Biofuels

Why we need alternative fuels? What are the main candidates for biofuels? What is bioethanol? What are the production schemes for bioethanol? How does bioethanol become a good solution? economic issues environmental issues Problems and suggested solutions

Contents

Current Energy Crisis

Most of the energy used today comes from fossil fuels
Oil Coal Natural Gas Oil

Projected depletion
Natural gas
50-60 years 150 years

Coal

220 years

Problems with Fossil Fuels

Greenhouse gas emissions
Global Warming issue
Heat is trapped in the atmosphere which causes the Earth to warm up

Pollution

Dependence upon foreign oil Non-renewable

Air pollution-cars and trucks Water & Land pollution-oil spill Thermal pollution- heated water disrupts ecosystem

19 million barrels of oil per day $792,000/minute on imported oil

Why we need alternative fuels?

Continuous depletion of limited fossil fuel stock. Ensure protection and betterment of the environment. National security- to be dependent on foreign nations for energy

List of Countries By Oil Import

Rank 1 2 3 4 5 6 7 8 9 10 Country/Region

World
United States European Union China Japan India Germany Netherlands South Korea France Singapore Italy

Oil - imports (bbl/day) 68,190,000 10,270,000 8,613,000 5,080,000 4,394,000 3,060,000 2,671,000 2,577,000 2,500,000 2,220,000 2,052,000 1,800,000

Date of information 2009 est. 2009 est. 2009 est. 2011 est. 2009 est. 2009 est. 2009 est. 2009 est. 2011 est. 2009 est. 2009 est. 2009 est.

Consumption of petroleum products in India

Transport (Petrol, Diesel, CNG, Aviation Fuel) : 51%
Industry (Petrol, Diesel, Fuel Oil, Naphtha, Natural Gas): 14% Domestic (LPG and Kerosene): 18%

Agriculture (Diesel): 4%
Others: 13%

Facts and Figures

Indias crude oil import is around 140 million tonnes (2009-10) which is 81% of total oil consumption in the country (Ministry of Petroleum and Natural Gas, 2009). Import bill of >75 billion dollars Indias National biofuels policy in 2009: 20% bioethanol and biodiesel blend in petrol and diesel by 2017

Global Ethanol Production and Projections

Global Biodiesel Production and Projections

Biofuels/Bioproducts Technologies
Biochemical Platform

Thermo-chemical Platform
Biomass gasification Black liquor gasification

Chemical Platform
Biodiesel

Who are the main candidates for biofuels?

Bioethanol Biodiesel

Biobutanol ???

Annual Fuel Ethanol Production by Country (Millions of U.S. liquid gallons per year)
World Country/Region rank 2011 2010 2009 2008 2007

1
2 3 4 5 6 7 8 9 10

United States
Brazil European Union China Thailand Canada India Colombia Australia Other World Total

13,900
5,573.24 1,199.31 554.76

13,231
6,921.54 1,176.88 541.55

10,938
6,577.89 1,039.52 541.55 435.20

9,235
6,472.2 733.60 501.90 89.80 237.70 66.00 79.30 26.40

6,485
5,019.2 570.30 486.00 79.20 211.30 52.80 74.90 26.40

462.3

356.63

290.59 91.67 83.21

87.2

66.04

56.80 247.27

22,356.09

22,946.87

19,534.993

17,335.20

13,101.7

Energy Density of Fuels (MJ/kg)

Bagasse (Cane Stalks) 9.6

Chaff (Seed Casings)

Dried plants (C6H10O5)n Wood fuel (C6H10O5)n Pyrolysis oil Methanol (CH3-OH) Ethanol (CH3-CH2-OH) Butanol(CH3-(CH2)3-OH) Biodiesel Methane (CH4)

14.6
10 16 16 21 17.5 19.9 22.7 23.4 26.8 36 37.8 55 55.7

http://en.wikipedia.org/wiki/Energy_content_of_biofuel

Energy Density of Fuels Contd..

Hydrogen (H2) 120 142

Coal
Crude Oil Gasoline Diesel Natural Gas

29.3 33.5
41.868 45 48.3 48.1 38 50

Uranium-235 (235U)

77,000,000

What is bioethanol?
Ethanol derived from agricultural sources, as distinct from petrochemical sources, is referred to as bioethanol.

