219 0003 FPR
219 0003 FPR
219 0003 FPR
NNFCC, Biocentre,
York Science Park,
Innovation Way,
Heslington, York,
YO10 5DG.
This is the final report of a 3 month project (RD-219-0003) which started in July 2013. The
work was funded through a contract for £15,000 from HGCA.
While the Agriculture and Horticulture Development Board, operating through its HGCA division, seeks to ensure that the
information contained within this document is accurate at the time of printing, no warranty is given in respect thereof and, to the
maximum extent permitted by law, the Agriculture and Horticulture Development Board accepts no liability for loss, damage or
injury howsoever caused (including that caused by negligence) or suffered directly or indirectly in relation to information and
opinions contained in or omitted from this document.
Reference herein to trade names and proprietary products without stating that they are protected does not imply that they may
be regarded as unprotected and thus free for general use. No endorsement of named products is intended, nor is any criticism
implied of other alternative, but unnamed, products.
HGCA is the cereals and oilseeds division of the Agriculture and Horticulture Development Board.
ii
Contents
Aim and scope of this study ................................................................................................... i
Executive Summary ...............................................................................................................ii
1. Bio-based plastics market ................................................................................................. 1
1.1 The EU Bioeconomy .................................................................................................... 1
1.2 Market drivers for bio-based plastics ........................................................................... 2
1.3 Market forecasts .......................................................................................................... 5
1.4 Summary ..................................................................................................................... 6
2. Lactic acid production and markets ................................................................................... 7
2.1 Lactic acid ................................................................................................................... 7
2.2 European PLA market ................................................................................................. 8
2.3 PLA classifications..................................................................................................... 10
2.4 Competitor analysis ................................................................................................... 11
2.5 Summary ................................................................................................................... 13
3. UK Grain Milling industry ................................................................................................. 13
3.1 Background ............................................................................................................... 13
3.2 Wheat ........................................................................................................................ 15
UK production .............................................................................................................. 15
Milling products and residues ....................................................................................... 16
Residues ...................................................................................................................... 18
3.3 Oats........................................................................................................................... 19
UK production .............................................................................................................. 19
Milling products and residues ....................................................................................... 20
3.4 Barley ........................................................................................................................ 22
3.5 Summary ................................................................................................................... 22
4. Lactic acid production from milling residues .................................................................... 23
4.1 Utilisation of milling co-products for chemical production ........................................... 23
4.2 Process overview for the production of lactic acid from cereal residues ..................... 25
Pretreatment ................................................................................................................ 26
Saccharification............................................................................................................ 26
LA fermentation............................................................................................................ 26
Acidification.................................................................................................................. 27
Purification ................................................................................................................... 27
Concentration .............................................................................................................. 28
4.3 Summary ................................................................................................................... 28
5. Feasibility assessment .................................................................................................... 29
iii
5.1 Feedstock requirements ............................................................................................ 29
5.2 Economic assessment ............................................................................................... 31
6. Conclusions .................................................................................................................... 33
7. Further recommendations ............................................................................................... 35
Bibliography ........................................................................................................................ 36
Appendix 1 – Chemistry of PLA .......................................................................................... 37
Appendix 2 – PLA characteristics and considerations ......................................................... 39
List of Figures
List of Tables
iv
List of abbreviations
PET: Polypropylene
v
Aim and scope of this study
The aim of the study was to determine if UK derived cereal residues and associated
products provide an economic and technically feasible route to produce lactic acid (LA) at
sufficient scale to provide the raw material for a UK world-scale (30,000 tpa) polylactic acid
(PLA) plant.
Attention is given to the current state of the EU bioplastics and PLA market, processes
required for conversion of cellulosic feedstocks to LA, availability of residues from wheat, oat
and barley milling operations and value chain development prospects. Many of the study
parameters were based on earlier results (Reineck, 2008), for which feasibility of a
30,000tpa UK PLA plant using starch-based feedstocks was assessed.
i
Executive Summary
The production of poly-lactic acid (PLA), a biodegradable and bio-based polymer, from
cereal milling residues (wheat, barley, oat, starch) at large scale represents a market
opportunity in the UK provided five crucial parameters are in place: 1) a supportive political
framework, 2) market attractiveness, 3) technological feasibility, 4) feedstock availability, and
5) economic viability. In consideration of these parameters, this study assessed the potential
for developing a UK lactic acid (LA) plant capable of providing sufficient LA for a 30,000
tonnes per year (tpa) PLA plant, utilising cereal milling residues as feedstock.
A review of the EU political framework for bio-based products and evaluation of the existing
and near-future PLA market demonstrated that a supportive environment exists in the UK for
large-scale production of LA. Brand owners are continually seeking to demonstrate their
products are environmentally sustainable through introducing bio-based ingredients and bio-
based packaging, while consumers are increasingly keen to support environmentally-friendly
products. In accordance, the PLA market in the EU is expected to grow 13% by 2025, with
demand expected to outstrip supply. Meanwhile, growing competition between food markets
and industry for traditional agricultural crops have meant that utilisation of non-food cellulosic
feedstock is becoming increasingly attractive. As a consequence, there can be expected to
be high future demand in the EU for LA derived from cellulosic biomass.
