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DIRECT TRANSESTERIFICATION FOR BIODIESEL EXTRACTION FROM MICRO-ALGAL BIOMASS: A REVIEW Rahul Chamola Assistant Professor,Department of Mechanical Engineering Dev Bhoomi Institute of Technology Dehradun-248007 Uttarakhand, India Ayush Gupta Assistant Professor,Department of Mechanical Engineering Dev Bhoomi Institute of Technology Dehradun-248007 Uttarakhand, India Vijay Singh Chauhan Assistant Professor,Department of Mechanical Engineering Dev Bhoomi Institute of Technology Dehradun-248007 Uttarakhand, India Tirath Singh Assistant Professor,Department of Mechanical Engineering Dev Bhoomi Institute of Technology Dehradun-248007 Uttarakhand, India Abstract The biodiesel production has gone through fast growth over the past decade. Microalgae have large scale cultivation resources. The non edible biodiesel resources have potential to meet the future energy demand without any environmental loss. Despite the umpteen advantages microalgal biodiesel is still facing technical and economical challenges. The complexity and the production cost related issues have been studied by many researches and scholars all over the globe for the optimum biodiesel extraction. This article reviews about the recent development and process parameters affecting the biodiesel production by insitu-transesterification. This article also reviews about the recent techniques which are being used for large scale production. It has been studied that insitu transesterification is being used for economic production of bio fuels and the process parameters viz. reaction temperature, reaction time, types of catalyst and methanol to algae ratio play a significant role in commercial biodiesel production. There is a focus on insitu transesterification which is most efficient and economic oil production process for wet as well as dry micro-algal biomass. Furthermore, all other issues related to the biodiesel production such as viscosity purification and processing time are taken into consideration. Keywords: microalgae, innovation in biodiesel extraction, insitu transesterification, Biofuel Non-edible feedstock, 1. Introduction Biodiesel is derived from vegetables oil has a great potential as a substitute of diesel fuels. Biofuels are generated from mainly two sources namely edible and non edible biofuels. Edible biodiesel resources are usually employed for maximum biodiesel extraction. Almost 95% of world's total biodiesel is produced from edible biodiesel resources. However, edible biodiesel resources such as soybean, rapeseeds, sunflower and palm oil are associated with sever environmental problems like deforestation, vital land availability and climate change[1]. The limitations of edible resources can be minimized by the introduction of non-edible biodiesel resources viz. Jatropha Curcas, neem seeds, mahua and algae. Algae are kept in the category of third generation biofuel resources. These resources are most efficient and eco-friendly and excessively being adopted as sustainable future fuels. Algae are plant like organism without true roots, leaves and vascular bundle. They can be collected from different aquatic bodies such as pond, river and sea. Algae are of two types namely microalgae and macroalgae. Microalgae available in the size of micro to nano metre and known as single cell organisms[2]. Macroalgae on the other hand are known as seaweeds available in the size of 60 to 150 m in length. 2. Material and Method Various biodiesel extraction techniques have been introduced by the research scholars some of them are pyrolysis, gasification, micro-emulsification, two-step transesterification, International Journal of Applied Engineering Research ISSN 0973-4562 Volume 14, Number 9, 2019 (Special Issue) © Research India Publications. http://www.ripublication.com Page 180 of 184

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Page 1: DIRECT TRANSESTERIFICATION FOR BIODIESEL EXTRACTION FROM ... · related to the biodiesel production such as viscosity purification and processing time are taken into consideration

DIRECT TRANSESTERIFICATION FOR BIODIESEL EXTRACTION FROM

MICRO-ALGAL BIOMASS: A REVIEW

Rahul Chamola

Assistant Professor,Department of Mechanical Engineering

Dev Bhoomi Institute of Technology Dehradun-248007

Uttarakhand, India

Ayush Gupta

Assistant Professor,Department of Mechanical Engineering

Dev Bhoomi Institute of Technology Dehradun-248007

Uttarakhand, India

Vijay Singh Chauhan

Assistant Professor,Department of Mechanical Engineering

Dev Bhoomi Institute of Technology Dehradun-248007

Uttarakhand, India

Tirath Singh

Assistant Professor,Department of Mechanical Engineering

Dev Bhoomi Institute of Technology Dehradun-248007

Uttarakhand, India

Abstract

The biodiesel production has gone through fast growth over the

past decade. Microalgae have large scale cultivation resources.