Production schemes for bioethanol

Bioethanol is mainly produced in three ways.
sugar starch ethanol sugar ethanol ethanol

Cellulose and Hemicellulose

Direct conversion of sugar to ethanol

This is usually done using molasses. Molasses is a thick dark syrup produced by boiling down juice from sugarcane; especially during sugar refining. As molasses is a by product, ethanol production from molasses is not done in a large scale around the world. The main reaction involved is fermentation

C6H12O6

yeast

2 C2H5OH
ethanol

2 CO2
carbon dioxide

Sugarcane based Ethanol

Simplest of all the processes

Typical Composition of Molasses

Molasses Fermentation to Ethanol

Factors Affecting Fermentation

Corn Based Ethanol Production

a) Wet Milling Process
Starch is main product

b) Dry Grind Process

Conventional Corn Wet Milling Process

Corn Steep Tank Moisture Expeller Dewatering Screen
A B

Fresh Water

Primary Mill Hydrocyclones First Grind Tank Third Grind Screen

Secondary Mill

Second Grind Tank

Hydrocyclones

Pressure Fed Screens Fiber Process Water

Third Grind Mill (Fine Grind)

Degritting Cyclone

Mill Stream Thickener

Process Water

Process Water Process Water Clarifier Primary Centrifuge Gluten Thickener Centrifuge

Gluten Belt Filter Gluten

Starch

31.5 lbs of starch @$0.12/lb, $3.78

3.0 lbs of gluten meal @$0.16/lb, $0.48

1 bushel of corn
11.4 lbs of gluten feed @$0.035/lb, $0.40

1.6 lbs of germ oil @$0.23/lb, $0.37

$2.30

$3.78 +$0.48 + $0.40 + $0.37 = $5.08

Starch Based Ethanol Production

Corn Sorghum

Potato
Barley Wheat

Dry Grind Ethanol Process

Corn Dry Grind Facility

2.7 gal (10.2 L) of Ethanol

One bushel of Corn (24.5 kg or 56 lb)

15 lb (6.8 kg) of DDGS

Ruminant Food

Conventional Dry Grind Process

Corn

Grinding (Hammermill) Water Mash CO2 Overhead product (Recycled back)

Blending Alpha-Amylase

Liquefaction

Ethanol

Dehydration column Yeast & Glucoamylase Thin Centrifuge Saccharification & Stillage Fermentation Stripping/ Rectifying column Syrup Wet Grains

Evaporator

DDGS

Dry Grind Ethanol Process: Current Scenario

Gluco-amylase Corn Alpha-amylase Mash Grinding Slurry Tank Cooking Liquefaction

Fresh Water
CO2 Saccharification + Fermentation CO2 Scrubber

Scrubber Water Beer Well Beer

Distillery Condensate Process Condensate

Distillation Whole Stillage

Molecular sieve

Backset (30 to 50% thin stillage)

(5 to 10% solids) Thin Stillage

Centrifuge Wet Grains

Ethanol

Evaporator Evaporator Condensate Syrup Dryer Solids Recycle DDGS

Condensate Water

CEREAL CHEMISTRY

Composition
What are the main component of cereal grains? Starch/carbohydrates

Protein
Oil Cellulose/hemicellulose/lignin

Corn Kernel Composition

The Chemists View of Carbohydrates

Carbohydrates are made of carbon, hydrogen and oxygen atoms. These atoms form chemical bonds that follow the laws of nature.

Simple Carbohydrates
Monosaccharrides are single sugars (most are hexoses).
Glucose serves as the essential energy source, and is commonly known as blood sugar or dextrose. Fructose is the sweetest, occurs naturally in honey and fruits, and is added to many foods in the form of high-fructose corn syrup. Galactose rarely occurs naturally as a single sugar.

Glucose

 2008 Thomson - Wadsworth

Sucrose

CH2OH

H
H OH HO H

HOH2C

CH2OH

OH OH

OH

OH

Maltose
CH2OH H
O

CH2OH H O H H H
O

H
OH HO H OH

OH

H OH

OH

The Simple Carbohydrates

Disaccharides are pairs of monosaccharides, one of which is always glucose
Condensation reactions link monosaccharides together. Hydrolysis reactions split molecules and commonly occur during digestion. Maltose consists of two glucose units. It is produced during the germination of seeds and fermentation. Sucrose is fructose and glucose combined. It is refined from sugarcane and sugar beets, tastes sweet, and is readily available. Lactose is galactose and glucose combined. It is found in milk and milk products.

