Presentation©E.Schmid-2011

“Biofuels Production & Analysis”

Overview of Biofuels Feedstocks

The sun is the primary energy source for phototrophic life forms (plants, algae and cyanobacteria) which use photosynthesis to convert electromagnetic energy (E= h x v) into water-derived reduction equivalents (NADH) and ATP which with CO2 is used to build simple sugars like glucose which can be turned into:•hydrocarbons: starch, cellulose, lignin and oil•nucleic acids (add nitrogen and phosphorous)•amino acids and proteins (add nitrogen and sulfur)

Photosynthesis & Its Products

AtmosphericCO2

H2O

Glucose/Fructose(C6H12O6)

Plant orAlgae

Sun

Graphic©ElmarSchmid-2010

SolarEnergy

CelluloseStarch

Oil

Lignins

O2

Photosynthesis

Biomass

Photosynthesis

Biomass: Starch and Cellulose

Biomass: Lignin

Glucose to Phenylalanine

Phenylalanine to Lignin 1

Biomass: Oil (Triglyceride)

Photosynthesis

Presentation©E.Schmid-2011

“Biofuels Production & Analysis”

Industrial Bioethanol Production =1st Generation Biofuel

Steps Of Industrial Bioethanol Production

• harvest feedstock (corn)

• mash and cook corn to release glucose

• ferment glucose with yeast to produce ethanol

• distill ethanol from mixture

• strain

• mix 15%-50% ethanol with 85% gasoline for use in automobiles

Industrial Bioethanol Production

Bioethanol

Corn

1 Grinder

2 Mash

H2O

T↑

3 Cooker 4 Fermenter +Distiller column

CO2

T

5MolecularStrainer

6Bioethanol

Storage7Transportation &

Distribution

Graphic©E.Schmid-2010

Presentation©E.Schmid-2011

“Biofuels Production & Analysis”

2nd Generation Biofuels

2nd Generation Biofuels

• Use corn stover, bagasse, energy cane (high in cellulose and lignin) for feedstock

• It is difficult to release and ferment the sugars from these feedstocks made from cellulose and lignin that make up the plant cell wall.

Barriers to Cellulosic BiofuelsCellulosic Ethanol Production

– The entire process is expensive– Grasses are difficult to transport and to store

(corn can be stored at the farm until it is transported to the ethanol facility, grasses are bulky for storage)

– Cellulosic enzymes are not as efficient as is desired*

• cellulose is difficult to breakdown• cellulosic enzymes are expensive to

produce– Efficient microbes for fermentation are still

being researched– The entire process has not been optimized

for commercial production

*Companies such as Genencor (Danisco)

In Rochester, NY and Novazyme in NC are working on the development of cellulosic enzymes.

Today we will look for the cellulosic enzyme, cellobioase, in mushrooms.

Presentation©E.Schmid-2011

“Biofuels Production & Analysis”

Hydrogen from Bacteria

Mira Costa College Educational biohydrogen reactor work station

Photo©E.Schmid-2010

Bacterial Production of H2 Fuel• Prepare and sterilize media in a spinner bottle.

• Inoculate with Enterobacter aerogenes.

• Culture at room temperature until hydrogen gas is produced.

• Run tubing to fuel cell which strips electrons from hydrogen atoms using a platinum catalyst.

• Electrons pass into wire to fan, activating fan.

• Protons pass to other side of fuel cell and combine with oxygen to produce water.

Biofuels from Microalgae

Why Biofuels from Microalgae?

Crop Oil Yield(kg oil / ha x

year)

Oil Yield(gal oil / ha x

year)

Corn 146 45

Soybeans 375 120

Peanuts 921 282

Rapeseed/Canola

1,000 306

Olives 1,051 322

Avocado 2,298 705

Palm oil 5,000 1,575/1,890

Algae Farming268,950 (Valcent)60,000 (Shell)

21,842 (Molina et al.)

33,000 (other)

82,50018,4056,70010,123

Comparison of Oil Production in Agricultural Plants

Microalgal Photosynthesis & Oils

AtmosphericCO2

H2O

Glucose/Fructose(C6H12O6)

Plant orAlgae

Sun

Graphic©ElmarSchmid-2010

SolarEnergy

CelluloseStarch

Oil

Lignins

O2

Photosynthesis

Biomass

Microalgae have a fast growth rate and can double in less than 24 hours.

