Dr Cliff

Susan Dansoh:
Scotcher: AssociateSenior 15:07:2015 – Renewable Energy.
Professor|Lecturer

Biofuels

October 2018
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Aims
 To introduce biofuels.
 To develop an understanding of the
various types of biofuel
technologies.
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Intended learning outcome

 To be able to identify the various
types of biofuel
 To understand of the various biofuel
technologies
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Agenda
 Introduction
 Types of biofuel
 Biofuel calculation/ exercise
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Liquid biomass (Biofuels)

Tend to be classified in terms of their generation:

 First generation
 Second generation; and
 Third generation.
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First generation biofuels

 Simple conversion process;
 Infrastructure in place;
 Derived from starch, sugars, fats
and oils found in food crops;
 High use of fertiliser and
pesticides;
 Has increased food prices; Majority of ethanol comes from corn
grown in the US and sugar cane from
 Low yield of ethanol from corn, Brazil
higher for sugar cane but still quite
low;
 Issues increasing due to targets
for biofuels for transport

Soyabeans used for biodiesel

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Interesting recent study

 http://www.biofuelsdigest.com/bdigest/2017/01/12/usda-releases-
lca-study-of-corn-based-ethanol/
 Report found that:
 GHG emissions associated with corn-based ethanol in the US
are about 43% lower than gasoline when measured on an
energy equivalent basis.
 Unlike other studies of GHG benefits, which relied on forecasts
of future ethanol production systems and expected impacts on
the farm sector, this study reviewed how the industry and farm
sectors performed over the past decade to assess the current
GHG profile of corn-based ethanol.
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Second generation biofuels

 Waste biomass (e.g. used cooking oil (UCO)
rather than virgin oil; London buses to use
10% UCO)
 Lignocellulosic biomass
 Agricultural residues
 Can still be grown on arable land – better if London bus fleet are going to use
not! Marginal land is more common 10% biodiesel from London’s used
 Feedstock should not need much water or cooking oil (UCO).
fertiliser to grow
 Switch grass is common choice in the US
 Jatropha and palm oil need crop land so
have become less popular (marginal land
with effluent water?)
 Greater processing and refining is required
Waste land and water for energy
otherwise biofuel can damage engines
crops in Palwal, India
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Third generation biofuels

 Algae on the sea is an interesting option – something the size of England
could fuel America
 Natural oil content of more than 50% - high yields
 Avoids competition with edible crops
 Can derive biodiesel, butanol, ethanol and methane

http://energyfortomorrow.yolasite.com/third-generation.php

 Unfortunately algae require vast quantities of nitrogen and phosphorus.

 The amount of fertiliser required would have a huge environmental and
economical impact
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Bioethanol production by
fermentation
 Alcohols (ethanol, propanol and butanol) can be
produced during fermentation of sugars and starches
by microorganisms and enzymes
 Ethanol fuel is made by enzyme digestion (to release
sugars from feedstocks such as wheat, corn, sugar
cane), fermentation of sugars, distillation and drying.
 Distillation requires large quantities of heat (bagasse?)
 Bioethanol can be blended with petrol in cars (E10, E5)
 Smaller energy density in comparison to petrol
 A large amount of energy is used for farming, transport,
processing, etc. thus the fossil fuel offset can be small
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Sugar fermentation process

The hydrolysis process cleaves chemical bonds by the addition of water.
Carbohydrates (e.g. sucrose) broken down into sugar molecules. Yeast is
added to the solution, which is then heated.
The yeast contains an enzyme called invertase, which acts as a catalyst and
helps to convert the sucrose sugars into glucose and fructose (both C6H12O6).

C12H22O11 + H2O → C6H12O6 + C6H12O6

sucrose water invertase fructose glucose

Sugar solutions that can then be fermented into ethanol. The fructose and
glucose sugars react with another enzyme called zymase - also contained in
the yeast to produce ethanol and CO2.
C6H12O6 → 2C2H5OH + 2CO2
Glucose/fructose zymase ethanol

Fermentation takes around three days, between 250°C and 300°C.

