CARBON CAPTURE USING THE MICROALGAE CHLORELLA VULGARIS IN A PACKED

BUBBLE COLUMN PHOTOBIOREACTOR

By

Kenneth Kofiga Zame

A Thesis Submitted

In Partial Fulfillment of the Requirements for the

Degree of Master of Science

In the Environmental Studies Program

YOUNGSTOWN STATE UNIVERSITY

August 2010

Digitally signed by ETD Program

DN: cn=ETD Program,
o=Youngstown State University,

ETD Program ou=School of Graduate Studies

and Research,
[email protected],
c=US
Date: 2010.10.31 17:00:10 -04'00'
 Carbon Dioxide Capture Using the Microalgae Chlorella vulagris in a Packed Bubble Colum
Photobioreactor

Kenneth Kofiga Zame

I hereby release this thesis to the public. I understand that this thesis will be made available from
the OhioLINK ETD Center and the Maag Library Circulation Desk for public access. I also
authorize the University or other individuals to make copies of this thesis as needed for scholarly
research.

Signature:
Kenneth Kofiga Zame, Student Date

Approvals:
Douglas Price, Thesis Advisor Date

Felicia P. Armstrong, Committee Member Date

Gary Walker, Committee Member Date

Lauren Schroeder, Committee Member Date

Peter J. Kasvinsky, Dean of School of Graduate Studies & Research Date

 iii

Acknowledgement

It is a pleasure to express my appreciation to those who made this thesis possible. I am thankful

to my supervisor, Dr. Douglas Price, whose encouragement, guidance and support throughout

my work on this thesis enabled me to successfully complete it. I would like to thank Dr. Gary

Walker and Dr. Lauren Schroeder for their support and guidance as members of the thesis

committee. Special thanks to Dr. Felicia Armstrong who is also a member of the committee for

her assistance and support not only on this thesis but also on my work as a teaching assistant at

the Geological and Environmental Science Department at Youngstown State University.

I would like to say thank you to Dr. Peter Norris (Interim Chair, Geological and Environmental

Sciences Department), Dr. Isam Amin, Dr. Colleen McLean, Ms. Shari McKinney and all faculty

members of the Department of Geological and Environmental Sciences at Youngstown State

University for their support in diverse ways.

I am also grateful to my family and friends for their support and encouragement.

Finally, I say glory be to God for everything.

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Table of Contents
Acknowledgements .......................................................................................................iii

List of Figures................................................................................................................vi

List of Tables.................................................................................................................vii

Abstract.........................................................................................................................viii

Chapter 1: Introduction..................................................................................................1

1.1 Greenhouse Gases and Global Warming……………………………………...1

1.2 Geological CO2 Sequestration………………………………………………...1

1.3 Chemical CO2 Capture………………….…………………………………….3

1.4 Biological Carbon Sequestration……….……………………………………..3

1.4.1 Forest Carbon Sequestration…………………………………………..4

1.4.2 Algae Carbon Capture…………………………………………………4

Chapter 2: Literature Review.........................................................................................6

2.1 Systems for Algae CO2 Sequestration………………………………………...6

2.2 Photobioreactors for Algae CO2 Capture……………………………………..6

2.3 Concept in Mass Transfer……………………………………………………..9

2.4 Resistance to Mass Transfer in Bioreactors………………………………….11

2.5 Requirements for Algal Photobioreactors…………………………………….12

2.6 Chlorella vulgaris for CO2 Sequestration in a Photobioreactor……..………12

2.7 Purpose of this Research……………………………………………………...13

Chapter 3: Methods, Procedures and Materials.............................................................14

3.1 Experimental Setup and Approach…………………………………………..14

3.2 Medium and Chemicals………………………………………………………16

 v

Chapter 4: Results and Discussion..................................................................................20

4.1 Material Balance on CO2..................................................................................20

4.2 Experimental Results………………………………………………………....21

4.2.1 Gas flow rate versus Outlet CO2 Concentration………………………..21

4.2.2 Gas flow rate versus Moles of CO2 Transferred………………………..22

4.2.3 Gas flow rate versus Moles of CO2 Transferred ……………………….24

4.3 Discussion of Results………………………………………………………….25

Chapter 5: Conclusions and Recommendations..............................................................27

References......................................................................................................................28
 vi

