WASTE TO ENERGY CONVERSION

ENERGY PRODUCTION FORM ALGAL BIOMASS-1

DR. PRASENJIT MONDAL

CHEMICAL ENGINEERING DEPARTMENT

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 Contents
 Biodiesel as an important option for energy production form algal biomass
 Bio oil production form algal biomass
 Conversion of algal oil to biodiesel
 Types of conversion process, mechanisms and comparison
 Factors affecting biodiesel yield
 Upgradation of algal oil to bio diesel using homogenous and heterogeneous
catalysts
 Quality parameters of algal bio diesel and its stability
 Challenges for microalgae and integrated scheme for utilization
 Bio jet fuels
 Research status on algae to oil
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 Important energy
production routes for algal
biomass

Biodiesel Bio-jet fuel Syngas Biogas Pyro-oil

Algal Oil Extraction Upgradation

Bio-oil Biodiesel/Bio-jet fuel
biomass Blending

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Bio oil production from algal biomass Conventional route

Solvent

Drying
Harvested Dry algal biomass Oil extraction
microalgae

Solvent Bio-oil + solvent Separation

Bio oil Oil extracted

biomass
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Mechanism of oil extraction using solvent
e Bulk organic
solvent film

Cell membrane
d
a b c a
Cell wall
b

Nucleus c
d

Schematic diagram of solvent

extraction mechanism (Adapted &
e modified from Halim et al. 2012).
Extraction of micro algal lipids using organic solvents
Micro algae Operating conditions / solvent
species used
Chlorella sp. ; Extraction method: Soxhlet extraction and Batch extraction
Botryococcus Solvents: Methylene chloride/ methanol (2:1 v/v);
braunii ; Soxhlet extraction:- methylene chloride/ methanol (2:1 v/v);
Phaeodactylum chloroform/ methanol/50 mM phosphate buffer (35:70:28 v/v/v/);
Tricornutum ; Chloroform/methanol (2:1 v/v);
Chlorococcum sp. hexane/ isopropanol (3:2 v/v);
Solvent to biomass ratio: 75 – 1000 ml solvent per g of biomass
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Mechanism for supercritical CO2 extraction
Schematic diagram of supercritical carbon-dioxide extraction
SCCO2 mechanism (Adapted & modified from Halim et al. 2012)
flow

c Static SCCO2
film
b

Mixture of micro algal biomass

a and diatoms
Some studies on the extraction of micro algal lipids by supercritical carbon dioxide
Microalgae Operating conditions Remarks
Nannochloro Extraction pressure(bar):- 400, 550, Increase in lipid extraction with
psis 700; Temp (°C):- 40, 55; SCCO2 flow Pressure at constant T
sp. rate:- 0.17 kg/min; Time:- 360 min; Increase in lipid extraction rate
polar modifier ,amount:- None with temperature at constant P.
Spirulina Extraction pressure(bar):- 316, 350, Optimum condition-400 bar, 13.7
Platensis 400, 450, 484; Temp (°C):- 40, 55; mL ethanol and 60 min.
SCCO2 flow rate:- 0.7 L/min;; Time:-
26.4,40, 60, 80, 94 min; Polar
modifier (amount):- Ethanol; 9.64,
11, 13, 15,16.36 mL
Some studies on the extraction of micro algal lipids by supercritical carbon dioxide
Microalgae Operating conditions Remarks
Chlorella Extraction pressure (bar):-200, Lipid yield increased with P at constant T
vulgaris 350; It decreased with T at constant lower P
Extraction temp (°C):-40, 55; (200 bar) and increased with T at
SCCO2 flow rate:- 0.41/min; constant high P (350 bar),
Time:- 500 min Optimum condition- 350 bar and 55 °C
Spirulina Extraction pressure(bar):- 100, Similar effect of temperature and
maxima 250, 350; Temp (°C):- 50, 60; pressure on total lipid yield like Chlorella
SCCO2 flow rate:-not specified; vulgaris
polar modifier ,amount:- Optimum condition-350 bar, 60 °C with
ethanol, 10 mol % of CO2 ethanol addition (10 mol%).
Single step oil extraction
Processed Gravity clarifier
Matured
algal culture
biomass
Extraction
tank
Low voltage Lipid
Power input
Return Water Bio oil
Culture to
Water recycling Biomass
CO2 for pH extraction
Return to bioreactor
Modification tank
Electromagnetic
Algae Field

Quantum Biomass
CO2 Fracturing
Modified & adopted from origin oil on
http://www.originclear.com/pdf/OriginOil_NAA_30_Apr_2009.pdf, Accessed
on 11-11-2017
 Biodiesel production route through algal biomass
Solvent Catalyst

Algal
Biomass Extraction of Conversion via Filtration/Distill
Oil Transesterification ation

