hydrothermal liquefaction of microalgaes for bio-oil production · utilization of algae in...

UTILIZATION OF ALGAE IN

HYDROTHERMAL SYSTEMS FOR

BIO-OIL PRODUCTION

L A S S E R O S E N D A H L , P R O F E S S O R

S A Q I B S O H A I L T O O R , A S S I S T A N T P R O F E S S O R

3rd Danish Algae Conference

09-10th October 2013, Grenaa, Denmark

Department of Energy Technology Aalborg University

Denmark

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OUTLINE • BIOMASS RESEARCH PROGRAMME AT AAU

• ENERGY OUTLOOK

• BIOMASS CONVERSION TECHNOLOGIES AND BIOFUELS

• HYDROTHERMAL LIQUEFACTION (HTL)

• HTL BIO-OIL FROM MICROALGAES

• MACROALGAE AS A FEEDSTOCK AND CHALLENGES

• HTL-A PROMISING ROUTE FOR MACROALGAE

• CONCLUSION

• LARGE SCALE LAB FACILITY-HTL AT AAU



Biomass Research Programme at AAU

• Geographically, the Biomass research program has activities at both Aalborg and

Esbjerg Campuses of the Department of Energy Technology

• Almost 15 group members, Lasse Rosendahl is group leader

• Development of advanced thermochemical conversion and upgrading processes for a

wide range of biomass feedstocks, and a wide range of products and end use

applications

• State-of-the art experimental facilities to test and analyse processes and to generate

validation data



Collaboration Partners

Vattenfall Heat Nordic, DONG Energy, NIRAS, Babcock&Wilcox Vølund, Andritz,

Brancheforeningen for Biogas (DK), FHF (DE), Zhejiang University (CN), Brigham Young

University (USA), South Dakota State University (USA), National Academy of Science of

Ukraine, Zhejiang University (CN), Tianjin University (CN), CAS-GIEC (CN), NTNU (N),

Agder University (N), Århus University (DK), Paul Scherrer Institute PSI (CH), CanMet

ENERGY (CA)

Industrial Advisory Board (IAB) for sustainable bio-fuels

Steeper Energy, MAN Diesel & Turbo, Shell Denmark, Scandinavian Airlines SAS, Port of

Frederikshavn, Port of Aalborg, Stena Line, SCANIA Danmark, Vestas Aircoil



Ongoing Research Projects

• Innovationsnetværket for biomasse (2010-2014)

• FLEXIfuel-optimizing fuel flexibility through high quality bio-oils,

Sino-Danish Research

• Collaboration within Sustainable and Renewable Energy 2010

(2011-2014). Partner: Zhejiang University

• Towards an enabling plasma-aided biomass/waste-to-energy

technology, FTP2011 (2011-2013) [submitted]

• Center for Energy Materials CEM (DSF)

• Development of bio-oil dewatering and fractionation processes

and testing of upgraded bio-oils as engine fuel and feedstock for

the production of lubricants (GREEN-OIL)



Ongoing PhD Projects

• Large Scale Bioenergy Lab: Methanation as an option for dynamic small scale biogas

upgrading in the region of Southern Denmark-Schleswig-K.E.R.N. Germany (Lars

Jürgensen)

• FLEXIfuel-optimizing fuel flexibility through high quality bio-oils(Thomas Helmer

Pedersen)

• Bio-oil Production- Process Optimization and Product Quality (Jessica Hoffmann)

• Large Scale Bioenergy Lab-Identification, Analysis, Mapping and Management of

Sustainable Biomass Resources in the Region of Southern Denmark-Schleswig-

K.E.R.N. Germany (Ane Katharina Paarup Meyer)



Hydrothermal Liquefaction Facilities

400 mL system:

400 mL autoclave equipped with stirring, a cooling coil, a heater and an

external high pressure injection pot. The system is rated for 350 bar and

500℃.

1 L system:

A semi-continuous system consisting of a 1 L autoclave equipped with a high

pressure injection pot and a batch disposal system. The disposal system

consists of a flash-drum and condenser which enables repeatable

experiments without disassembling the system. The system is rated for 350

bar and 500℃





Batch reactors

1L batch reactor

Centrifuge

Small Rotary evaporator

Big Rotary evaporator

Datalogging & remote set points-SCADA software



Elemental Analyzer (CHNS)&Bomb calorimeter FTIR GC/MS

Karl Fischer titration&viscometer

Fuel testing

• MiniLab™ Gas Turbine Lab

• SprayView™ Fuel Atomization Verification System Lab

• Engines

Miscellaneous

• Hach-Lange TOC-X5 for measuring total Organic content

• Mettler Toledo pH-meter

• Kern moisture analyzer • Heating cabinets

ENERGY OUTLOOK

World marketed energy consumption, 2006-2030

World carbon dioxide emissions, 2006-2030

We are near peak oil! At the current consumption level

the estimated 1250 billion barrels of global crude oil

reserves would last approximately 42 years.