To date, there has been little activity in developing LA from milling by-products. However, by
analysing the technologies and production pathways needed for production of LA and PLA
from cereal residues, we found numerous technologies that have been commercialised for
LA and PLA production from cellulosic biomass and several processes that have focused on
the conversion of milling residues to fermentable sugars, thus indicating technical feasibility.
In consideration of these processes, a potential production pathway for conversion of milling
residues to LA was constructed.
This study further demonstrates that there is good potential in the UK for developing value
chains based on production of LA from cereal milling residues – notably wheat
bran/middlings and oat husks/hulls – in sufficient volumes to supply a 37,500 tpa LA plant
(equivalent to the feedstock requirement of a 30,000 tpa PLA). Most encouragingly, it was
discovered that a single oat milling facility exists in the UK which alone produces almost
sufficient residue volumes to supply a facility of this scale.
ii
The main findings of the study are summarised in Summary Table 1.
Summary Table 1. Cumulative results scheme from feasibility analysis for production of PLA
from cereal milling residues in UK
Wheat Oat
Waste wheat Wheat Wheat Residual Oat
middlings husks/
milled grain bran germ starch bran
(wheatfeed) hulls
Abundance/
High High Low High Low Low High
availability
Total carbohydrate 80%
63% 47% 63% Up to 90% 83% 67%
content (wet basis) (endosperm)
Industrial Food/ Food/ Food/ Food/ Feed/
Competitive uses Feed
(periodic) feed feed industrial feed energy
Technological 1G/ 2G/ 1G/ 2G/ 2G/
2G/ 1G/
feasibility/ C6 C6+C5 C6+C5 C6+C5 C6+C5
C6+C5 Ferm C6 Ferm
maturity Fermentation Ferm Ferm Ferm Ferm
Economic
Good Good N/A Good Good N/A Good
competitiveness
Water content
(transportation/ 20% 10% 14% 10% Very low 12% 5%
storage)
Overall
Low High Low High Low Low High
attractiveness
Ultimately, this study shows that there is a strong and growing market for LA and PLA, the
production pathways from cellulosic feedstocks are becoming commercialised and therein
lies potential to develop value chains from cereal milling residues in the UK. However, little
work has been done to date regarding the manufacture of LA from milling residues, and
therefore this opportunity can be expected to have significant risks, especially in regards to
technical feasibility.
iii
1. Bio-based plastics market
1.1 The EU Bioeconomy
The oil-based economy provides the foundation for modern society; with fossil resources
meeting much of our energy, chemical and material needs. However, growing concerns over
climate change and oil price volatility has stimulated great interest within Europe of
facilitating a transition to a bioeconomy. According to the European Commission, the
bioeconomy “integrates the full range of natural and renewable biological resources - land
and sea resources, biodiversity and biological materials (plant, animal and microbial),
through to the processing and the consumption of these bio-resources”1. The bioeconomy
has the potential to provide sustainable and renewable replacements for all commodities and
products currently derived from fossil fuels.
The European Union has already taken an important step towards establishing an era of
low-carbon, resource efficient, sustainable and inclusive economic growth in Europe with the
decision to formulate a bioeconomy strategy and action plan 2. As the European Commission
rightly acknowledges, the bioeconomy has the potential to contribute not only to tackle global
problems such as climate change, CO 2 emissions reduction and sustainable economic
growth, but also to furthering research and innovation excellence in Europe, and more
sustainable agricultural policies linked to regional and rural development.
• A reform of the European Common Agricultural Policy (CAP). The reform will
result in an investment of over €100 billion between 2014 and 2020 for ensuring that
EU agriculture ‘meets the challenges presented by soil and water quality, biodiversity
and climate change’ 3.
• Development of the Horizon 2020 research and innovation program. The
initiative will provide nearly €80 million funding between 2014 and 2020 to drive
economic growth and create jobs within the EU. A bio-based industry PPP (BRIDGE
2020) 4 has been established as part of the program and will receive investments of
1
http://ec.europa.eu/research/consultations/bioeconomy/introductory_paper.pdf
2
European Commission. 2012. Innovating for Sustainable Growth: A Bioeconomy for Europe.
3
http://europa.eu/rapid/press-release_IP-13-613_en.htm
4
Bio-based Industries Consortium. 2013. Bio-based and Renewable Industries for Development and Growth in
Europe.
1
€1 billion from the Commission and €2.8 billion from industry to develop new value
chains, optimise feedstock usage and bring novel technologies to maturity.
Within the bioeconomy, bio-based plastics have the potential to deliver many of the
proposed benefits of the bioeconomy. Bio-based plastics are simply plastics derived from
biomass instead of oil. Some bio-based plastics are structurally and functionally identical to
fossil-based plastics (e.g. Bio-PET), while other bio-based plastics may only be derived from
biological resources (e.g. polylactic acid). Bio-based plastics have many advantages over
traditional plastics including the potential to have a lower carbon footprint, reducing
dependency on fossil resources and opportunities for developing products with novel
characteristics (e.g. compostability).
