If optimum growth conditions were to
be maintained, this equates to 9.6 doublings over a 24hour period. The original
cell density was 5x107 cells.ml-1, equal to a biomass dry weight of 0.7kg.m-3 by
use of the graph in figure 6.1. 40 Our original mass was therefore 128x103 kg. If
this doubles 9.6 times, a mass of 1.23x106 kg will be produced daily, with an
average rate 14.2kg.s -1.

Figure 6.1; Relationship of optical density to algae cell number and dry weight biomass.

The next process to be determined is how to make use of this algal biomass. The
composition of Chlorella sorokiniana has been determined previously and table
6.1 below displays the chemical composition of each constituent of the algae.41
From this we can determine the suitability for this algal biomass for a fuel using
the Milne formula.

49
Table 6.1; Chemical composition of biomass

The dry high heating value of Chlorella sorokiniana proves to be 15.6 MJ.kg-1.
This value is typically regarded as too low to be used as a fuel. It is however,
higher than all four biomasses quoted in table 5. If the algal biomass was to be
dried and placed directly in the burner with coal, then 221MWth or 5%, of the
stations requirements will be supplied by algal biomass. This is the equivalent of
saving 7.4 kg.s-1 of coal. The carbon dioxide released by burning the algal
biomass will be filtered through the algae farm after combustion, re-fixing the
carbon dioxide. This cycle would continue during the plants operation, essentially
storing and recycling the carbon from the original coal combustions.

6.2 A NAEROBIC DIGESTION

The anaerobic digestion of the algal biomass can obtain greater amounts of
energy than its direct use as a biofuel. Anaerobic digestion is the degradation of
carbonaceous matter by micro organisms with the absence of oxygen, producing
carbon dioxide and methane with a reduction in biomass.42 A typical reactor will
be maintained at a temperature of 35oC, ‘fed’ once or twice a day at a rate of 1.7
kg(VS).m 3.d-1. The volatile substrate (VS) will be retained for 20 to 30 days and
will reduce by about 60%. The typical gas composition produced by anaerobic
digestion of algae is in the order of 70% methane (CH4), 25% carbon dioxide
with the remaining volumes consisting of water vapour, nitrogen and hydrogen
sulphide.43 Table 6.2 shows how much methane can be produced from various

50
biomass samples. Kelp, the closest mentioned biomass to algae, can produce
methane at a rate of 0.4 m3.kg-1 of added volatile substrate. Theoretically, the
yield could achieve 0.51 m3.kg -1 assuming the empirical formula for kelp to be
C 2.32H 3.73O 1.48.44 Algae may be expected to perform better due to the simpler
individual cell structure.

Table 6.2; Ra nge of biochemical methane potential data from biomass or waste
feedstock.

Methane has a high calorific value of 55.5 MJ.kg-1, a far more efficient value for a
fuel. Using the methane production rate of 0.4m3.kg-1 for kelp and recalling our
dry algal production rate of 14.2 kg.s-1, methane can be produced at a rate of
5.68 m3.s-1. Directing this methane directly into the power plant furnace,
315MWth (7.3%) can be supplied by this process. This has actually released
more energy from the same yield of algae burnt as biomass. The remaining solid
matter is typically used as crop fertiliser or animal feed. The process of anaerobic
digestion has however created carbon dioxide once again. If 5.68m3 methane is
70% of the gasses produced and carbon dioxide occupies 25%, then carbon
dioxide is produced at a rate of 2.03m 3.s-1. If this was to be released to the
atmosphere, we have still reduced the carbon emissions of the coal power plant

51
by 99% but there is no reason why this small amount of carbon dioxide cannot
be directed back through the photobioreactor.

The problem arises however at the long retention time due to the slow rates of
digestion. If the reactors can be ‘fed’ at a rate of 1.7kg(VS).m -3.d-1, then the total
volume of anaerobic digesters would lie around 723.5x10 3m 3. If each reactor
were 10m in diameter and 10m tall, 116 reactors would be required, requiring a
land area of 11.6km 2, the equivalent of a 108m square.

6.3 BIODIESEL

Biodiesel is a proven fuel in the transport industry and a technology that has
been around for over 50 years.8 Typically derived from plant and animal oils,
namely soybeans and sugar cane, it has been involved mainly with road vehicles.
The vastly more rapid growth of algae, along with its higher oil content will
greatly reduce the amount of land required to produce biodiesel, as can be seen
in table 6.3. It also has the advantage of not requiring agricultural land and
displacing food crops, a major issue surrounding energy crops. Use of algae for
biodiesel is yet to be put into commercial practice, but has interest from the air
transport industries looking for a ‘green’ fuel.