List of Figures

Fig. 1.1: Carbon Capture and Storage Options……………………………………………..2

Fig. 2.1 Open ponds for Algae CO2 Sequestration………………………………………….6

Fig. 2.2: Vertical Column Photobioreactor…………………………………………………..8

Fig. 2.3: Horizontal Column Photobioreactor………………………………………………..8

Fig. 2.4: Plate Photobioreactor……………………………………………………………….8

Fig. 2.5: Typical Gas-Liquid interface……………………………………………………….9

Fig. 2.6: Counter-current gas-liquid interface……………………………………………….10

Fig. 3.1: Schematic of Packed Bubble Column……………………………………………...15

Fig. 3.2: Packed Bubble Column equipment for Experiment………………………………..15

Fig. 3.3: Packed Bubble Column Photo bioreactor system for Experiment…………………16

Fig 4.1: Molar CO2 flow rate effect on outlet CO2 concentration at different alga

Culture Concentrations and CO2 inlet compositions………………………………...22

Fig 4.2: Gas flow rate effect on outlet CO2 concentration at different

CO2 inlet concentrations……………………………………………………………..23

Fig 4.3: Gas flow rate effect on outlet CO2 concentration at different

Algal culture concentrations at 5% CO2 composition……………………………….24

Fig 4.4: Molar Gas flow rate effect on % of CO2 transferred at different

Algal culture concentrations………………………………………………………....25

 vii

List of Tables

Table 2.1: Prospects and limitations of various algae photobioreactor systems ………..7

Table 3.1: Chemical Components of Bold 3N Medium………………………………..17

Table 3.2: Chemical Components of P-IV Metal Solution……………………………..18

Table 3.3: Chemical Components of Soilwater…………………………………………19

Table 3.4: Chemical Components of Vitamin B12 ……………………………………..19

Table 4.1: Result of varying inlet CO2 gas flow rate and corresponding

Outlet CO2 gas concentration at algal concentration of 0.21g/l and

Flow rate of 200 mL/min……………………………………………………….21

Table 4.2: Result of varying inlet CO2 gas flow rate and corresponding

Outlet CO2 gas concentration at algal concentration of 0.35g/l and

Flow rate of 200 mL/min……………………………………………………….21

Table 4.3: Result of varying inlet gas flow rate at algal Concentration of

0.21 g/L and inlet CO2 concentration of 5.0 mol% ……………………………22

Table 4.4: Result of varying inlet gas flow rate at algal Concentration of

0.21 g/L and inlet CO2 concentration of 5.0 mol%............................................23

 viii

Abstract

In response to increasing pressure to reduce carbon emissions, algae photobioreactors have

become central to finding environmentally-sustainable mitigation strategies for carbon capture.

Although a good number of photobioreactors have been proposed, only a few of them can be

practically used for large-scale algal CO2 sequestration and for that matter mass production of

algae. One of the major factors that limit their practical application with algal mass cultures is

mass transfer. Against this background, the purpose of this research was to test a scalable bench

scale photobioreactor with a capacity to enhance the mass transfer of CO2 (gas) into a fresh water

Chlorella vulgaris algal culture (liquid) phase. To achieve this, a packed vertical column being

referred to as a Packed Bubble Column Photobioreactor (PBCP) was used to increase gas-liquid

contacting surface area enhancing the mass transfer of the gas into the liquid phase.

The dynamics of the PBCP showed more moles of CO2 were transferred with higher composition

of inlet CO2 at same algal culture composition. Higher algal culture concentration showed lower

composition of CO2 in the outlet gas from of the reactor. CO2 increased in outlet gas composition

with increasing rate of moles of CO2 into the reactor. During 45 minutes of steady state semi-

continuous experimental test runs with 350 mL of algal culture at 0.21 and 0.35 g/L and CO2 (of

5.0 – 9.5% composition at flow rate of 25.0 mL/min to 112 mL/min); CO2 transferred into the

algal culture phase was typically in the range of 10 to 30%. These results have shown that the

PBCP is able to significantly enhance the transfer of CO2, and reductions of carbon dioxide

greater than 30% are achievable with higher algal cultures and CO2 composition in the reactor.
 1

Chapter 1 – Introduction

1.1 Greenhouse Gases and Global Warming.

Since the beginning of industrialization, the concentration of carbon dioxide gas in the

atmosphere has increased resulting in induced global warming (Ramanathan, 1988). Carbon

dioxide release into the atmosphere from anthropogenic sources alone in 1997 was 7.4 billion

tons and it is estimated that this would rise to 26 billion tons per year by the year 2100. Carbon

dioxide (CO2) contributes the highest proportion of the global greenhouse effect, due mainly to

its higher concentration in the atmosphere (Global Warming, 2010). World temperatures could

rise by 1.1 to 6.4 °C (2.0 to 11.5 °F) during the 21st century and sea levels would probably rise

by 18 to 59 cm (IPCC, 2007). Consequences of global warming include droughts, flooding,

expanding deserts, heat waves, ecosystem disruption, increasingly severe weather, and loss of

agricultural productivity (Morrissey et al, 1997). Over the years many attempts have been made

to reduce atmospheric carbon dioxide through geological, chemical and biological sequestration.