Whilst there is a realisation from policy-makers that the economy will be dependent on fossil-
derived products for some considerable time, there is also a drive to ensure that
replacement technologies are incentivised in order to close this time frame and protect the
market from the increasing volatility of fossil prices.
There are many other benefits of bio-based plastics over fossil-plastics. The branding
opportunity afforded by “green” and “environmentally-friendly” products is one of the most
attractive benefits of bio-based plastics. A 2013 survey undertaken by the European
Commission of 25,000 citizens across the EU-27 assessed the attitudes of European
consumers towards green markets (European Commission, 2013). The survey identified that
more than 80% of EU citizens surveyed currently buy environmentally-friendly products while
77% of citizens are willing to pay a premium for such products, highlighting the importance of
green marketing on consumer behaviour.
Moreover, the main brands regularly seek extra functionality in their material chain in order
to make product improvements. Bio-based plastics offer opportunity for developing such
novel properties. The most notable development to date is the development of
biodegradable and compostable bio-based plastics. While the majority of fossil-based
plastics will persist in the environment almost indefinitely, many bio-based plastics (such as
PLA) will decompose naturally through hydrolysis or photodecomposition. Such bio-based
plastics, therefore, have more advantageous end-of-life options than fossil plastics; bio-
based plastics can be used in industrial composting facilities or potentially anaerobic
digesters. Bio-based plastics may, in the future, be valorised higher than fossil plastics on
account of the incentives that exist for the use of biomass in energy generation. However, a
2
greater degree of market penetration and improved methods for measuring the biogenic
content of waste streams are required before this benefit can be fully realised.
A comprehensive list of the existing key market drivers for sustainable plastics is shown in
Table 1, with those most relevant to the Polylactic acid (PLA) market in bold
3
Table 1. Key Market Drivers for Sustainable Plastics
Commercial availability
Available in commercial quantities (i.e. not pilot plant or development)
+ Production capacity keeps pace with demand - Production capacity lags far behind demand
- No announcement of new capacity
Location of production plant
+ non-GM source (i.e. European) - GM is an issue for polymers such as PLA produced
from starch in USA
4
1.3 Market forecasts
European plastics demand is growing in line with gross domestic product (GDP) whilst
packaging – a significant market for plastics – is growing faster than GDP.
5
European bioplastics. Bioplastics: Facts and Figures.
5
Figure 2. Current and projected market shares of bio-based plastics5
Demand for bio-based plastics in Europe is expected to grow significantly in the long term on
account of the positive branding opportunities afforded by environmentally-friendly products
and the expected increase in price of comparative fossil-derived materials. Additional
opportunities may be created through regulatory interventions such as compostable bags
being exempt of a ban or charges placed on plastic bags. Assuming an average GDP growth
of 2.5% annually for the next 15 years, the European plastics market is projected to grow
from around 48 million tons in 2010 to over 70 million tons by 2025 (Reineck, 2011). By
further assuming that 20% of the plastic supply chain will be bio-based by 2030 (the industry
consensus view is 20–30%), European demand for bio-based plastics is estimated to be
9.25 million tons in 2025, representing a total market share of 13%. To meet this demand will
require a substantial increase in existing production capacity.
1.4 Summary
Due to climate change and oil price volatility concerns, EU policies and regulations have
been developed to incentivise the use of bio-based feedstocks in the fuel, chemical and
energy markets. Supported by strategies and regulations that prioritise bio-based products,
research and development funding schemes and investment incentives have supported the
commercialisation of innovative technologies making use of biological technologies and
facilitated market penetration of bio-based plastics.
6
their products by introducing bio-based ingredients in their supply chains. As a result, the EU
bio-based plastics market is expected to grow significantly in the near future.
Lactic acid (LA) is a platform chemical that is commercially manufactured from sugars
through large-scale fermentation. LA is most commonly produced from glucose, derived from
the processing of starch from cereal crops such as corn or wheat. However, there are
increasing concerns over the utilisation of traditional agriculture crops in non-food
applications due to potential indirect impacts on food prices and land use change (e.g.
deforestation). This is particularly evident in the biofuels industry, where investment in the
EU has stalled due to uncertainties over how such impacts should be addressed in policy.
Given the growing importance of sustainability in brand development, there is significant
interest in the utilisation of lignocellulosic feedstocks such as straw, wood and crop residues
for production of renewable chemicals in order to avoid potential negative interactions with
food markets. As it is feasible to produce LA by fermentation of both C6 and C5 sugars,
therein lies potential to utilise lignocellulosic biomass for commercial production of LA.
According to Bozell and Petersen (2010), LA is one of the top ten most attractive bio-based
chemicals for production by sugar biorefineries. LA can be converted into a multitude of
chemicals and materials such as PLA, ethylene glycol, lactate esters, and acrylic acid/esters
(Figure 3).
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Historically, the major markets for LA have been food, pharmaceuticals and cosmetics.
Approximately 70% of current production is used in the food industry, much of which is used
in the production of cheese and yoghurt (Martinez et al., 2013). LA can further be used to
provide acidity in food and beverages while lactate derivatives are often used as flavourings.