The Complex Carbohydrates

Glycogen
Storage form of glucose in the body Provides a rapid release of energy when needed

Starches
Storage form of glucose in plants Found in grains, tubers, and legumes

2008 Thomson - Wadsworth

Starch and Cellulose

Both polymers of glucose Starch-abundant energy storage molecule Cellulose-abundant structural molecule

Starch
Amylose linear 2-5 Thousand glucose units

CH2OH H H OH HO H OH O H H O H

CH2OH H OH H O H H OH O H

CH2OH H OH H O H H OH O H

CH2OH O H H OH H H OH OH

Amylopectin branched

Starch

30-500 Thousand glucose units

Amylopectin

Starch

Cellulose

Types of Commercial Corn Starch

Regular Dent 23% amylose 77% amylopectin

Waxy
High Amylose

99-100% amylopectin
50% amylose or 70% amylose

Dry Grind Ethanol Process

Corn Dry Grind Facility

2.7 gal (10.2 L) of Ethanol

One bushel of Corn (24.5 kg or 56 lb)

15 lb (6.8 kg) of DDGS Ruminant Food

Dry Grind Ethanol Process: Current Scenario

Gluco-amylase Corn Alpha-amylase Mash Grinding Slurry Tank Cooking Liquefaction

Fresh Water
CO2 Saccharification/ Fermentation CO2 Scrubber

Scrubber Water Beer Well Beer

Distillery Condensate Process Condensate

Distillation Whole Stillage

Molecular sieve

Backset (30 to 50% thin stillage)

(~10% solids) Thin Stillage

Centrifuge Wet Grains

Ethanol

Evaporator Evaporator Condensate Syrup Dryer Solids Recycle DDGS 57

Condensate Water

Corn Storage
Where the corn is stored before it is sent to milling

Milling
Ground into Meal

Jet Cooking
Sterlization Release of bound sugars and dextrins Reduction in viscosity (Gelatinization) Solubilization of sugars

Mashing
Heat and Enzymes Fermentation Sugars

Fermentation
Cooled and Mixed Fermented mash

Yeast - Major Characteristics

Unicellular Fungi Eukaryotic Facultative anaerobes Capable of forming colonies on solid culture media (see pictures on the right). Occur worldwide Over 1,500 species described

Yeast - Reproduction
They reproduce either asexually (most common) or sexually. Asexual reproduction is through budding or binary fission. Sexual reproduction (if any) results in the formation of the appropriate spore structure. Fission Budding

Saccharomyces cerevisiae

Spores
Schizosaccharomyces octosporus

 Industrial and Commercial Applications

Food Industry ~ Beer ~ Bread ~ Cheese ~ Wine ~ Yogurt Pharmaceutical Industry ~ Insulin ~ Vaccine Adjuvants Energy ~ Fuel Ethanol

1 gram dry weight yeast equates to approx. 48.7 billion cells.

Yeast Growth Requirements

Water Carbon Source Oxygen or Sterols and unsat. Fatty acids) Nitrogen Source (inorg. Ammonium ion, urea, amino acids, small peptides) Vitamins Inorganic ions

 Fermentation can be defined as an energy yielding process where yeast converts organic molecules (such as sugar) into energy, carbon dioxide or/and ethanol depending on the respiration pathway. Yeast can respire in anaerobically and aerobically. However, yeast gets more energy from aerobic respiration, but in the absence of oxygen it can continue to respire anaerobically, though it does not get as much energy from the substrate.

C6H1206 2 CH3CH2OH + 2 CO2 + 2 ATP C6H1206 + 6O2 6CO2 + 6H2O + 16-18 APT

Sluggish Fermentation
Stuck or sluggish fermentations occur when the rate of sugar utilization becomes very slow or protracted, especially toward the end of a fermentation. When the sugar content is high and vital nutrients are lacking, a stuck fermentation can occur. An inadequate level of assimilable nitrogen is often the culprit.

When the feed substrate to the reactor is not monosaccharide e.g. sucrose (C12H22O11), yeast enzyme cause glycosidic bond to break in a process called hydrolysis

Pathway
Sugars are converted via glycolytic pathway (also known as Elden-Myerhof-Parnas or EMP pathway). Energy Carrier Adenosine TriPhosphate (ATP)
Nicotinamide Adenine Dinucleotide (NAD+)

Energy and the yeast cell

The yeast cell requires energy for three main activities. i) Chemical energy: to synthesize complex biological molecules (i.e. make more yeast cell components)

ii) Transport: energy must be expended to transport nutrients in and out of the cell.
iii) Mechanical energy: cells need to move structures internally and this requires energy (i.e. budding).

Typical Yeast Growth Curve

Stress Factors Affecting Yeast

Yeast Metabolism
Glycerol (Osmoprotectant) Succinnic acid Lactic acid Acetic acid Acrolein