52
Table 6.3; Comparison of some sources of Bio-diesel

Table 6.4 compares oil extracted from Botryococcus braunii by ethyl acetate with
class-C heavy oil and shows that the oil has a similar calorific value whilst
containing less nitrogen and sulphur. When burnt, bio-diesel is relatively
environmentally friendly as it is significantly less polluting than conventional
petro-diesel. 45

Table 6.4; Comparison between Extract and Cass-C Heavy Oil

Manufacturing bio-diesel from algal oils and lipids involves two stages, removal
of oil and chemical alteration into diesel, figure 6.2. Oil is extracted from the cell
culture by liquefaction or use of a solvent. 46 Super critical carbon dioxide can be

53
used, is non-toxic and cheap.47,48 Alternatively, acetone, methanol and n-hexane
can be used as solvents whilst breaking the cell wall will increase the extraction
yield of oils. 17,49 After evaporating the solvent, biodiesel can be obtained from
the extracted oils by transesterification, the process of converting the relative
components into mono-methyl-esters. 50,43 Biodiesel production for an algal farm
depends upon the species used, its relative lipid content and the growth rates
that can be achieved. The remaining solid algal residue can be used as animal
feed or be anaerobically digested.

Figure 6.2; Process flow schematic for bio-diesel production

It must be appreciated that the burning of biodiesel produced from a carbon

dioxide sequestration plant is simply releasing the removed carbon dioxide over a
wider area. The emissions have had two uses before their release, but unless
petro-diesel combusti on reduces at the rate of biodiesel production, there will be
no net carbon dioxide reductions in the atmosphere.

54
7. C ARBON STORAGE

Aside from biomass and oils, other compounds naturally produced by algae are
also of valuable use. β-carotene, omega-3 and eicosapentaenoic acid (EPA) are
of use in the pharmaceutical industry for heart and blood disorders,51 whilst the
oils extracted from algae can be used in building materials and bio plastics.52
Mixing Chlorella vulgaris with polyvinyl chloride (PVC) between 10-30% can
provide stable moulds, sufficiently strong for use for typical PVC building
materials. The use of a by-product of photosynthesis, polysaccharides, can be
added to concrete to pre-harden, removing the need of concrete compaction.
This is a rather undeveloped area, but the production of biodegradable, bio-
plastics would receive much interest.

55
8. HARVESTING

The harvest of algae currently proves to be a major challenge for industrial algal
cultivators.53 There are a number of methods available, compared in table 9. The
style of algae determines which harvesting methods are most suitable. The
easiest forms to harvest are those that flocculate together and sink in still water,
forming a dense sedimentary mass. A larger flocculation will sink more rapidly,
allowing greater rates of harvest. Flocculation can be induced by the addition of
chemicals, but this will increase costs and may contaminate by-products. After
harvesting, there remains much water which must be removed by heated
evaporation before the algae can be used for its products.

Table 8.1; Biomass recovery options

56
9. CONCLUSIONS

This review looked at the possibilities of using algae to remove carbon dioxide
from power plant flue gas and was applied to a 1500MWe coal fired station
whilst addressing the possibilities for using the produced biomass as a fuel.

It has been shown that the algal species Chlorella sorokiniana can be grown from
the flue gas emissions of a coal fired power plant in the South Western regions
of the United Kingdom. The entire carbon dioxide emissions from a 1500MWe
coal fired power plant can be absorbed in a 2x2km field of Chlorella sorokiniana
with a starting algal concentration of 5x107 cells.ml-1. This has been predicted to
produce algae at an average rate of 14.2kg.s-1. The algae produced cannot be
directly burnt as biomass in the furnace as all the carbon dioxide would be re-
released, requiring further sequestration whilst only providing 5% of the fuel
demand. Anaerobic digestion will provide 7.3% of the fuel demand, but will
require vast volumes of anaerobic digesters.

If algae were to be used to remove carbon dioxide from power plant emissions,
the produced biomass must be refined into suitable materials. The most viable
product is biodiesel; however it’s burning will re-release the stored carbon
dioxide. Some species can achieve relative lipid contents of 50-70%wt. These
species typically have far lower growth rates than that of Chlorella sorokiniana
although some Chlorella species have been found to produce hydrocarbons. Oils
extracted can be used to manufacture biodegradable bio-plastics, however much
research is required to make this a viable product.