1.2 Geological Sequestration

In geological sequestration, gas phase CO2 as well as supercritical liquid CO2 can be stored in

geological formations. Gas phase CO2 has also been successfully used over the years for

enhanced oil and gas recovery by injection into gas and oil reservoirs (DOE, 1999). The storage

of CO2 in the gas phase in geological formations would reduce storage capacities and limit fossil

fuel use to only decades. With gas phase CO2 sequestration, the gas could be released should

there be an accidental penetration in the formation (Gunter W.D et. al 2004; Kaarstad O. 2002).

Supercritical CO2 at pressures exceeding 7.38 MPa, is highly favored over gas phase storages as
 2

the holding capacity in geological formations is significantly increased. Supercritical CO2 is also

more reactive than in the gas phase and has the ability to combine chemically with metals to

form solid carbonates. However these geochemical reactions that form carbonates would take

centuries to millennia, and the possibility of leakage is very likely to occur as supercritical CO2

attacks concrete which is a normally the material for capping wells (Duguid A, et al 2004;

Perkins E, et al). Supercritical CO2 is also mobile and could poison a potable aquifer should an

underground fixture exist from the geological formation to the aquifer. Carbon capture and

sequestration is currently expensive (IEA GHG, 2000). Deep ocean injection of CO2 at depths of

100 meters, where CO2 would dissolve has been proposed. Another option proposed is to create

CO2 underwater lakes by piping directly onto the sea floor CO2 at depths greater than 3000

meters, where it would be denser than water. However ocean storage of CO2 is likely to cause

significant environmental problems as the CO2 would combine with water to form carbonic acid,

increasing the acidity of the water. As a result of this, shells of shellfish and corals will dissolve

and reproduction of sea creatures would also be affected. Alternatives are being considered as

potential problems and liabilities with geological sequestration are major.

Figure 1.1: Carbon Capture and Storage Options.

 3

1.3 Chemical CO2 Capture

Before CO2 is sequestered into geological or other storage sites, it must be purified or enriched

beyond the 5-15% concentration typically found in the products of combustion (Kohl, A. O and

Nielsen R, 1997). The two main methods used to purify CO2 for sequestration are: 1) absorption

– desorption separation and 2) oxygen based combustion. Monoethylamine (MEA or amine) is

commonly used in the absorption – desorption method to absorb the CO2 from the combustion

gas. The CO2 is then stripped (desorbed) in a separate heated chamber as a relatively pure gas.

The oxygen–based combustion removes the nitrogen from the combustion air before combustion

with the fossil fuels such as coal or natural gas. This results in combustion products of CO2 and

water which eliminates the task of having to remove nitrogen, as it is nonreactive and difficult to

separate from CO2 (Kohl, A. O and Nielsen R,1997). To run an amine scrubbing system for CO2

separation, it is estimated that about one-third of the energy output of a power plant would be

required (Alstom Power Inc., 2001). This leads to significant cost of the energy produced.

Activated carbon powder impregnated with potassium carbonate has also been demonstrated to

chemically adsorb CO2 as high as 8 to 17% in the flue gas. The activated carbon is regenerated

by stripping off the CO2 gas at a higher temperature. When compared to other processes such as

the conventional amine process, this approach is efficient, provides low utility cost and is

energy-conservative (Ebune, 2008).

1.4 Biological Carbon Sequestration

Biological (or terrestrial) sequestration involves the net removal of CO2 from the atmosphere by

plants and micro-organisms and its storage in vegetative biomass and in soils. Advantages of

biological sequestration include: 1) net sequestration of relatively large volumes of carbon at

 4

comparatively low cost, 2) protection or improvement of soils, water resources, habitat, and

biodiversity, and 3) promotion of more sustainable agriculture and forestry practices (Climate

Change Connection, 2010).

1.4.1 Forest Carbon Sequestration

Forests as natural sinks sequester CO2 in cellulosic structure of trees and humus soil. With about

600 power plants in the United States; land, energy and the cost required to plant trees to

sequester significant quantities of CO2 makes this option unattainable as each coal power plant

on the average produces about 4 million tons of CO2 annually (Union of Concerned Scientist,

2010). Carbon stored in soils oxidizes quickly into the atmosphere or water. Forests also release

the carbon stored in trees in at most decades as the forests burn or the trees are uprooted or

damaged severely. An example is Hurricane Katrina destroying about 320 million large trees in

the Gulf Coast forest (NASA, 2007).

