J. Algal Biomass Utln.

2009, 1 (1): 18 28 PHYCO SPECTRUM INC

NOVEL SOLVENT EXTRACTION FOR EXTRACTION OF OIL FROM ALGAE BIOMASS GROWN IN DESALINATION REJECT STREAM
L. Govindarajan1 Nitin Raut2 and Ahmed Alsaeed3 Department of Mechanical & Industrial Engineering Caledonian College of Engineering Sultanate of Oman govindarajan@caledonian.edu.om Abstract Renewable and carbon neutral biofuels are necessary for environmental and economic sustainability. The viability of the first generation biofuels is however questionable because of the conflict with food supply. Algae based biofuels are considered as a viable alternative as the oil productivity of many algae exceeds that of oil crops. This algae based biomass has the ability to meet the partial energy demands and helpful in protection of the environment. Extraction of fuels from microalgae biomass is a challenging task as it is critical in determining the overall economics of fuel production. It has been found that the conventional extraction methods employed warrant either modernized equipment or requires difficult process conditions. The focus of the novel extraction method is to use the combination of solvent extraction and magnetic stirred agitation to expel the oil from the biomass. This methodology is proved to be cost effective when compared to extraction methods like super critical extraction, nano-assisted extraction which are widely under research. This research work aims to use the magnetic stirrer based extraction for sustainable biofuel production. The research work has been found to be successful in its nascent attempt of using natural algae biomass for the extraction of oil. This research work may lead to new dimension if the magnetic stirred or electromagnetic assisted agitation is employed on a commercial scale.
1

Senior Lecturer, Department of Mechanical & Industrial Engineering; Author to whom correspondence is to be addressed.
2

Assistant Professor, Sohar University B.Sc (Hons.) Process Operations & Maintenance Student

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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

Introduction There are several methods tried to extract oil from algae that includes

together is estimated to draw more than 95% of the total oil in the algae. Soxhlet extraction method employs a series of steps that includes washing, or filtration with the use of organic solvent, such as hexane or petroleum ether. Gasification is the process by which carbonaceous materials (hydrocarbon) are converted to a synthesis gas (syngas) by means of partial oxidation with air, oxygen and/or steam at high temperatures in the range 800 900C. Biomass with high moisture is gasified directly to methane rich fuel gas without drying. In addition, nitrogen in the biomass is converted to ammonia during the reaction. Microalgae cell

mechanical systems, chemical, thermal, plasma and microwave techniques. Most of the traditional methods do not offer the long-term solutions or they rely on the solvents. Oil press is the simplest method and most popular of the techniques

employed in commercial scale. Mechanical methods include expression / repelling press. Algae oil is extracted by using suitable solvents. In solvent based methods, care must be taken to avoid exposure to vapors and direct contact with the skin, any of which could cause serious damage. The two commonly employed

precipitates derived from centrifugation, which are of high moisture content, are thus good raw materials for liquefaction. Direct hydrothermal liquefaction in sub-critical water conditions is a technology that can be employed to convert wet biomass material to liquid fuel. The chemical methods are (i) Hexane solvent and (ii) Soxhlet extraction. Hexane solvent extraction can be used in isolation or can be used along with the oil press / expeller method. After mechanical method,

remaining pulp is mixed with cyclohexane to expel the remaining oil. Oil dissolved in cyclohexane and the pulp is out of the solution. Oil and separated from

liquefaction is performed in an aqueous solution of alkali or alkaline earth salt at about 300 C and 10 MPa without a reducing gas such as hydrogen and/or carbon monoxide. Pyrolysis is conversion of biomass to biofuel, charcoal and gaseous
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cyclohexane by distillation. These two stages (cold press & Hexane solvent)

J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

fraction by heating the biomass in the absence of air to around 500 C, or by heating in the presence of a catalyst at high heating rate and with short gas residence time to crack into short chain molecules and then being cooled to liquid rapidly. The longer residence times can cause secondary cracking of the primary products, reducing yield and adversely affecting the biofuel properties. In addition, a low heating rate and long residence time may increase the energy input. Fast pyrolysis process has been also used maximizing the liquid yield. The advantage of fast pyrolysis is that it can directly produce a liquid fuel. If flash pyrolysis is used, the conversions of biomass to bio-crude up to 80% efficiency are reported. Literature Review Mohamed El Hattab et al (2007) used three different methods:

identified were C11 hydrocarbons for HD method, sesquiterpenes for FMAHD method and sulphur compounds for SFE method. Michele and Peckol (2000) conducted a laboratory effectiveness experiment of to assess (N and the P)

nutrient

application to indigenous, marine microbial populations as a bioremediation technique to respond to oil spills along the coastline. They also investigated the effects of various concentrations (10 ppm to 1 ppt) of No. 2 fuel oil, commonly transported oil, on growth rates of the intertidal macroalgae Fucus vesiculosus. Bioremediation may be a viable clean-up alternative for petroleum contamination of temperate ecosystems, particularly in areas of heavy shipping traffic, which probably support a relatively large background population Sarmidi of oil-

degrading

organisms.