In the pharmaceutical industry, LA can be used in a variety of applications including blood
coagulants, topical wart preparations and anti-inflammatory drugs (Taskila and Ojamo,
2013). However, it is the polylactic acid (PLA) market that can be expected to be the primary
driver of LA market growth in the future.
PLA is a 100% bio-based polymer produced through the polycondensation of LA that offers
unique functionality (the chemistry of PLA synthesis is described in Appendix 1). PLA was
first discovered in the 1930s but was only commercialised as an industrial polymer in the last
15 years.
PLA has emerged as the world’s leading niche bioplastic, with global sales of over
100,000 tpa, and is expected to remain so for at least the next 10 to 15 years. The Nova
Institute has indicated that some 25 companies have developed a cumulative production
capacity of more than 180,000 tpa of PLA6. The largest producer is NatureWorks, in the US,
with a capacity of 140,000 tpa. Nova has further estimated that global production capacity
will increase to 800,000 tpa by 2020. By this time, Europe could be responsible for between
140,000 tpa and 180,000 tpa of supply.
An earlier market study commissioned by the NNFCC, forecasted total EU PLA demand to
grow from the current ~30 ktpa to 184 ktpa in 2015, reaching 650 ktpa in 2025 based on
forecast annual growth from 2015 to 2025 of 13% 7. Accounting for supply and demand
estimates, this results in a market gap of between 166 and 206 thousand tpa PLA by 2020
(Table 2).
6
Nova Institute. 2012. Bio-based Polymers in the World - Capacities, Production and Applications: Status Quo
and Trends towards 2020.
7
NNFCC. 2008. Techno-Economic Assessment of Potential PLA Manufacturing Plant in UK.
8
Table 2. Forecasted supply and demand of PLA in Europe
The largest opportunity for PLA market development in the near future is in thermoformed
sheet, mainly used for rigid food packaging trays and yoghurt pots etc., which is projected to
account for over 40% of demand for PLA in the EU in 2015. The oven-ready meal tray is a
target application, to replace crystalline polyethylene terephthalate (cPET).
PLA demand for injection moulded rigid packaging is projected at 16 thousand tons (kt).
On this basis, total demand for PLA for rigid packaging is forecast to be 91 kt or close to
50% of the market in 2015. A target application is the microwavable ready-made soup pot,
replacing PP.
Clear Film (including biaxially oriented “BOPLA” film) is projected to account for 18 kt PLA in
2015, mainly for wrapping fresh produce, convenience foods and short shelf-life items.
Co-Blended Biopolymer (CBP) film is a major market opportunity for PLA, projected to
consume over 18% of PLA in Europe in 2015. CBP utilises hard, rigid PLA to provide
stiffness and strength in a blend with soft, flexible starch polymer (TSP) or polyester (PBAT).
The main applications for CBP films are in the non-food area, including shrink-wrap for
secondary packaging, compostable waste bags and biodegradable shopping bags.
Fibre is expected to grow strongly from a small base, notably in carpet and textiles, as is
Paperboard Coating, with hot drinks cups as the main application.
3D Printing is only a nascent industry but with potential to grow substantially in the future.
PLA is one of the most suitable products to use as a print material on account that it sets
quickly and is resistant to warping.
The rigid packaging applications are expected to require formulated PLA. In the remaining
segments, customers buy polymer which they then formulate to produce film, CBP and
injection moulding compounds.
9
As a result of the presence of leading retailers and major packaging producers in this
sophisticated marketplace, the UK is expected to account for 10–20% of the EU total
consumption and there is an excellent opportunity for a UK plant to capture 20% of the EU
market.
Due to the chiral nature of lactic acid, several forms of PLA exist, each one having distinctive
characteristics, properties, potential market applications, and potential market demand and
price. PLA can be produced as homopolymers using single enantiomers of lactic acid i.e.
PLLA contains only L-lactic acid and PDLA contains only D-lactic acid. PLA can also be
produced as a random polymer of L and D lactic acid.
Specialised grades of PLA are currently produced in very small volumes and are generally
targeted at the high value biomedical engineering sector. Most of the PLA currently available
on the market is produced by Natureworks at its Blair Nebraska plant, and can be
characterised as first generation PLA.
First Generation PLA is a random copolymer of LLA with typically 3–6% DLA, which for
practical purposes does not crystallise. As this type of PLA is practically amorphous, it has
properties typical of an amorphous material: glassy, brittle, etc. Fibre and film (biaxial
oriented poly(lactic acid)) based on drawing and stretching, are natural applications for this
material. First general PLA is, however, limited in its application areas.
Second Generation PLA is PLLA, which provides improved properties when used alone or
in blends with minor amounts of PDLA to form stereo complex-PLA. PDLA and PLLA form a
highly regular stereocomplex with increased crystallinity, melting temperatures and heat
deflection temperature which can be increased by physically blending PLLA with low
concentrations of 3–10% of PDLA.