Further research is required in order to determine if the assumptions made in

this study are accurate, specifically regarding the Chlorella sorokiniana carbon
dioxide fixation rate and optimisation of this process. Determining carbon dioxide
fixation rates for hydrocarbon producing algae will prove most valuable as

57
realistic production values of biodiesel can be obtained, providing an economic
enticement in support of the environmental incentive. Research involving
hydrogen producing species may reveal further fuel possibilities and genetic
engineering may open yet further doors in improving algal photosynthetic rates
in flue gas specific environments.

58
 REFERENCE

1
HM Government, Department of Trade and Industry, 2007. Meeting the Energy Challenge. A
White Paper on Energy.

2
IEA Greenhouse Gas R&D Programme; CO 2 Capture and Storage.
http://www.co2captureandstorage.info/what_is_co2.php

3
Friends of the Earth, 2007. Briefing Note: Carbon Offsetting.
http://www.foe.co.uk/resource/briefing_notes/carbon_offsetting.pdf

4
Eiichi Ono, Joel L. Cuello, 2004. Selection of optimal microalgae species for CO2 sequestration.
University of Arizona.
http://www.netl.doe.gov/publications/proceedings/03/carbon-seq/PDFs/158.pdf

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 APPENDIX I

CALCULATIONS

Coal power plant emissions:

Assumptions;
Efficiency = 0.35
Coal ultimate analysis = 80% C; 13% O; 6% H; 1% S.
Coal HHV = 30MJ.kg-1
Flue gas composition by vol. = 13% CO2; 0.005% SO 2; 3.8% O 2; 82.9% N 2.

1500/0.35 = 4285.7 ˜ 4300MWth

4300/30 = 143.3 kg.s-1 (coal)
143.3*0.8 = 114.6 kg.s-1 (C)

44/12 = 3.67
3.67*114.6 = 420.2 kg.s-1 (CO2)
420.2/44 = 9.55 kmol.s-1
1 mol gas occupies 24.5E-3 m 3
9.55E3*24.5E-3 = 234 m3.s-1 CO2
234/0.13 = 1800 m3.s-1 Total

Carbon dioxide fixation volume/length/area:

Assumptions;
Optimum Chlorella gas flow = 1.25 L.min-1
Constant carbon dioxide fixation rate = 0.14 g.L-1.hr-1 (0.0023 kg.m -3.s-1)
Reactor diameter = 130 mm
Gap between each tube = 120 mm
420.2/0.0023 = 182696 ˜ 183E3 m 3
0.13 2*? /4 = 0.013 m 2
183E3/0.013 = 14,076,923m ˜ 14E6 m

(4*0.13)+(4*0.12) = 1.0m
1*14E6/4 = 3.5E6 m2
v (3.5E6) = 1870.8 ˜ 1870 m

Algal biomass production rate:

Assumtions;
Linear growth stage
Constant flue gas output
Doubling time = 2.5 hours
Original cell density = 5E7 cells.ml-1= 0.7 kg.m -3

24/2.5 = 9.6 day-1

0.7*183E3 = 128.1E3 kg
9.6*128.1E3 = 1229760 ˜ 1.23E6 kg.day-1
1.23E6/(24*602) = 14.2 kg.s-1

HHV Chlorella sorokiniana:

Assumptions;
Milne formula
Composition as given in table 2
Generic formulae and HHV of composition as given in table 5

HHV = 0.695*16.16 + 0.119*9.39 + 0.1*28.25 – 0.0153*0.069 = 15.6MJ.kg-1

Coal equivalent
Assumptions;
HHV Chlorella sorokiniana = 15.6 MJ.kg-1

15.6*14.2 = 221.52 MJ.s-1

221.52/30 = 7.4 kg coal
7.4/143 = 0.052 ˜ 5%

Anaerobic digestion:
Assumptions;
CH4 production rate of 0.4 m 3.kg -1
HHV CH4 = 55.5 MJ.kg -1
70% CH4, 25% CO 2 , 5% other.

0.4*14.2 = 5.68 m 3.s-1

55.5*5.68 = 315.2MJ.s-1
315.2/30 = 10.5 kg coal
10.5/143 = 0.073 ˜ 7.3%

(5.68/0.7)*0.25 = 2.03 m3.s-1 CO 2

(2.03/234)*100 = 0.87 %
100-0.87 = 99.23% reduction in CO2