Globally, the share of biofuels in road transport increases from 1% today to 7% in 2030. Total

biofuel demand increases tenfold, from 15.5 Mtoe in 2004 to 146.7 Mtoe in 2030.

Biofuels Demand in Road Transport, by Region

Bio-Fuel



BIOMASS CONVERSION TECHNOLOGIES AND

BIOFUELS

• 1st generation biofuels

– Biofuels made from sugar, starch, and vegetable oil

• Bioethanol

– ETBE

• Vegetable Oil

– FAME

• 2nd generation biofuels

– Biofuels derived from lignocellulosic crops. e.g. waste biomass, the stalks of

wheat, wood, and Non-food crops!

• Bioethanol

• Fischer-Tropsch Diesel

• Bio-oil

• 3rd generation biofuels

– Biofuels derived from algae.



HYDROTHERMAL LIQUEFACTION (HTL)

• High temperature, high pressure thermochemical process

• Feedstock can be directly converted without an energy consuming drying step

• HTL does not require drying as gasification or pyrolysis, it uses water as a reaction medium

• The main products are a bio-oil, char, water-soluble substances and gases

Reaction Pathways for Liquefaction

• Hydrolysis of the biomass

• Depolymerization of the main components

• Chemical and thermal decomposition of monomers dehydration, and decarboxylation.

• Recombination of reactive fragments



Preparation of feedstock

Slurring the feedstock within a liquid carrier

Heating and pressurizing the slurry to reaction conditions

Biomass

Bio-oil

• High heating value • Low oxygen content • Storage stable

• Yield 30-40 wt.% (DM)

• Feedstock flexible • High water content

1. the relative permittivity (dielectric constant), εr , of water decreases quickly when the temperature increases → electronegativity

of the oxygen is reduced → water molecule becomes less polar → higher affinity for hydrocarbon molecules

2. The dissociation of water dramatically increases with the increase of temperature → The increase in the dissociation constant

will increase the rate of both acid - and base - catalyzed reactions in water far beyond the natural acceleration.



Biomass

feedstock

Biomass

Catalyst

Water

HTL Process

Inlet

400°C

300 bar

HTL Process

Outlet Bio-oil recovering

Biomass

decomposition

Polymerization



HTL BIO-OIL FROM ALGAE

• Expected high abundance in future

• Higher potential lipid yields than other biomass

• Does not compete with food markets

• Can utilize N and P-rich wastewater as a nutrient source

• Has potential to sequester CO2

Experiments were conducted on Nannochloropsis salina and Spirulina platensis at subcritical and

supercritical water conditions.

• To explore the feasibility of extracting lipids from wet algae, preserving nutrients in lipid-

extracted algae solid residue, and recycling process water for algae cultivation.

• Production of bio-oil



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Experimental detail

• Spirulina platensis and Nannochloropsis salina were obtained from commercial sources

Natur-Drogeriet, Denmark and Solix Biofuels, LLC, USA, respectively.

• In each experimental run 50 g of dry algae sample were mixed with 150 ml of distilled water

• The sample was charged into the autoclave premixed as a slurry (200ml)

• Nitrogen was introduced to purge the residual air in the autoclave for 5 minutes

• 20 minutes retention time.

Spirulina Salina

400mL reactor



Raw Material

Liquefaction products

Water solution Water insoluble fraction

Acetone solution Acetone insoluble fraction

Heavy oil Residue Water soluble fraction (Organics Dissolved) Gas products

Liquefaction

Filtration

Evaporation

Drying

Extracting with acetone

Filtration

Separation procedure



Properties of algae's

a Fixed carbon content is the difference between 100% and the sum of moisture, ash and volatile matter percentage. b O composition was determined by subtraction from 100% the sum of C, H, N and S percentages.

Spirulina Platensis Nannochloropsis salina

Thermogravimetrical analysis results (%) Moisture 5.88 4.95

Volatile matter 85.64 86.76 Ash 1.19 2.48

Fixed carbon (by difference) a 7.29 5.81

Chemical composition (%) Protein 60 37

Carbohydrates 19 33 Fats 6 12

Moisture 7 5 Elemental Composition (%)

C 42.26 55.16

H 5.86 6.87

N 3.47 2.73

S 1.15 1.27

O b 47.26 25.60

Calorific value (MJ/kg)

Calorific value 20.40 25.40



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T (o

C)

Time (min.)

Algae spirulina at T=350 oC, P=195 bar

T

P

2.5 oC/min.

Retention time

1.5 bar/min.