The non edible biodiesel resources have potential to meet the

future energy demand without any environmental loss. Despite

the umpteen advantages microalgal biodiesel is still facing

technical and economical challenges. The complexity and the

production cost related issues have been studied by many

researches and scholars all over the globe for the optimum

biodiesel extraction. This article reviews about the recent

development and process parameters affecting the biodiesel

production by insitu-transesterification. This article also

reviews about the recent techniques which are being used for

large scale production.

It has been studied that insitu transesterification is being used

for economic production of bio fuels and the process

parameters viz. reaction temperature, reaction time, types of

catalyst and methanol to algae ratio play a significant role in

commercial biodiesel production.

There is a focus on insitu transesterification which is most

efficient and economic oil production process for wet as well

as dry micro-algal biomass. Furthermore, all other issues

related to the biodiesel production such as viscosity purification

and processing time are taken into consideration.

Keywords: microalgae, innovation in biodiesel extraction,

insitu transesterification, Biofuel Non-edible feedstock,

1. Introduction

Biodiesel is derived from vegetables oil has a great potential as

a substitute of diesel fuels. Biofuels are generated from mainly

two sources namely edible and non edible biofuels. Edible

biodiesel resources are usually employed for maximum

biodiesel extraction. Almost 95% of world's total biodiesel is

produced from edible biodiesel resources. However, edible

biodiesel resources such as soybean, rapeseeds, sunflower and

palm oil are associated with sever environmental problems like

deforestation, vital land availability and climate change[1]. The

limitations of edible resources can be minimized by the

introduction of non-edible biodiesel resources viz. Jatropha

Curcas, neem seeds, mahua and algae. Algae are kept in the

category of third generation biofuel resources. These resources

are most efficient and eco-friendly and excessively being

adopted as sustainable future fuels.

Algae are plant like organism without true roots, leaves and

vascular bundle. They can be collected from different aquatic

bodies such as pond, river and sea. Algae are of two types

namely microalgae and macroalgae. Microalgae available in

the size of micro to nano metre and known as single cell

organisms[2]. Macroalgae on the other hand are known as

seaweeds available in the size of 60 to 150 m in length.

2. Material and Method

Various biodiesel extraction techniques have been introduced

by the research scholars some of them are pyrolysis,

gasification, micro-emulsification, two-step transesterification,

International Journal of Applied Engineering Research ISSN 0973-4562 Volume 14, Number 9, 2019 (Special Issue) © Research India Publications. http://www.ripublication.com

Page 180 of 184

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super critical transesterification and insitu transesterification.

Out of these techniques insitu transesterification is the most

useful economic and efficient process for biofuel generation

from biomass. It is a chemical reaction in which triglyceride

reacts with an alcohol in presence of homogenous or

heterogeneous to produce free fatty alkyl ester (FFEAs). The

transesterification reaction is shown below.

Alcoholic Group + Triglycerides = Glycerol + Fatty Methyl

Esters

Where R', R'' are alkyl groups [3].

3. Types of Transesterification

Commonly known Transesterification techniques are base

catalyst, acid catalyst, enzyme catalyst and supercritical

transesterification. Base catalyst method is broadly used for oil

generation. It can't be reuse or recycled. It has been found that

acid catalysts are slower than that of base catalyst and most

suitable for high lipid containing oil. Enzyme catalyst

technique is technique laborious in process and not useful for

commercial production of biodiesel. Talking about

supercritical transesterification high temperature around 250°C

and pressure is required for the oil extraction. In this process

use of catalyst is optional.

Numerous researches have been reported on transesterification

process. Chamola R et al.[4] have been conducted insitu

transesterification of dry algae with Methanol, acid catalyst

(H2SO4) and base catalyst (NaOH). they found that acid catalyst

has significant role in biodiesel extraction than that of base

catalyst, reported maximum yields of 89.58% and 87.42% for

acid and base catalyst respectively at 50°C in 60.4 min. Shirazi

et al.[5] have been conducted insitu transesterification of dry

algae with methanol, hexane and moisture content. 99.32%

yields have been reported by using Response Surface

Methodology (RSM) and Centre Deviation Method (CDM).