Third Generation PLA is stereo complex-PLA based on blends of equal quantities of PLLA
and PDLA. With 50:50 blends the temperature stability is maximised, providing superior
10
polymer properties. Commercialisation of these products on a large scale would depend on
development of the market and large scale production of DLA.
All PLA produced by Natureworks is shipped in the form of beads (pellets) to customers
which convert the beads into film, sheet, fibre, injection mouldings, etc. In this respect,
Natureworks and PLA are typical of the plastics industry, whereby resin (polymer) producers
do not produce rods or sheets, as this is their customer’s business.
The characteristics of PLA and potential for developing new PLA grades are key to
understanding the market potential for PLA. These are described in detail in Appendix 2. The
polymer is biorenewable, offers high tensile strength and low density, is biodegradable,
demonstrates compostability in accordance with EN13432 and is easily embossed (or
printed onto). PLA also offers attractive end-of-life options when considered against the
‘waste hierarchy’ introduced by the EU Waste Framework Directive 8. Many waste PLA
streams can be readily processed through mechanical and chemical recycling. Meanwhile,
PLA film and fibre that is not easily recycled can be composted in accordance with EN13432
or can be converted to renewable energy by straight combustion, gasification or pyrolysis.
Second generation PLA has the properties required to replace oil-based plastics such as
polypropylene (PP) and polyethylene terephthalate (PET) in high value packaging
applications. Growth of demand for second generation PLA as a replacement for oil-based
plastics will be driven by PLA’s combination of 100% bio-based content and its unique
functionality.
Market discussions in the UK and EU confirm strong interest in PLA with improved
functionality – especially high temperature resistance properties offered by 2G and 3G PLA
– and that would be available in commercial quantities from an EU (non-GM) source, as a
replacement for oil-based plastics.
There are approximately 25 companies worldwide involved with the production and sales of
PLA. An overview of some of the major players in the industry is shown in Table 3, indicating
existing assets and interest in technologies that utilise lignocellulosic feedstocks.
8
European Commission. 2008. Directive 2008/98/EC. Waste Framework Directive.
11
There are also a number of other companies involved in the manufacture of the upstream LA
for both food and industrial markets. These include Archer Daniels Midland, Galactic and
several Chinese companies such as B&G and CCA Biochemical Company.
NatureWorks is by far the largest manufacturer of PLA in the world, with its commercial
facility in Nebraska, USA responsible for around 75% of global capacity. However, many
PLA pilot and demonstration plants have been, or are being, developed around Europe. This
includes Plaxica’s and TMO’s facilities in the UK.
Cellulac has made notable progress with the development of LA from non-food sources such
as straw, spent brewer’s grains, DDGS and lactose. Corbion-purac and Plaxica have also
demonstrated an ambition to optimise processes for utilising cellulosic feedstocks.
12
Company Existing assets Interest in lignocellulosic
technologies
Myriant • Developed technology to produce
optically pure DLA and LLA using a
one-step biosynthetic process that has
been licensed to Purac
NatureWorks • Produces a range of Ingeo™ PLA • Ambitions to develop Ingeo process
grades from plant sugars using to use cellulosic sugars in future
fermentation for LA synthesis
• Operating a140,000 tpa capacity PLA
plant in Nebraska, USA and planning a
new facility in Thailand
TMO Renewables • Patented bacterial (Geobacillus) • Experience in engineering bacteria
platform that converts sugars into LA for fermentation of cellulosic sugars
• Upgrading a demonstration unit in and ambition to produce PLA from
Guildford, UK to produce 3,000 tpa non-food feedstocks
non-GM PLA
2.5 Summary
Significant growth is expected in both the global and EU PLA market in the near future with
new varieties of PLA with improved properties undergoing development. This can be
expected to increase the number of available applications of the polymer, and thus the
overall PLA market, while also creating further opportunities for developing improved value
chains. Meanwhile, the growing importance for brand owners of applying sustainable
practices in product development can be expected to further increase the attractiveness of
utilising PLA over functionally similar fossil-based plastics.
The consequence is that there is a projected gap in supply and demand of PLA and in the
EU, indicating a promising investment landscape for a LA plant in the UK. Previous efforts
have demonstrated the viability of such a plant, utilising starch as feedstock (Reineck, 2008)
The UK grain milling industry is well established in the UK, with the flour milling sector alone
consisting of over 30 companies – operating around 50 sites – with a combined annual
turnover of around £1 billion 9. The principle product of the industry is flour, utilised for food
markets. However, the milling process often results in a wide variety of by-products/residues
9
http://www.nabim.org.uk/content/1/36/the-flour-milling-industry.html
13
that, while often used in low value markets, may also be used as a source of cellulosic sugar
in industrial applications.
The milling industry uses a variety of different milling technologies that can broadly be split
into two different processes: wet milling and dry milling.
Wet milling
Wet milling is the traditional process used for production of starch from wheat (or maize).
Wet milling involves steeping the grain in water to soften the seed kernel followed by
grinding and separation of the starch, gluten and fibre by filtration. Wet milling for starch
production generates large quantities of co-products – primarily fibre (bran), sugar syrup
(sweeteners) and gluten protein (germ) – the revenues of which are often critical to the
economic viability of starch mills.