Spirulina oil and solids Full product Water phase

Results

Salina oil and solids

Run Algae sample T (C) P (bar) Oil (g) Solids (g) Oil yield (%)

1 Spirulina 310 115 15 5 30

2 Spirulina 350 195 19 3 38

3 Spirulina 375 255 19 0-1 38

4 Salina 310 107 23 16 46

5 Salina 350 175 17 14 34



Product analysis

GC-MS, elemental analyzer, calorimeter and nutrient analysis were used to analyze bio-

crude, lipid-extracted algae and water samples produced in the hydrothermal liquefaction

process.

Samples Process

conditions

C

(%)

H

(%)

N

(%)

S

(%)

O

(%)

Calorific

value

(MJ/kg)

Spirulina (dry) 42.26 5.86 3.47 1.15

47.26 20.4

Nannochloropsis salina (dry) 55.16 6.87 2.73 1.27

25.60 25.4

O-1.1 310C, 115 bar 71.29 8.01 7.66 0.81

16.82 35.2

O-1.2 350C, 195 bar 70.69 8.05 7.22 0.77

10.06 34.3

O-1.3 375C, 255 bar 68.61 7.82 7.01 1.13 15.4 30.2

O-2.1 310C, 107 bar 72.36 8.64 2.75 1.00

18.20 27.7

O-2.2 350C, 175 bar 77.20 9.01 2.75 1.00

8.71 38.1

LEA-1.2 24.56 2.61 2.07 0.30

6.62 13.1

LEA-2.1 67.93 7.75 2.65 0.93

9.30 33.6

LEA-2.2 67.65 7.26 2.63 1.76

10.57 32.5



Oil & water phase analysis

• According to GCMS, the major components in the water phase are L-Proline compounds,

hydrocinnamic acids, glycerol, and benzenepropanic acid, 4-hydroxyphenylethanol and C16 fatty acids.

• Oils obtained from the Spirulina contain 40.7%, of hexadecanoic acid, 10.1% of arachidonic acid, 13.9% of

octadecadienoic acid, 13.6% of cis-9-Octadecanoic acid and other components in small fractions.

• Most of the compounds detected in the bio-crude from Salina are similar to those obtained from

Spirulina biomass although the Salina sample contains more lipids, mainly C16 triglycerides, than the

Spirulina.

Fresh dry

Nannochloropsis

salina

Sample LEA-2.1

Crude Protein (CP), % 36.6 34.3

Acid Detergent Fiber (ADF), % 24.5 22.9

Neutral Detergent Fiber (NDF), % 39.6 36.6

Total Digestible Nutrients (TDN), % 87.4 68.4

Fat , % 12.02 2.69

Summary of nutrient values of algal biomass



Macroalgae as a feedstock and challenges

• High ash content (up to 50 wt%)

• High alkali metal content (high K and Na)

• High nitrogen and sulphur content (up to 3.5 wt% N)

• Low heating value (10-15 MJ/kg)

Thermal processing routes for macroalgae

• Ash chemistry restricts the use of macroalgae for direct combustion and gasification

• Pyrolysis produces a significant proportion of nitrogen containing compounds and high char

yield, The fate of nitrogen is potentially problematic in using these as fuels and some further de-

nitrogenation maybe necessary.

• The most suitable conversion technologies for macroalgae will most likely be those which are

most tolerant to the ash and alkali metals.



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HTL-A promising route for macroalgae

• Tolerate high moisture content

• Tolerate high ash content

• Most of the potassium and sodium is distributed in the aqueous phase and most of the calcium

and magnesium is distributed in the residue



CONCLUSION

• The carbon, hydrogen, and oxygen content of the bio-oil from microalgae is approaching that

of heavy crude

• The water phase from HTL of microalgae contained all required nutrients for algae growth.

Further studies are needed to determine if this water phase is suitable for algal cultivation

• The high nutrient value found in the lipid-extracted microalgae sample, can be use as animal

feed additives

• According to literature, HTL of macroalgae can potentially produce bio-oil and possible value-

added chemicals. However, to improve the yield and quality of bio-oil, more work is needed,

especially using different catalysts and other solvents.



LARGE SCALE LAB FACILITY-HTL

• Continuous Hydrothermal Liquefaction (HTL) facility (CBS-1)

• 15 kg/h feed, processing conditions up to 450 oC, 350 bar

• Oil production capacity: 1-3 kg/h

Full product





CBS-1

Acknowledgement

Prof. Lasse Rosendahl Prof. Jens Bo Nielsen Prof. Erik Søgaard Prof. Shuguang Deng New Mexico State University, USA

• Rudi P Nielsen

• Jessica Hoffmann

• Thomas Helmer Pedersen

• Harvind Reddy

• Dorte Spangsmark

• Linda B. Madsen



Thank you for your attention!



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