A Salam et al.[6] have worked with marine as well as fresh

water microalgae for biodiesel generation. They used methanol,

hexane and different catalyst to reduce the cost of the biodiesel

production. Velasquez Orta and Harvey[7] conducted a

research on chlorella Vulgaris oil in presence of methanol and

a suitable catalyst. They claimed 77.6% yield with methanol to

oil ratio 600. 94.9% fatty acid methyl ester (FAMEs) is

obtained by Dong et al.[8] during two step transesterification

and direct transesterification using amberlyst-15 and base

catalyst. Spirulina Chlorella and pond water algae have been

applied by Nautiyal et al.[9] for the oil extraction through

transesterification process. It has been suggested that hexane

could be better solvent for high yield.

Im et al.[10] reported biodiesel yield using supercritical

transesterification with chloroform ethanol and H2SO4. They

studied the involvement of moisture content decreases the

output values. Transesterification of dry algae using solvents

viz. n butanol, chloroform, ethyl ether, hexane, acetone and

petroleum to check which has vital role on the output yield for

oil production. Zhang et al.[11] found that n hexane and

petroleum ether are best solvent due to miscibility with

alcoholic products. Kaism and Harvey [12] performed

transesterification on jatropha curcus using alkali catalyst at

60°C. They reported maximum FAME yield of 95%. A

research has been conducted by Hass and Wangner [13] using

wet biomass and acid catalyst at 65°C. Maximum yield of 96%

was recorded with methanol/oil ratio 308:1.

3. Process Parameters in Insitu Transesterification Process

Direct transesterication crucially depends upon process

parameters like processing time, processing temperature,

methanol/algae ratio and catalyst concentration. some of the

study has take processing time in between 60 to 180 min and

operating temperature range is suggested in between 60 to

80°C[14].

Effective methanol/algae ratio has been suggested as (8% to

20%)(W/W). Batch reactor is used to extract biodiesel from

algal biomass which takes lots of steps are listed below in flow

chart[15].

Fig 3:- Flow-Chart for Biodiesel Extraction

Experimental procedures were done in a batch reactor as shown

in the figure. The reactor was heated with an electric heater at

COLLECTION

CLEANING

DRYING

CRUSHING

PARAMETERS SELECTION

INSTRUMENT PREPARATION

TRANSESTRIFICATION

SEPARATION

International Journal of Applied Engineering Research ISSN 0973-4562 Volume 14, Number 9, 2019 (Special Issue) © Research India Publications. http://www.ripublication.com

Page 181 of 184

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a constant temperature was sensed by a thermocouple. in a

batch reactor mixture of methanol, algae, n-hexane and

chloroform is prepared by weighing in chemical balance. A

magnetic stirrer is used for the proper agitation and heat

transfer rate along with a condenser.

According to research analysis, Oil production experiments are

mostly decided by Response Surface Methodology (RSM) and

Central Composite Design(CCD) through design expert

software 11. The software has analysis of variance (ANOVA)

feature to establish the statistical significance of process

parameters on the output. the optimization is also conducted

through the software in order to choose process variables to

optimize the production yield.

Fig 4:- Diagram of Reactor [4]

statistical analysis is done by using regression equation,

generated by the software. furthermore, gas chromatography (G

C) is used to optimized the experimental samples. the process

is processed for 30 minutes at 230°C with nitrogen as a carrier

gas. study shows that G C analysis was performed by many

research scholar using European standard EN 14103:2003.

equation mentioned below is used to calculate the yield and

stock solution i.e., Methyl heptadecanoate and n-heptane is

used to determine the FFA content.

% of ME = ∑𝑨−𝑨𝑬𝑰

𝑨𝑬𝑰∗

𝑪𝑬𝑰− 𝑽𝑬𝑰

𝒎∗ 100

Where,

∑A - Total peak area from the methyl ester in C14 to that in

C24:1;

AEI- Peak area corresponding to methyl heptadecanoate;

CEI - Concentration of the methyl heptadecanoate solution (mg/

ml);

VEI - Volume of the methyl heptadecanoate solution (ml);

m - Mass of the sample (mg).