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Ethanol

C2H5OH
During combustion ethanol reacts with oxygen to
produce carbon dioxide, water, and heat

C2H5OH + 3 O2 → 2 CO2 + 3 H2O + heat

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Cellulosic ethanol
 Wood, grasses and other lignocellulose waste (non-food)
feedstocks can be used to make biofuels.
 Lignocellulose feedstock is more abundant than corn and
http://www.intechopen.com/books/biomass-now-
cane and has better carbon credentials. sustainable-growth-and-use/lignocelluloses-
feedstock-biorefinery-as-petrorefinery-substitutes

 Requires greater processing to release sugar monomers

 Difficult production challenges mean that cellulosic
ethanol is just emerging
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Cellulosic ethanol process

http://www.ifpenergiesnouvelles.com/Research-themes/New-energies/Producing-fuels-from-biomass/Biocatalysts-one-of-IFPEN-s-
expertise-field-Questions-to-Frederic-Monot-Head-of-the-Biotechnology-Department-at-IFPEN
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Cellulosic pre-treatment

 Acid hydrolysis

Goal is to reduce crystallinity of cellulose

(C6H10O5)n + nH2O -> nC6H12O6

 Two stage pre-treatment of lignocellulosic biomass using acid

hydrolysis
1. Dilute sulphuric acid (H2SO) 0.7% sulphuric is used to depolymerise
hemicellulose at a low temp 140°C – 190
2. Using 0.4% sulphuric acid at a higher temperature 190 – 215 °C is
carried out to yield the more resistant cellulose fraction, thus making
it available for enzymatic hydrolysis
The liquid hydrolates are then neutralised and recovered from the
process.
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Cellulosic pre-treatment

Enzematic saccharificaation/ hydrolysis:

 The hydrolysis of soluble polysaccharides to form simple sugars

 Concentration, temperature and time influence sugar and acetic acid

yields
 Can produce degradation products (furfural and HMF
hydroxymethylfurfural) which inhibit or delay the fermentation process.
 https://www.youtube.com/watch?v=ziYKhp3Clm0
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Biodiesel production
 Main process is Transesterification
 The process of exchanging the organic group of an ester
with the organic group of an alcohol
 Biodiesel made by reacting lipids (soybean oil, used
cooking oil, animal fat) with alcohol to produce fatty acid
esters or a mono alkyl ester (heat and pressure)
 Biodiesel can be:
 Blended with diesel (B20, B5, etc.) or
 Used neat!
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Transesterification
 Feedstock oils processed to
remove impurities (dirt, water)
[virgin oils, waste vegetable
oils, animal fats, algae,
halphytes, even sewage
sludge]
 Tritrated to determine
concentration of free fatty acids
 Transesterification reacts lipids https://www.e-education.psu.edu/egee439/node/684

(fats and oils) with alcohol

(usually methanol, sometimes
ethanol) to produce biodiesel
and by-products
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Transesterification
 Base catalysed
transesterification uses
sodium and potassium
hydroxides to facilitate the
reaction
 Other reaction methods
include the use of high
temperatures (supercritical https://www.e-education.psu.edu/egee439/node/684
process) and ultrasonic waves
 Biodiesel purified by removing
other by-products (glycerol,
alcohol, water)
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Disadvantages
 Not enough vegetable oil and animal fat is made in the world to replace
fossil fuels
 Land requirements to grow enough biomass are extreme
 Has led to deforestation and damage to ecosystems
 Farmers growing crops for biofuels; less food = higher food prices
 Increase in corrosion from oxidation of unsaturated molecules and
increased water content from moisture absorption
 High viscosity can clog fuel filters and injection engines
 Crystallises at low temperature (-15 – +15)

Advantages
 Increasing economy (GDP)
 Improves energy security
 Reduces GHG emission (50 – 80%)
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Bio-refineries

Bio-refineries are sometime categorised into 3 types

 Phase I – single feedstock, single process and single
major product
 Phase II – single feedstock, multiple processes and
multiple major products
 Phase III – multiple feedstocks, multiple processes and
multiple major products
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Example of Phase I bio-

refinery
Single feedstock and single process

Established and proven to be economically viable

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Example of Phase II bio-

refinery
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Example of Phase III bio-

refinery
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4th generation??
 Efficient 'carbon capturing'
process for taking CO2 out of
the atmosphere.
 The carbon-rich biomass (algae/
fast growing trees) is converted
into fuel and gases.
 The carbon dioxide can be
captured by pre-combustion,
oxyfuel or post-combustion
processes.
 The greenhouse gas can then http://global.mongabay.com/news/bioenergy/2007/10/quick-look-at-
fourth-generation.html
be geo-sequestered
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Festival power calculation