1.4.2 Algae Carbon Capture

Algae represent about 0.5% of global biomass yet produces about 70% of the net oxygen on

earth. In the process CO2 is sequestered by photosynthetic means in large quantities and algae

biomass rich in lipids which can be used for biofuels is produced (Hall J, 2008). Algae thus

offers an alternative and sustainable solution in two main ways; 1) value-added sequestration of

CO2 through conversion to biomass and 2) biomass which can be use to produce renewable fuels

(biofuels and/or biogas). There exist over 40,000 species of algae and cyanobacteria

(photosynthetic prokaryotic organisms), in many forms and under different conditions that can
 5

be optimized to sequester carbon dioxide through photosynthesis. These include microalgae

species such as Chlorella, Spirulina and Dunaliell.

 6

Chapter 2 – Literature Review

2.1 Systems for Algae CO2 Sequestration

Algae can be used in open systems (open ponds) as shown in Figure 2.1 and closed systems

(closed photobioreactors) as show in Figures 2.2, 2.3 and 2.4 to sequester carbon. Open systems

can be natural waters (lakes, lagoon, ponds) and artificial ponds or containers. Open ponds are

easier to construct and operate than closed systems. Limitations to open ponds include poor light

utilization by algae cells, evaporative losses of water, diffusion of CO2 to the atmosphere, and

requirement of large areas of land. Other problems include contamination by predatory

microorganisms and other fast growing heterotrophs. Closed photobioreactors have attracted

much interest because they especially allow better control for higher CO2 capture and yield of

biomass (Ugwu C. U et al, 2008).

Figure 2.1 Open ponds for Algae CO2 Sequestration

2.2 Photobioreactors for Algae CO2 Sequestration

A good number of photobioreactors have been proposed for CO2 mitigation using algae, and for

that matter algae growth, however only a few of them can be practically used for mass
 7

production of algae. One of the major factors that limit their practical application in algal mass

cultures is less efficient mass transfer of CO2 (Ugwu et al, 2008). Table 2.1 below presents the

prospects and limitations of various photobioreactor systems for alga culture systems.

Table 2.1 Prospects and limitations of various algae photobioreactor systems (Kaarstad O.
2002)

Photobioreactor System Prospects Limitations

Vertical - Column Good mass transfer, good mixing Small illumination surface
with low shear stress, low energy area, their construction
consumption, high potentials for require sophisticated
scalability, easy to sterilize, readily materials, shear stress to algal
tempered, good for immobilization cultures, decrease of
of algae, reduced photo inhibition illumination surface area upon
and photo-oxidation. scale-up

Flat-plate Large illumination surface area, Scale-up requires many

suitable for outdoor cultures, good compartments and support
for immobilization of algae, good materials, difficulty in
light path, good biomass controlling culture
productivities, relatively cheap, temperature, some degree of
easy to clean up, readily tempered, wall growth, possibility of
low oxygen buildup. hydrodynamic stress to some
algal strains.

Tubular Large illumination surface area, Gradients of pH, dissolved

suitable for outdoor cultures, fairly oxygen and CO2 along the
good biomass productivities, tubes, fouling, some degree of
relatively cheap. wall growth, requires large
land area.
 8

Figure 2.2: Vertical Column Photobioreactor

Figure 2.3: Horizontal Column Photobioreactor

Figure 2.4: Plate Photobioreactor

 9

2.3 Concepts in Mass Transfer

Gas absorption involves the mass transfer from the gas phase to the liquid phase where the gas

molecules diffuse from the main body of the gas phase to the gas-liquid interface, then cross this

interface into the liquid side, and finally diffuse from the interface into the main body of the

liquid. The interface can represent any location in the gas absorption equipment where the gas

contacts the liquid. A typical gas-liquid interface is show in Figure 2.5 below.

Figure 2.5: Typical Gas-Liquid interface

 10

Three gas flow regimes can visualized, as listed below:

o Fully developed turbulent region where most of the mass transfer takes place by eddy

diffusion

o A transition zone with some turbulence

o A laminar film with molecular diffusion

Normally for analysis as well as development of various correlations of mass transfer

phenomena the Two-Film Theory of mass transfer is used. Figure 2.6 shows the two gas film

interface that can be represent at any point in the gas absorption equipment where the gas

contacts the liquid (Separation Processes, 2010).

Figure 2.6: Counter-current gas-liquid interface

 11

2.4 Resistance to Mass Transfer in Bioreactors

Resistance to mass transfer in bioreactor equipment can be encountered in eight (8) different

ways;

1) In the gas film

2) At the liquid-gas interface

3) In the liquid film surrounding the gas interface

4) In the liquid phase

5) In the liquid film surrounding the solid (microorganism)

6) At the liquid-solid (microorganism) interface

7) In the solid phase

8) At the site of reaction (within the microorganism)

These resistances occur in series and the largest would be the rate controlling step. The entire

mass transfer is normally modeled using a single mass transfer correlation (Harvey W. Blanch,

Douglas S. Clark. 1997).