Microalgae utilize the available sunlight much more efficiently than terrestrial green plants. Most microalgae have a solar conversion efficiency of about 4-5% which is higher than in plants . Microalgae are metabolically very versatile and many value products cancan be produced, including antioxidants, poly-unsaturated fatty acids, oils, and fish and cattle feed.

Large scale cultivation of microalgae removes significant amounts of the greenhouse gas CO2 from the atmosphere, leading to net 0 CO2 when combusted (burning fossil fuels adds CO2 to the atmosphere)

Large scale cultivation of microalgae under controlled, contamination-free conditions can be achieved in closed loop photobioreactors.

Microalgae Advantages

Commercial Tubular Closed Loop Algae Photobioreactor

Taken from the website of Bioprodukte-Prof. Steinberg GmbH, Germany

Bubble Column Photobioreactor Work Station

Photo©E.Schmid-2010

Fuels can be produced in a sustainable, renewable way - algae areharvested and quickly regrown within days or weeks within photobioreactor

environments.

Fuels, e.g. biodiesel, burns carbon-neutral when combusted in internalcombustion engines or other energy conversion devises.

Microalgae oils and fuels are non-toxic and highly bio-degradable.

Biodiesel is a drop-in fuel and may be used in any diesel vehicle with no engine conversion necessary. In 2012, the Navy is piloting the use of 50%/50% drop-in biofuels and fossil fuels in their vehicles in Hawaii; in 2016 the Navy will convert all its vehicles (except nuclear powered) to this mix.

Algae can grow in low grade water, waste water and even marine water.

Microalgae Advantages, continued

Microalgae Supply Chain

• A triglyceride is composed of one glycerol molecule chemically linked with three fatty acids

Glycerol

Fatty acide.g. Stearic acid (C18:0)

Fatty acid can be saturated or unsaturated

+

3x

Triacyl-Glyceride

(“Oil” or “Fat”)

Components of Fats, Oils or Triglycerides

Oil Extraction Methods: Mechanical Extraction

• Since oils are lipophilic they are often extracted from biological materials, e.g. seeds or algae, with the help of lipophilic (organic) solvents.

• Important organic solvents used for oil extraction are:1. n-Hexane2. Chloroform (CHCl3)3. Isopropanol

• Many different manual and automatized oil extraction methods have been developed, such as:1. Folch method2. Soxhlet method3. Accelerated solvent extraction (ASE) method

Oil Extraction Methods: Chemical Extraction

Steps of the Folch method• Algae dry biomass• Algae cell disintegration (Mortar, Ball milling,

sonication)• Chloroform/methanol (2:1)• Vortex• Centrifugation• Chloroform transfer into new tube• Chloroform (pure)• Vortex• Centrifugation• Chloroform transfer & pooling• Solvent evaporation

Biodiesel• Biochemically, the raw material for biodiesel

production are triacylglycerides (TAGs)• Depending on the degree of saturation of the fatty

acids, TAGs are referred to as oils or fats• Biodiesel is produced via a

process called transesterification

Unsaturated C16–18 Fatty Acid Methyl Esters (FAME)

(“Biodiesel”)

Triacylglycerides (TAGs)

Transesterification usingMethanol and Base (Methoxide)

OilsOils FatsFats

Biodiesel

Biodiesel

Biodiesel Analysis• Fatty acid methyl esters (FAMEs) can be detected and

analyzed by different methods including:1. Gas chromatography (GC)2. High pressure liquid chromatography (HPLC)

• Gas chromatography is highly sensitive but requires prior derivatization of FAME sample

• HPLC-based analysis requires special detection system called evaporative light scattering detection (ELSD)

• Both methods give typical product peaks of the analyzed FAME sample

Typical Result Of FAME Analysis With HPLC-ELSD

13 min0 min

Yielded information:1. Retention time2. Area under the curve (peak) quantity

Another Alternative?Pyrolysis of Duckweed

http://www.youtube.com/watch?v=4bJVvEd-cRk