Dry milling
In the dry milling process, the entire grain is ground into a fine powder, known as meal,
before being slurried through the addition of water.
Dry milling is a less versatile process than wet milling and results in the production of a lower
amount of by-products. However, the process is frequently used in modern grain ethanol
refineries where whole grain is milled before fermenting to ethanol as it results in higher
efficiency with lower capital and operational costs. This process can be adjusted so that LA
is the fermentation product instead of ethanol. The single by-product of an ethanol dry mill is
distillers’ dried grains with solubles (DDGS) which is typically sold as a high protein animal
feed.
A variety of different technology options for milling also exist, including hammer milling, roller
milling and pearling.
• Hammer milling is used in grains with low husk content. Hammer milling operates
via grinding and friction, and is supported by a sieving device, that separates the
product from the recycling stream. The process is capable of either wet or dry
grinding.
14
• Roller milling is often used when grain has high bran content 10. This process is
typically used for flour production and results in the production of various side-
product streams. In a typical dry mill, 70–80% of product is flour, with the remaining
20–30% consisting of bran, germ and a mixed stream of bran/flour/germ
(middlings) 11.
In addition to the various different processing options used by millers, a variety of different
grains are also utilised. Three different cereal grains are commonly milled in the UK: wheat,
oats and barley.
3.2 Wheat
UK production
Wheat is by far the most abundant cereal crop in the UK with yearly production volumes
often exceeding 15 million tonnes. However, annual fluctuations in crop yield can often be
large on account of weather conditions. For instance, 2012 crop yields were almost 15%
lower than in 2011 due to extended periods of wet weather early in the year (Figure 4).This
also had a negative impact on grain quality with 152,000 tonnes of wheat grain classed as
‘out of specification’ or supplied to ethanol and starch producers in 2012 (DEFRA, 2013).
10
The ethanol textbook. Chapter 2. D.R. Kelsall and T.P. Lyons
11
http://www.nabim.org.uk/content/1/60/flour-production---consumption.html
15
20000 9
Harvest (x1000 Tonnes per year)
Broadly speaking, wheat grain can be split into two different varieties: milling wheat and feed
wheat.
Milling wheat is high in protein e.g. >13% dry matter and is most frequently used for making
bread flour in the UK. Approximately 6 million tonnes of milling wheat is processed by the UK
milling industry every year.
Feed wheat is a low grade wheat variety that is most often used as animal feed. The grain is
also used as a feedstock for ethanol production in the UK. Feed wheat is not regularly milled
on account of its lower protein content.
Products
Flour
Flour is the principle product of wheat grain milling and contains the wheat endosperm.
Approximately five million tonnes of flour is produced in the UK on an annual basis with the
majority (around 80%) used in the food market for production of breads, cakes and other
baked goods (Table 4). The remainder is used in industrial applications for production of
starch and ethanol.
12
FAOSTAT
16
Table 4. Annual production of wheat flour in the UK 13,14
Starch
Wheat starch can be produced either directly via wet milling or from flour through dry milling.
The process of starch production from wheat flour is presented in Figure 5.
13
https://www.gov.uk/government/publications/cereal-usage
14
https://www.gov.uk/government/publications/animal-feed-production
17
There are three varieties of starch produced in the flour making process: slurry, dry powder,
and glucose syrup:
1. Starch slurry has only 30% starch content and is the poorest quality grade. On
account of its low purity, it is expensive to store and transport.
2. Dry starch is that which is most frequently manufactured and usually contains around
90% starch content.
3. Glucose syrup is a niche product that is produced via starch hydrolysis. It requires
further saccharification steps (breaking the polymer down into smaller units) as well
as concentration (removal of water).
Total consumption of starch in the EU was estimated at 10 million tonnes in 2011 15. From
the total volume consumed, 57% was used as a starch based sweetener in food
applications, 23% as native starch and 20% as modified starch. By far the largest non-food
application in the EU is within paper, board and corrugating industries, although the use of
starch and starch derivatives for production of biopolymers like PLA is gaining interest.
While well-established markets for starch already exist in the EU, bio-based polymers offer
large potential for developing improved value chains. However, utilisation of starch for
production of LA in the UK has previously been assessed in Reineck (2008) and is therefore
not considered any further in this study.
Residues
Wheat bran
Wheat germ
Wheat germ accounts for approximately 3% of the wheat grain and contains starch, proteins,
vitamins and oils (Reineck, 2008). Germ is often mixed with bran during pearling and used in
15
http://www.aaf-eu.org/european-starch-industry/
16
http://www.hgca.com/publications/documents/cropresearch/PR425_Final_Project_Report.pdf
18
wholegrain bread production. The product is rather expensive at a selling price of around
£560 per tonne, largely on account of its high protein content.
Wheat middlings
Wheat middlings are a by-product of the milling process and consist of a mixed stream of
milling wheat residues composed of roughly 60% wheat bran, 25% wheat milling residues,
and 15% screenings (figures sourced from personal communication with an industry
representative). Middlings are a low value product with a selling price of approximately £142
per tonne. More than 800,000 tonnes are produced annually in the UK, most of which is
used as an animal feed additive.