Biodiesel
Mechanism of transesterification Modified from Prafulla D. P. et al., 2012

CH2 OOC R1 R1 COO R

CH2 OH

Catalyst
CH OOC R2 + 3ROH R2 COO R + CH OH

CH2 OOC R3 R3 COO R CH2 OH

Triglyceride Alcohol Esters Glycerol

Schematic of transesterification reaction, where, R1, R2 and R3 are long chains of

carbons and hydrogen atoms, called fatty acid chains.
 Different types of transesterification processes
Different methods for biodiesel production

Oscillatory flow reactor (OFR)

Catalyzed
assisted trans esterification in the
transesterification
presence of NaOH as catalyst
process
Microwave technology
Homogeneous-Base cat.
assisted trans esterification
Homogeneous-Acid cat. in presence of KOH as cat.

Heterogeneous-Base cat. Ultrasonic technology

assisted transesterification
Heterogeneous-Acid cat. in presence of KOH as cat.

Enzyme catalyzed Co-Solvent method for

biodiesel production
Mechanism of base catalyzed transesterification
Pre-step OH + ROH RO + H2O

or NaOR RO + Na+
O O
Step.1. R’ C + RO R’ C OR
OR” OR”
O O
Step.2. R’ C OR + ROH R’ C OR + RO
OR” R”OH+
O
Step.3. R’ C OR R’COOR + R”OH
R”OH+
Where R” = CH2
CH OCOR’ R’ = carbon chain of fatty acid
R = alkyl group of the alcohol Schuchardt U. et al., 1998.
CH2 OCOR’
Mechanism of acid catalyzed transesterification
O O+H OH
H+

R’ R’ OR” R’ +
OR” OR”

OH R OH H O
-H+/R”OH
+ O O
R’ +
+ H OR” R +
R’ OR” R’ OR

R” = OH
OH
R’ = carbon chain of fatty acid
R = alkyl group of the alcohol
Schuchardt U. et al., 1998.
 Mechanism of transesterification with heterogeneous catalyst contd..
R-OH R-O- H+
Modified from
O -R
Ca O Kouzu et al., 2008,
O
CH2 - O - C - R1
CH2 - O - C - R1
Fuel (87)
O
R-O- H+ O
O 2798–2806
CH – O – C – R2 +
O CH – O – C – R2
Ca
O
O
CH2 – O - C - R3 O -R CH2 – O - C - R3
CH2 - O - C - R1 CH2 - O
O
O
O
O CH – O – C – R2 + R1 – C – O - R
O
CH – O – C – R2
O CH2 – O - C - R3
CH2 - O
O CH2 – O - C - R3 CH2 - OH
O
CH – O – C – R2 + R-O- H+
O CH – O – C – R2 + Ca O
O
CH2 – O - C - R3 Ca O
CH2 – O - C - R3
 Factor affecting biodiesel yield contd..

1. Oil temp. O
O
2. Reaction temp. + H2O + ROH
R’ OR
3. Ratio of alcohol to oil R’ OH
4. Catalyst type & conc.
5. Intensity of mixing O O

6. Purity of reactions + NaOH + H2O

R’ OH R’ ONa

R’ = Carbon chain of the fatty acid

Soni et al., 2012 R = alkyl group of the alcohol
Comparison among base, acid and enzyme catalyzed esterification reactions
Characteristic Base catalyzed Acid catalyzed Enzyme catalyzed
Reaction rate   
Effect of free fatty acid in oil  - -
Cost of catalyst   
Catalyst used NaOH, KOH H2SO4, HCl Lipozyme IM 60,
Novozyme 435
Chances of deactivation of cat.   
Possibility of catalyst recovery   
Problems in product recovery   
By-products   -
Effect of alcohol used - - Soni et al., 2012  18
 Comparison of different types of transesterification processes
Processes Advantages Disadvantages
Catalyzed  Primitive and mostly used  Performance can be
process
transesterification highly affected with
 Well proven
catalyst types
 Various types of catalysts such as
homogeneous, heterogeneous,
biocatalysts etc. can be used
Catalyzed  Improved solubility and high  Co-solvents are volatiles
and are not environment
transesterification mass transfer rate between oil , friendly
using co-solvent solvent and catalyst  Solvent separation from
final product increases
Soni et al., 2012 production cost
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 Comparison of different types of transesterification processes
Processes Advantages Disadvantages
Oscillatory flow reactor (OFR)  Improved heat and mass  Not well proven
assisted catalyzed transfer between medium
transesterification
Microwave technology assisted  Energy requirement is less  Scale up is
catalyzed transesterification difficult

Ultrasonic technology assisted  Improved mass transfer  Not well proven

catalyzed transesterification rate between media
Soni et al., 2012
 Cost effective
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Thanks