(2009)

presented a brief review on the main conversion processes of microalgae

hydrodistillation (HD), focused microwaveassisted hydrodistillation (FMAHD) and supercritical fluid extraction (SFE) for the extraction of volatile metabolites of the brown alga Dictyopteris membranacea. The oils obtained were analyzed by GCMS (identification and determination of

becoming energy. As microalgae have high water content, not all biomass energy conversion processes can be applied. By using thermochemical processes, oil and gas can be produced, and by using biochemical processes, ethanol and biodiesel can be produced. It has been observed from the literature survey that there is a need to try for a novel methodology for extraction of oil
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metabolites) and the results were compared. The main chemical classes of compounds

J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

that must also be simple enough to provide cost effectiveness to large scale extraction. The extraction plays an important role in determining the overall economics of the algae based biofuel production process. Experiments

Algae

biomass

were

obtained

from

seawaters of Al Athiba, Sultanate of Oman and transferred to a bath containing seawater collected in the vicinity of algae substrata. Biomasses were allowed to grow in a laboratory scale photo bioreactor as shown in Fig. 1.

Fig. 1 Algae Biomass in Laboratory Scale Photobioreactor

After appreciable growth has been established, algae biomass was made to assimilated to desalination reject stream by injecting 20 cc of biomass each day. Finally after appreciable growth period, algae biomass was separated from the medium, filtered and dried. Algae were grounded with motor and pestle. Grounded algae were dried for 20 min at 80C in an incubator for

removing water. Dry weight of the algae obtained was found to be 29.1 grams in a medium of 150cc. About 15 grams weight of hexane was mixed with the dried ground algae to extract oil. Solvent extraction was carried out with magnetic agitation for four hours to expel the oil and was kept for an hour to achieve gravity separation. The extracted oil was evaporated to release
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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

solvent. The amount of oil, pH, density and viscosity were recorded. Results and Discussion After the satisfactory establishment of biomass growth from the preliminary kinetic study, the medium of growth was

changed

to

desalination

reject

stream

obtained from desalination plant in Ministry of Defense, Oman. The concentration polarization of the brine was found to be four times that of the inland feed water. Composition of the desalination reject stream was given in Table 1.

Table 1 Analysis of Desalination Reject Stream (Medium Used for cultivating Algae Biomass) Parameters Color Odor pH Electrical Conductivity Total Dissolved Solids Total Hardness Calcium Hardness Magnesium Hardness Total Alkalinity(Alk) Bicarbonate Alk Carbonate Alk Hydroxide Alk mS/cm-1 mg/L ppm as CaCO3 ppm as CaCO3 ppm as CaCO3 ppm as CaCO3 ppm as CaCO3 ppm as CaCO3 ppm as CaCO3 Units Hazen Units Values 5 - 10 None 7.58 7.13 4944 1740 900 203.88 600 600 0 0

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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

Turbidity Calcium as Ca2+ Magnesium as Mg2+ Sodium as Na+ Potassium as K+

NTU ppm ppm ppm ppm

0.94 24.51 167 1480 25

Chloride Sulphate Nitrate Fluoride Bromide Silicates as SiO2

ppm ppm ppm ppm ppm ppm

1467.311 1226.027 20.378 1.940 Not detected 47.197

Scm-1 microsiemens per centimeter ppm parts per million mg/L milligrams per liter NTU Nephelometric Turbidity Units FRC Free Residual Chlorine

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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

The assay of the biomass separated was carried out to determine the nature of species present. It was found to contain the species of Polysiphonia, Ectocarpus,

analyzed

by

combination

of

gas

chromatography and mass spectroscopy (GCMS-QP5050A Make: SHIMADZU) and Table 2 shows the composition analysis of major components present in the oil. Magnetic stirrer based agitation was

Diatoms, Meuisnopedia and Cyanobacteria. Detailed study was carried out to use only one methodology for the removal of oil. The reason is the time required to repeat the same from the start if the method fails to yield satisfactory results. Then the oil was

attempted in additional to the conventional solvent extraction. Composition analysis carried out then complements the extraction approach used in the study.