The resistance of the gas film within the bubble (1) can be neglected relative to the liquid film

surrounding the bubble (4) as gas-phase diffusivities are typically much higher than liquid-phase

diffusivities. Interfacial resistance to transport [for (2) and (6)] is small and can also be

neglected. Transport through the liquid is rapid when the liquid is adequately mixed; hence (4)

may also be neglected with adequate mixing (Harvey W. Blanch, Douglas S. Clark. 1997). In

the case of microbial particle of single cell of size 1 to 2 micron, their small size (could have

large surface interfacial area) relative to that of a gas bubble and result in the liquid film
 12

surrounding the gas bubble, and thus becoming the rate determining step. The rheology of the

liquid also has a strong influence on the rate of mass transfer (Harvey W. Blanch, Douglas S.

Clark. 1997).

2.5 Requirements for Algal Photobioreactor

Availability and intensity of light are the major factors controlling the productivity of

photosynthetic cultures. Light intensity requirement of microalgae are relatively low compared to

higher plants (Eiichi Ono et al, 2010). In microalgae, the biomass productivity is a function of

the cell concentration in the culture at steady state and the growth rate is governed by the amount

of light (average irradiance) which is the rate controlling factor. The growth rate increases with

increasing irradiance to a maximum irradiance limit beyond which the growth is inhibited – a

phenomenon known as photo inhibition (Lee, Y.K, 1999). Photo inhibition is often suspected as

the major cause of reducing algal productivity (Eiichi Ono et al, 2010). Like any other living

organism, algae require nutrients to sustain, grow and thrive. These nutrients are similar to what

plants requires and consist mainly of nitrogen, phosphorus, potassium and trace amounts of iron

and other metals. Growth media for algae are prepared by using mixtures of these nutrients

suitable for the maintenance of the algal culture.

2.6 Chlorella vulgaris for CO2 Sequestration in a Photobioreactor

Several species of microalgae have been tested to grow in CO2 concentration over 15% v/v

(Eiichi Ono et al, 2010). Chlorella sp. is one of the most studied and researched algae for use in

CO2 sequestration. Chlorella vulgaris algae are unicellular from 5 to 10 micron in size

(Chlorella vulgaris, 2010).

 13

2.7 Purpose of this Research

In response to increasing pressure to reduce carbon emissions, fossil-fired utilities are pursuing

deep geological sequestration as one of the options for handling the enormous quantities of CO2

being introduced to the atmosphere. However for environmentally-sustainable mitigation

strategies for carbon capture, the use of algae has become central as it also offers a potential for

producing renewable transportation fuels like biodiesel. Although a good number of

photobioreactors have been proposed, only a few of them can be practically used for large scale

algal CO2 sequestration and for that matter mass production of algae. One of the major factors

that limit their practical application in algal mass cultures is mass transfer.

The purpose of this research was to test a scalable bench scale photobioreactor with a capacity to

enhance the mass transfer of CO2 (gas) into a Chlorella vulgaris algal culture (liquid) phase. To

achieve this, a packed vertical column being referred to as a Packed Bubble Column

Photobioreactor (PBCP) was used. It was proposed that as the liquid (algal culture) trickles

downwards through the pores of the packing counter-currently to the gas (CO2) flow, gas-liquid

mixing and for that matter contacting surface area would be increased and this would enhance

the mass transfer of the gas into the liquid phase.

 14

Chapter 3 - Methods, Procedures and Materials

3.1 Experimental Setup and Approach

A schematic of the packed bubble column is shown in Figures 3.1 and 3.2. The bench-scaled

experimental setup of the packed bubble column photobioreactor as shown in Figure 3.3 consists

of a transparent polycarbonate absorption column packed with glass beads. Gas in the range of 4

– 10% CO2 was obtained by mixing air (supplied from a Welch compressor and vacuum pump)

with CO2 from a tank (PAXAIR) in a mixing chamber (17 cm internal diameter by 10 cm

height) and through rotameters to control the flow. The gas was fed at the bottom of the

photobioreactor through a gas sparger which was 2 cm below the bottom of the packing. The

algal culture was sprayed at 200 mL/min at the top of the column 4 cm above the tip of the

packing. The culture (liquid) trickled downwards through the packing in counter-currently to the

gas flowing upwards. The algal culture collects into a holding flask from which it is semi-

continuously re-circulated using a mechanically actuated diaphragm (MAD) pump (Liquid