3.3 Oats
UK production
Oat grains are highly nutritious, containing a very high protein and lipid content. The grain is
typically used in porridge and muesli cereals, although it can also be ground into flour for
production of oat bread, cakes and biscuits. A minor fraction is also used in cosmetics
manufacturing. Production of oats in the UK is low in comparison to wheat, with annual
yields usually between 600,000 and 800,000 tonnes (Figure 6).
17
https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/263471/cerealuse-statsnotice-
05dec13.pdf
18
https://www.gov.uk/government/publications/animal-feed-production
19
2000 7
Harvest (x1000 Tonnes per year)
Products
Oat flakes are the predominant product of oat milling in the UK. Cleaned groats, produced
from de-hulling of the raw oat grain, are processed to produce flakes using large rollers.
Flakes are less refined than flours and consist of the endosperm, germ and bran of the oat.
Oat flakes are regularly used in food applications, notably breakfast cereals such as
porridge, muesli and granola. Annual production in the UK is approximately 200,000 tonnes
every year (Table 6).
Oat flour
Oat flour can be produced by de-branning of cleaned groats. The flour itself is usually free of
bran, containing just the endosperm of the oat. Oat flour can be used in similar applications
to wheat flour although is differentiated by its absence of gluten. Oat flour can therefore be
marketed towards niche food markets such as gluten-free applications. Oat flour production
in the UK is relatively low at just under 100,000 tonnes per annum (Table 6).
19
FAOSTAT
20
Table 6. Annual production of oat products in the UK 20
Residues
Oat germ
Oat bran is a very nutritious milling co-product very rich in cellulose and hemicellulose. It is
produced via de-branning of oat grains during the production of oat flour. On account of the
low volumes of wheat flour produced in the UK, oat bran production is similarly low. Much
like wheat bran, oat bran is used in food and feed applications.
Oat husks/hulls
Oat grains contain an outer material known as the husk (or hull). It is a cellulosic material
rich in C6 and C5 sugars that comprises up to 40% of the grain by mass. During the milling
of oats, this outer layer is removed by the de-hulling process. The most common use for oat
husks is an animal feed. However, alternative uses include animal bedding, bioenergy (via
combustion) and biofuel production. An estimated 182,000 tonnes of oat husks are produced
in the UK every year.
21
Table 7. Annual production of oat milling by-products for 2012
20
https://www.gov.uk/government/publications/cereal-usage
21
https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/263471/cerealuse-statsnotice-
05dec13.pdf
21
3.4 Barley
Barley is a typical monocotyledon grass species widely cultivated in the UK for its grain.
Around 5 million tonnes of barley is grown in the UK every year, much of which is used
either by the brewing industry for production of beer or as an animal feed. While barley is
regularly milled as part of the brewing process, it is not milled for flour production; as a
consequence there are no milling residues produced from barley in the UK, aside from post-
distillation by-products. On account of this fact, barley is not considered further in this study.
3.5 Summary
Grain milling is a mature industry in the UK although margins are often small. Consequently,
the value of by-products is often an important factor in ensuring economic viability. However,
these residues often serve low value markets such as animal feed. Therefore, any
opportunity to increase profitability by adding value to by-products can be expected to be an
attractive prospect to the grain milling industry.
There are several milling by-products produced in significant volumes in the UK, namely
wheat bran/middlings, wheat germ, oat bran and oat husks/hulls, where availability could
potentially be sufficient to provide feedstock for large-scale industrial applications such as LA
production (Table 8).
22
Table 8. Annual production of cereal milling by-products for 2012
Annual production
(‘000 tonnes)
Wheat milled 6,305
Bran 946
Germ 189
Oat milled 474.6
Bran 86.9
Germ 8.7
Husks/hulls 182.2
Barley milled 0
22
https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/263471/cerealuse-statsnotice-
05dec13.pdf
22
4. Lactic acid production from milling residues
4.1 Utilisation of milling co-products for chemical production
Over recent years, interest in developing chemicals and fuels from cereal crop residues has
increased substantially. However, commercial operations have largely been limited to the
production of bioethanol from crop harvest residues (e.g. stover, straw etc.) in respect of
biofuel mandates in the EU and US and the relative availability of these feedstocks.
For instance, several cellulosic ethanol biorefineries utilising corn stover (leaves, stalks and
empty cobs of maize) as feedstock are nearing completion in the US; Du Pont are
developing a 30 million gallon plant in Nevada, Iowa 23 while Poet-DSM are constructing a
25 million gallon facility in Emmetsburg, Iowa 24. Abegoa and Quad County Corn are also in
the process of developing similar facilities. More advanced biorefineries can be expected to
come online in the near future in the US as the nation aims to meet its cellulosic biofuel
target under the Renewable Fuel Standard (RFS) of 16 billion gallons by 2022. Meanwhile,
Beta Renewables has constructed Europe’s first commercial advanced bioethanol plant in
Crescentino, Italy, with 3 further cellulosic refineries to follow. The Crescentino facility
produces approximately 40,000 tonnes of bioethanol per year employing wheat straw, rice
straw and arundo donax as feedstock– a fast growing lignocellulosic crop 25. The
development of EU legislation to provide greater support to advanced biofuels can be
expected to stimulate further deployment of such facilities in the future.