Table 2 Composition Analysis of Oil from Algae Biomass by Gas Chromatography Mass Spectroscopy Component Formula Mass weight Mass% g/mol Nonane,3-methyl-5-proplC13H28 128.2 282.55 1.68 2 2.98 2.77 1.68

Hexadecane,2,6,10,14-tetramethl-(CAS)Phytane C20H42 Hexatriacontane 7-methyl-2,2-dimethyl-2h-chromen-5-amine Nonadecane (CAS) n-nonadecane

HTCC36H74 506 C15H15NO3 C19H40 257 268.52

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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

Hentetracontanol Docosanoic acid Heneicosane Eicosane 2,6,10,14-tetramethylhexadecane

C41H84O C22H44O2 C21H44 C20H42 C16C34

593.10506 340.58 296.57 282.5475 226.44116

3.45 3.63 5.02 3.91 3.61

The growth of the biomass was continuously analysis monitored by conducting This

arrangement used to mix the solvent and biomass. This stirring was continued for four hours to extract the optimum quantity of oil from the biomass. Fig. 3 shows the total components present in the oil as detected.

using

spectrophotometer.

includes % transmission, concentration and optical density as growth parameters.

Simultaneously mass of biomass were also recorded. Fig. 2 shows the magnetic stirring

Fig. 2 Solvent Extraction of Oil from the Algae Biomass

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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

Fig. 3 Composition Analysis of Oil from Algae Biomass (Gas Chromatography Mass Spectroscopy)

Conclusions From the research conducted for the extraction of oil from algae biomass grown in process industry effluent i.e. desalination reject stream, the following conclusions were drawn: (i) Extraction of oil from the algae biomass is feasible with simple magnetic stirring combined with solvent extraction was employed

which

makes

the

system

cost

effective. (ii) The composition analysis of oil is found to similar to the previously conducted research works. (iii) Desalination reject stream with a plenty of chemicals and high ionic concentration factor is found to be a viable medium for the growth of algae biomass and for biofuel

extraction.
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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

This work also gives scope for detailed study for optimizing the solvent to biomass ratio and for large scale cultivation of algae. Design of magnetic stirring based solvent extraction needs a careful and detailed study. Acknowledgments The authors wish to express their gratitude for the support extended by the authorities of Caledonian College of

Ahmed Alsaeed. 2009 Extraction of Fuel from Microbial Biomass Grown in Process Industry Effluents, Technical Project Level 4, B.Sc(POM) Caledonian College of

Engineering, Oman Ahn, E., M. Koncar, M. Mittelbach, and R- Man. 1995 A Low-waste Process for the Production of Biodiesel, Sep. Sci. Technol. 30:2021-2033. Bakheet Hassan Fadhi. 2009 Kinetics Study of Bioenergy from Microalgae, Technical Project Level 4, B.Sc (POM) Caledonian College of Engineering, Oman. Govindarajan et al, 2009 Treatment of Desalination Reject Stream & Conversion of energy using Microalgae, Research proposal submitted to Middle East Desalination Research Centre (MEDRC), Oman. Michele L. Wrabel and Paulette Peckol 2000 Effects of Bioremediation on Toxicity and Chemical Composition of No. 2 Fuel Oil: Growth Responses of the Brown Alga Fucus vesiculosus, Marine Pollution Bulletin,

Engineering, Oman in carrying out the research work. This is also due to various experts who helped this research from its inception stage that includes Dr.R.Senthil Kumar, Mr. Moussa Al Mazoroui and Mr. Taher Al Balushi, CCEO and Sivasubramanian, Director, Dr V.

Vivekananda

Institute of Algal Technology, India. Our appreciations are due to Sultan Qaboos University, Oman for providing the facilities in determining the composition of oil and microbial assay. We would like to express our thanks especially to Dr. Mahad

Baawain, Dr, Mohammed Algambashi, Mr. Sardar Farouk, Sultan Qaboos University for their encouragement and support throughout the execution of the project. References

Volume 40, Issue 2, pp 135-139. Mohamed El Hattab, Gerald Culioli, Louis Piovetti and Semch Eddine Chitour and Robert Valls. 2007 Comparison of various extraction methods for identification and determination of volatile metabolites from the brown alga Dictyopteris membranacea ,

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J. Algal Biomass Utln. 2009, 1 (1): 18 28 PHYCO SPECTRUM INC

Extraction of oil from algal biomass

Journal of Chromatography A, Volume 1143, Issues 1-2, , pp 1-7. Paul S. Cobian. 2008 Armando Aguilar , Purification Of Waste Vegetable Oil For Biodiesel Chemica Production, And Department Of

Materials

Engineering,

California State Polytechnic University, Pomona. Sarmidi Amin. 2009 Review on biofuel oil and gas production Energy processes Conversion from and

microalgae,

Management Volume 50, Issue 7, pp 18341840.

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