Source: https://commons.wikimedia.org/wiki/File:DJ-Loco.jpg
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The EU view

Source: http://task42.ieabioenergy.com/wp-
content/uploads/2017/10/ETIP_Bioenergy_Kerckow.pdf
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The EU view

Source: http://task42.ieabioenergy.com/wp-
content/uploads/2017/10/ETIP_Bioenergy_Kerckow.pdf
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The EU view
 The EU’s 2015 Indirect Land-Use Change
Directive makes significant changes regarding
land use.

 It introduces a ‘crop cap’: no Member State’s

share of biofuels from food crops can exceed
7% of transport energy.
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The UK view
Renewable Transport Fuel Obligations (RTFO).
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Renewable Transport Fuel

Obligations (RTFO).
 Fuel suppliers in the UK need to show that a
percentage of the fuel they supply comes from
renewable and sustainable sources.
 Fuel suppliers who supply at least 450,000 litres of fuel
a year are affected.

 Only rewards the production of biofuels that deliver

greenhouse gas savings and don’t cause environmental
damage with a more stringent crop cap of 1.5% than
the EU ILUD.
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Renewable Transport Fuel

Obligations (RTFO).
Results of recent consultation.
 The target level under the obligation will rise to 7.25
percent from April 2018.
 Increasing to 9.75 percent in 2020 and
 To 12.4 percent by 2032.
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The US view
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The problem
 U.S. energy security has long been a concern in the
road transportation sector as domestic production has
declined.

 It was also felt that there was a need to drive

investment in the development and production of
cellulosic and advanced biofuels that yield
significantly less carbon pollution than conventional
ethanol, gasoline, and diesel fuels.
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The proposed solution (RFS)

 Empowered by the Energy Security and Independence
Act 2007 (ESIA 2007);
 Also gives rise to the Renewable Identification Number
(RIN) mechanism;
 RINs are accredited to renewable fuel producers per
gallon of fuel produced.
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The proposed solution (RFS)

There are five classifications
(termed by ‘D-numbers’) of
renewable fuel in the RFS:
 Cellulosic Biofuel (D3);
 Biomass-Based Diesel (D4);
 Advanced Biofuel (D5);
 Renewable Fuel (D6); and
 Cellulosic Diesel (D7), which is
not shown.
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The proposed solution (RFS)

 The classification is based on ‘Pathways’ and is mainly to
do with source and process
 The use (such as motor or jet fuel), has no bearing on the
classification which is more concerned with the
greenhouse gas reduction that adoption of the specific
biofuel will achieve.
 Each D-number category has a separate volume
obligation;
 However, D6 (Renewable Fuel) is a catch-all class;
 Any renewable fuel that can fit the other classes can also
be used for D6.
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The proposed solution (RFS)

 The EPA sets a volume obligation of RINs (which increases

annually except for ethanol) and;
 Requires fuel importers and refiners to meet the obligation
by submitting RINs that they have either generated
themselves or bought from renewable fuel producers
through a RIN market.
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 This regulation has been controversial and recognises

that not all renewable fuel is created equal.
 Ethanol can only be used to satisfy the D6 obligation, and
a fuel in this categorisation cannot be upgraded to other
classes.
 The federally mandated volumes of ethanol remain
relatively flat from 2015 onwards.
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Ethanol
• Main problem with US ethanol is the volume of corn, a
staple food in most societies, that it requires.
• In 2001, 35% of the corn harvested in the United
States was used to produce ethanol
• By 2007 this proportion had risen to 71%.
• The U.S. is currently the world’s largest bioethanol
producer at some 14Bgal/yr
• This rapid rise in production has been partially blamed
for increasing the price of corn and other grains in
developing countries.
• There are also disputes over whether corn-based
ethanol produces fewer overall greenhouse gas
emissions than fossil fuel.
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Emission requirements
 Stipulations on each D category
about the GHG reduction
required.
 LCA should consider:
 Crop yields
 Fertiliser use;
 Changes in land use and
carbon in soil
 Efficiency of conversion
process
 Generation of electricity from
any residual material
 Rebound effect
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LCAs can differ