Mectronics Inc. MAD Pump with a suction lift) at a flow rate of 200 mL/min. The diaphragm

pump was used to minimize any stress to the algae cells. Light energy for the photosynthetic

fixation of CO2 by the algae was provided by a cool fluorescence light source. For the effect of

gas velocity on mass transfer of CO2 to the liquid phase the gas volumetric flow rate was

increased from 25 to 112 mL/min at constant concentration of CO2. For the effect of algal culture

on CO2 transfer into the algal culture, the experiment was carried out at different concentrations

of algae culture (0.21 to 0.70 g/L). The inlet and outlet gas concentrations to the column were

monitored using CO2 Venier Gas sensors to determine steady state composition and analyzed

using a Gas Chromatograph (Varian CP – 3800 Gas Chromatograph).

 15

Equipment Properties.

Column Height 45.0cm

Packing Height 25.5cm

Column Diameter 5.0 cm

Glass Bead Diameter 12mm

Figure 3.1: Schematic of Packed Bubble Figure 3.2: Packed Bubble Column
Column Equipment for Experiment

The algal mass concentration of the culture was determined by filtering 10 mL samples of the

culture and determining the dry weight. All experiments were with 350 mL of culture at a

recirculation rate of 200 mL/min. Gas samples were analyzed for CO2 concentration after 45

minutes of steady state CO2 concentrations. The pH was continuously monitored during the

experiments using a Vernier pH sensor and it ranged from 6.8 to 7.9

 16

Figure 3.3: Packed Bubble Column Photo bioreactor for Experiment

3.2 Medium and Chemicals

The microalgae Chlorella vulgaris on proteose agar medium in a 25 ml screwed-cap tube was

obtained from UTEX in University of Texas at Austin. This was cultured for 3 days in 10 mL of

Bold 3N Medium; an artificial fresh water medium for axenic cultures in a test tube. This was

transferred into a 250-mL flask and the medium made up to 50 mL and cultured for 5 days. This

was further cultured in a 1-L flask with 400 mL of the medium. Table 3.1 outlines the chemical

(nutrient) components in Bold 3N medium.

Preparation of 1 Liter Bold 3N Medium (UTEX):

1. To approximately 850 mL of deionized H2O, add each of the components in the order

specified (except vitamins) while stirring continuously.

2. Bring the total volume to 1 L with deionized H2O.

 17

3. Cover and autoclave medium (at 240oF).

4. When cooled add Vitamin B12 and store at refrigerated temperature.

Table3.1: Chemical Components of Bold 3N Medium

Stock Solution Final

# Component Amount
Concentration Concentration

NaNO3 (Fisher
1 30 mL/L 10 g/400 mL H2O 8.82 mM
BP360-500)

CaCl2·2H2O (Sigma
2 10 mL/L 1 g/400 mL H2O 0.17 mM
C-3881)

MgSO4·7H2O (Sigma
3 10 mL/L 3 g/400 mL H2O 0.3 mM
230391)

K2HPO4 (Sigma P
4 10 mL/L 3 g/400 mL H2O 0.43 mM
3786)

KH2PO4 (Sigma P
5 10 mL/L 7 g/400 mL H2O 1.29 mM
0662)

NaCl (Fisher S271-

6 10 mL/L 1 g/400 mL H2O 0.43 mM
500)

7 P-IV Metal Solution 6 mL/L

Soilwater: GR+
8 40 mL/L
Medium

9 Vitamin B12 1 mL/L

Details of chemical composition of P-IV Metal Solution, Soilwater and Vitamin B12 are

presented in Tables 3.2, 3.3 and 3.4 respectively.

 18

Preparation of 1 Liter P-IV Metal Solution:

1. To approximately 950 mL of deionized H2O, add the nutrients in the order listed while

stirring continuously. Note: The Na2EDTA should be fully dissolved before adding other

components.

2. Bring total volume to 1 L with deionized H2O.

3. Store at refrigerator temperature.

Table 3.2: Chemical Components of P-IV Metal Solution

## Component Amount Final Concentration

1 Na2EDTA·2H2O 0.75 g/L 2 mM

(Sigma ED255)

2 FeCl3·6H2O (Sigma 0.097 g/L 0.36 mM

1513)

3 MnCl2·4H2O (Baker 0.041 g/L 0.21 mM

2540)

4 ZnCl2 (Sigma Z-0152) 0.005 g/L 0.037 mM

5 CoCl2·6H2O (Sigma 0.002 g/L 0.0084 mM

C-3169)

6 Na2MoO4·2H2O (J.T. 0.004 g/L 0.017 mM

Baker 3764)

Preparation of 200 mL Soilwater: GR + Medium:

1. Combine all components listed.

2. Cover the medium container and steam for 2 consecutive days, 3 hours on each day.

Pasteurization is a gradual rising of temperature to approximately 95°C in 15 minutes.