4. Factors Affecting Insitu Transesterication Process

FAME yields are influenced by the wet and dry algal biomass,

reaction temperature, biomass grain size, agitation speed,

reaction time and catalyst selection during insitu

transesterification process.

4.1 Effect of Moisture Content

Some of the studies show that the output results are good with

dry algae biomass. Actually the availability of water leads

hydrolysis and as a result of which biodiesel disintegrates from

solvent. Hass et al.[16] conducted a study on transesterification

of soybean with 0% and 2.6% water content. They concluded

that methanol consumption increased from 40% to 60% for dry

and wet biomass respectively.

4.2 Effect of Biomass Particle Size

Biomass grain size has an important role in the consumption of

solvent. Scholars have notes that as the particle size increases

less solvent is required for the oil extraction. Methanol-to-dry

algae ratio has crucial impact on the transesterification. Patil et

al.[17] reported 85.75% of yield at 250°C in 30 minutes for wet

biomass of Nannochloris. 5.82% methyl ester yield is collected

in the processing of wet chlorella biomass (75% moisture) with

methanol to dry algae ratio of 8:1.

4.3 Effect of Co-Solvent for the Process

Hexane and chloroform is most widely used co-solvent for the

transesterification method. Hexane and chloroform improves

the solubility of oil and enhance the output[18]. Hexane is

preferred over chloroform because of its cost and availability.

4.4 Selection of Catalyst for the Oil Extraction

As it is already has been discussed that homogenous as well as

heterogeneous catalyst can be used for the biofuel production.

Selection of catalyst should be proper because it helps in

fragmentation of hard micro-algae cell wall. NaOH, KOH,

Ca(OH)2, Mg(OH)2, H2SO4, NaOCH3 and HCl are some

homogenous catalysts are being used by many researchers[19].

Furthermore, homogenous catalyst can be divided into two

categories acidic and basic. Studies showed that H2SO4 and

HCl are most effective for utmost output.

Commonly known heterogeneous catalyst are CaO, MgO,

BaO, SrO, SrCO3 and MgCO3[20]. According to some study

both catalysts are outstanding to boost the oil production with

the increase in consumption.

4.5 Effect of Agitation

Sivaramkrishnan and muthu kumar [21] reported as mixing

speed increases from 150 to 180 rpm FAME also increase.

They also suggested that output value doesn't changes with

International Journal of Applied Engineering Research ISSN 0973-4562 Volume 14, Number 9, 2019 (Special Issue) © Research India Publications. http://www.ripublication.com

Page 182 of 184

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exceeding the mixing speed more than 450rpm.

4.6 Effect of Reaction Time and Temperature

It has been observed that reaction time for oil production is kept

in a particular range from 60 to 180 min. Qian et al.[22] have

conducted transesterification of rapeseed oil for 5 hour and they

achieved output yield of 98% . They concluded that high

reaction time doesn't affect product yield. The best yield results

are obtained for the range of 1 to 3 hours. Temperature on the

other hand increases the solubility and high temperature

reduces the viscosity of vegetable oil. According to a study

when temperature changes from 35 to 55°C almost double

value of output is obtained.

5. Conclusion

Recent developments in the insitu transesterification have been

reviewed. The present study was emphasized on the use of

direct transesterification for the sustainable development of fast

and economic biodiesel extraction process. The numerous

studies showed that the exploitation of edible biodiesel

resources can be compensated by the application of micro-

algae because of high grade oil and widely abundant.

The research data indicated that direct transesterification

resulted in maximum yields for FAEEs. In this case of insitu

transesterification with methanol and ethanol almost equal

yields are received but use of ethanol is a more economic, eco-

friendly and efficient pathway. It was further observed that

process variable had significant role on output. A comparison

study of conventional process and insitu transesterification is

discussed in this research.

5.1 Future Scope

Microalgal biomass can be directly processed using a suitable

catalyst and an alcohol in a batch reactor. Direct

transesterification as the name implies, used to convert

vegetable oil into fuel in one step. Mass production for

commercial applications, oil purification and upgrading of fuel

requires future attention and research.

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International Journal of Applied Engineering Research ISSN 0973-4562 Volume 14, Number 9, 2019 (Special Issue) © Research India Publications. http://www.ripublication.com

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