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RINs
 RINs are accredited on an ethanol energy equivalence
basis to incentivise higher energy density production.
 A gallon of renewable fuel with the same energy
density as ethanol (the EPA proposes to use 77,930
Btu/gal.) receives 1 RIN.
 A gallon of renewable fuel with double the energy
density of ethanol gets 2 RIN.
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RINs
 Tradable compliance commodities
 Incentivises biofuel production by requiring petroleum
refiners to purchase the produced biofuel (or the
corresponding RINs) in proportion to their U.S. share of
the refining market.
 The refiners bear the costs of the RINs, which are
nominally equal to the difference between a biofuel's
market price and its production cost.
 RINs can therefore be considered a subsidy to biofuel
producers paid by a tax on refiners.
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RINs
• Has been going for several years and RINs have been
worth only $0.01 - $0.04 for most of their existence.
• This though is likely to change soon!
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The proposed solution (RFS)

• To date, producers have tended to met their obligations

using ethanol.
• The required volumes of renewable fuel is increasing; and
• There is the prospect that ethanol will hit the ‘blend wall’.
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Blend wall
 A significant part of the limitation on take up of
biofuels in the U.S. is termed the ‘blend wall’ which is
effectively a limit on the volume of renewable fuels
can be mixed with conventional fuels for fear of
causing damage to engines/ invalidating engine
manufacturers’ warranty.
 Many of the reasons for the blend wall are stated in
the Renewable Fuels Association (RFA) article ‘Blend
Wall’ although from a somewhat biased stance
against ‘Big Oil’.
http://ethanolrfa.org/pages/big-oil-builds-the-blend-wall
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The proposed solution (RFS)

• Interesting webinar from USA on biofuel policy and RFS

from 2013.
• https://www.bing.com/videos/search?q=the+renewable+fue
l+standard&&view=detail&mid=AD6598D1952A1977B5C1
AD6598D1952A1977B5C1&&FORM=VRDGAR
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How’s it going
 The RIN prices have been low so far.
 Expected to be challenging to meet mandates going
forward:
 Specific quantities of fuel type and overcoming blend wall are
likely to need significant investment.
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How’s it going

As the RIN is market based, supply and demand of the

appropriate renewable fuels and the ability to sell it could
make the RIN prices volatile.
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How’s it going

In 2015, about 24% of the petroleum consumed by the

USA was imported from foreign countries, the lowest
since 1970.
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How’s it going
Interesting article on RFS
Main thrust is that there are a mass of administrative issues
to be overcome –
www.biofuelsdigest.com/bdigest/2017/07/25/the-time-has-
come-for-rfs-reform/

Looks like its here to stay!

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The future
Domestic transport
 Biofuels are a short term solution and most think electric
vehicles will take over in time, but biofuels are likely to be
part of the interim solution.

 How much of the solution and long interim is debateable!

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Interim solution?
 Currently use ethanol with existing internal combustion
engines.
 Engines designed to run on ethanol operate at much
higher compression ratios.
 Are more efficient with a more complete burn.
 Significantly less emissions at source.
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Interim solution?

Nissan solid oxide fuel cell electric vehicle

Source: http://www.autoexpress.co.uk/nissan/95990/nissan-
announces-world-s-first-bio-ethanol-fuel-cell-car
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The future

Urban transport likely to switch to Electric soonest.

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The future – aviation fuel???

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Any questions
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The future
Road transport.
Electric vehicles vs biofuel Presentation

1 Hr to craft a short presentation – Max 15 mins:

Team 1
Why Electric Vehicles are better and more likely to succeed
than biofuel vehicles.

Team 2
Why biofuel Vehicles are better and more likely to succeed
than Electric vehicles.
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The future
Road transport.
Electric Vehicles vs Biofuel Presentation

Team 3
1 Hr to review what the literature says and develop an
opinion before the presentations.

Each member of team 3 has to talk for 2 mins about:

1. Their initial view point and why it you were convinced
2. If/ how this opinion was opposed
3. How effective was

Winner will be the team voted by Team 3 to have the most

convincing argument.