 19

Then increase the temperature to just over 98°C for the 3 hour duration. Cooling occurs

gradually at room temperature.

Table 3.3: Chemical Components Soilwater

# Component Amount Final

Concentration

1 Green House Soil 1 tsp/200 mL H20

2 CaCO3 (optional) 1 mg/200 mL H2O 0.05mM

(Fisher C 64)

Preparation of 200mL Vitamin B12

1. Prepare 200 mL of HEPES buffer (50 mM)

2. Adjust the pH to 7.8

3. Add Vitamin B 12 (0.1 mM) wait until fully dissolved

4. Sterilize using a 0.45 µm Millipore filter. Store in dark at freezer temperature.

Table 3.4: Chemical Components of Vitamin B12

# Component Amount

1 HEPES buffer pH 7.8 (Sigma 2.4 g/200 mL dH2O

H-3375)

2 Vitamin B12 0.027 g/200 mL dH2O

(cyanocobalamin, Sigma V-
6629)
 20

Chapter 4 - Results and Discussion

4.1 Material Balance on CO2

Based on the assumption that the molecules of a gas experience no intermolecular forces and that

the molecules occupy no volume, the idea gas law (PV = nRT) gives an accurate description of

the behavior of real gases at low pressure and temperatures. At room conditions of 25oC (298K)

and atmospheric pressure of 1 atmosphere at which the experiment was carried out, the molar

volume, Vm is given by Equation (1) below, where R is the ideal gas constant.

(R = 0.08206 L.atm. K-1. mol-1).

RT
Vm   24.465 L / mole (Eqn. 1)
P

The moles of CO2 transferred, N (mol/min) is given by;

N  G1 yCO2 ,1  G2 yCO2 , 2 (Eqn. 2)

Where: G1 yCO2 ,1 = Moles of CO2 in the inlet gas stream, (mol/min)

G2 yCO2 , 2 = Moles of CO2 in outlet gas stream, (mol/min)

yCO2 ,1 = Mole fraction of CO2 in the inlet gas stream

yCO2 , 2 = Mole fraction of CO2 in the outlet gas stream

G1 = Molar flow rate of inlet gas, (mol/min) given by:

F1
G1  (Eqn. 3)
Vm

Where: F1 = Flow rate of inlet gas, (mL/min)

G2 = Molar flow rate of outlet gas, (mol/min) given by:

 21

G2 

G1 1  yCO2 ,1  (Eqn. 4)
1  yCO2 , 2

4.2 Experimental Results

4.2.1 Gas flow rate versus outlet CO2 concentration

Tables 4.1 and 4.2 list the data collected for experiments where the total inlet gas flow, the inlet

carbon dioxide composition and the algal concentration were varied.

Table 4.1: Results of varying inlet CO2 gas flow rate and corresponding outlet CO2 gas
concentration at algal concentration of 0.21 g/l and flow rate of 200 mL/min.
Outlet Gas CO2
Inlet Gas Stream Stream Transferred
Concentration of
Flow Rate Concentration of CO2 CO2 Molar Flow CO2
(mL/min) (Mol %) rate × 10-3 (mol/min) (mol %) %
25 5.31 0.05 3.62 33.03
50 5.16 0.11 4.13 20.90
50 4.58 0.09 3.98 13.63
67 4.56 0.12 3.87 15.64
112 11.98 0.55 12.10 -
25 14.03 0.15 11.22 22.53
37 16.98 0.26 13.10 26.32
50 15.81 0.32 13.32 18.15
67 12.63 0.35 13.11 -

Table 4.2: Results of varying inlet CO2 gas flow rate and corresponding outlet CO2 gas
concentration at algal concentration of 0.35 g/L and flow rate of 200 mL/min.

Outlet Gas CO2

Inlet Gas Stream Stream Transferred
CO2 Molar Flow Concentration of
Flow Rate Concentration of CO2 (Mol rate × 10-3 CO2
(mL/min) %) (mol/min) (mol %) %
25 9.45 0.10 4.15 58.53
37 8.08 0.12 5.87 29.08
50 10.11 0.21 7.68 26.07
67 10.53 0.29 10.04 5.18
37 7.6 0.11 6.72 12.38
50 9.62 0.20 7.30 25.98
67 9.66 0.26 8.41 14.10
89 9.02 0.33 8.75 3.27
112 9.46 0.43 8.97 5.75
 22

Molar Inlet CO2 flow rate vs. outlet CO2

Concentration

Figure 4.1: Molar CO2 flow rate effect on outlet CO2 concentration at different alga culture
concentrations and CO2 inlet compositions.

4.2.2 Gas flow rate versus Moles of CO2 Transferred

Experimental data on effect of moles of CO2 fed to the reactor on the moles of CO2 transferred

into culture was investigated at constant inlet CO2 concentration and algal culture concentrations

are presented in Table 4.3 and Table 4.4 and relations in Figures 4.2 and 4.3.

Table 4.3: Result of varying inlet gas flow rate at algal Concentration of 0.21 g/L and inlet
CO2 concentration of 5.0 mol%
Inlet Gas Stream Outlet Gas Stream
Flow Rate Concentration of CO2 Molar Flow rate × 10- Concentration of CO2 Transferred
3
(mL/min) CO2 (mol %) (mol/min) CO2 (Mol %) × 10-6 (mol/min)
25 5.31 0.05 3.62 17.93
50 5.16 0.11 4.13 22.05
67 4.56 0.12 3.87 19.53
 23

Table 4.4: Result of varying inlet gas flow rate at algal Concentration of 0.21 g/L and inlet
CO2 concentration of 9.5 mol%

Inlet Gas Stream Outlet Gas Stream

Flow Rate Concentration of CO2 Molar Flow rate × 10-3 Concentration of CO2 Transferred
(mL/min) CO2 (Mol %) (mol/min) CO2 (Mol %) × 10-6 (mol/min)
50 9.62 0.20 0.15 51.10
67 9.66 0.26 0.23 37.31
112 9.46 0.43 0.41 24.89

Inlet Gas flow rate vs. Moles of CO2 Transferred at

Different CO2 mol% Concentrations

Figure 4.2: Gas flow rate effect on moles of CO2 transferred at different inlet CO2
concentrations
 24

Inlet Gas flow rate vs. Moles of CO2 Transferred at

Different Culture Concentrations

Figure 4.3: Gas flow rate effect on outlet CO2 concentration at different alga culture
concentrations at 5% CO2 inlet composition.

4.2.3 Gas flow rate versus Moles of CO2 Transferred

Figure 4.4 (obtained from data on Table 4.1 and 4.2) presents the relation between molar flow

rate of CO2 into the reactor and the CO2 transferred at 0.21 and 0.35g/L of culture.
 25

Inlet Molar Gas flow rate vs. % of CO2 Transferred at

Different Culture Concentrations

Figure 4.4: Molar Gas flow rate effect on % of CO2 transferred at different culture
concentrations

4.3 Discussion of Results

Figure 4.1 indicated a general trend of increase in CO2 composition in the outlet gas from the

reactor when increasing the molar rate of CO2 into the reactor. Algal concentration at 0.35 g/L

showed lower concentration of CO2 in outlet gas than at 0.21 g/L. This was confirmed in Figure

4.3 where at the same inlet concentration of 5% CO2 more moles of CO2 were transferred at

higher concentration (0.35 g/L) of culture. Figure 4.2 shows that at same culture concentration,

more moles of CO2 were transferred at higher composition (9.5%) of inlet CO2 compared to
 26

5.0%. The moles of CO2 transferred with culture at 0.21 g/L and 5% inlet CO2 composition in

Figures 4.2 and 4.3 show an increasing trend of CO2 transferred at lower feed rates, after which

further increase in inlet gas flow rate results in decreasing the moles of CO2 transferred. This

trend is replicated in Figure 4.1 for cultures at 0.21 and 0.35 g/L.

Figure 4.4 shows a general trend that higher percentages of carbon dioxide are absorbed at lower

inlet molar flow rates of carbon dioxide. Reductions of carbon dioxide greater than 30% are

achievable, which warrants further study for this style of reactor.

 27

Chapter 5 – Conclusion and Recommendation

Overall, this is an initial attempt in testing the dynamics of the mass transfer of CO2 with this

Packed Bubble Column Photobioreactor using Chlorella vulgaris microalgae. The results have

shown that the PBCP is able to substantially enhance the transfer of CO2; typically in a range of

10 to 30% into Chlorella vulgaris culture at 0.21 and 0.35 g/L. Further study should entail the

following:

1. Increasing the reactor length and diameter to determine the influence of holdup time and

gas velocity on the mass transfer of carbon dioxide.

2. Control of light source to understand the photo-inhibition effect on carbon dioxide

uptake.

3. Increasing the algal concentration further for enhance mass transfer and to determine

whether the system is controlled by carbon dioxide metabolism or mass transfer

resistance.

4. Long term study on algal viability and nutrient requirements.

5. Analysis of the algae composition to determine if biofuel precursors are formed.

6. Application of appropriate models to determine scale-up requirements.

 28

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