To date utilisation of grain milling by-products for production of renewable fuels and
chemicals remains largely in the research & development stage, although interest is growing
as potential opportunities for developing cereal-based biorefineries become established (10;
11). Such facilities could enable the production of a range of different valuable product
streams, utilising all the various chemical components of the biomass, including
lignocellulosic materials.
Latterly, significant efforts have been made to assess the potential for processing wheat
bran into platform chemicals. A strategy for the production and valorisation of succinic acid
from whole-crop wheat biorefining has recently been developed. The strategy outlines a
comprehensive processing pathway involving front-end milling, enzyme hydrolysis and a
combination of different fermentation technologies (conventional fermentation for flour and
23
http://biofuels.dupont.com/fileadmin/user_upload/live/biofuels/Feedstock_Program_2014.pdf
24
http://poet.com/cellulosic
25
http://www.betarenewables.com/press-release-detail/2/crescentinos-biorefinery-grand-opening
23
solid-state fermentation for wheat bran/middlings) (Lin et al.,2011). However, the commercial
feasibility of such an approach would still require verification. Further efforts have focused on
the potential to use wheat bran as a substrate for ethanol production (Palmarola-Adrados et
al., 2005; Okamoto et al., 2011). One study demonstrated efficient enzymatic hydrolysis of
non-starch carbohydrates following dilute acid pretreatment, with sugar production as high
as 80% of the theoretical yield (Palmarola-Adrados et al., 2005). Meanwhile, a separate
study showed efficient ethanol production from direct fermentation of wheat bran using a
novel fungal strain, with yields as high as 78.8% of the theoretical yield (Okamoto et al.,
2013)
There has also been interest in utilising wheat bran for LA production. However, much of the
research has concentrated on using it as a nutrient source, rather than a carbon substrate
(Li et al., 2010; John et al., 2006). It has been demonstrated that use of acid-pretreated bran
as a nutrient source for LA fermentation can enable conversion efficiency close to theoretical
yields (Li et al.,2010). In using wheat bran over yeast extract, nutrient supplement cost was
calculated to be reduced by approximately 9-fold. Similar results were also found for use of
protease treated wheat bran as a nutrient source (John et al., 2006). In the event that wheat
bran is also used as a carbon substrate for LA production, this research demonstrates that
fewer nutrient sources would be required than for fermentation of many other substrates,
thus offering potential to reduce comparable operational costs.
Efforts have also focused on using wheat bran as a substrate for LA production. Efficient
fermentation of wheat bran starch to LA (0.78g LA per gram of starch in wheat bran) using
solid-state fermentation has previously been demonstrated (Naveena et al., 2004) with a
further study affording similar results (Naveena et al., 2003). While there is clear potential to
use wheat bran as a substrate for commercial LA production on account of its high
carbohydrate content, it is clear that more research would be required to optimise the
parameters and demonstrate commercial process feasibility.
Research has also been conducted into the potential for using oat residues as a feedstock
for producing renewable platform chemicals. One study has assessed a range of different
pretreatment options for production of fermentable sugars from oat hulls with a view to
produce cellulosic ethanol (Perruzza, 2010). The study demonstrated that high xylose yields
(85% of theoretical) and glucose yields (89% of theoretical) could be achieved from
hydrolysis of oat hulls using ‘disc refining’ and ‘mercerisation’ pretreatments. It was further
shown that incorporation of a solid-liquid separation step was effective at removing
fermentation inhibitors and improved ethanol yields.
24
Finally, research has been conducted on the potential of lactic acid bacteria to ferment
sugars present in oat bran (Kontula et al., 1998). While two of the three strains assessed
were only capable of fermenting polymers containing C6 sugars, a Lactobacillus strain was
shown to be capable of fermenting both the C6- and C5-containg carbohydrates present in
oat bran.
Ultimately, little commercially oriented work has been done to date regarding the potential for
using cereal milling by-products for LA production. However, clear progress has been made
in commercialising technologies for LA production from cellulosic feedstocks, with Corbion-
Purac, Cellulac, Plaxica and Natureworks all attempting to scale production processes.
Cellulac’s proposed facility could be of notable relevance to this project on account that it
plans to utilise spent brewers grain from a distillery effluent, which can be expected to be of
similar chemical composition to milling by-products (although higher levels of lignin can be
expected).
4.2 Process overview for the production of lactic acid from cereal
residues
LA production from cereal residues would most likely include the following steps: 1)
advanced pretreatment of grain fractions; 2) saccharification of carbohydrates to fermentable
sugars; 3) fermentation of fermentable sugars to lactate salts; 4) acidification of lactate to
LA; 5) purification of LA; and 6) concentration of LA formulations. The purpose of each
process is described in Table 9.
The pathway described is regarded as the most commercially attractive process for the
production of LA from cereal residues, although alternative pathways do exist, e.g. via
chemical conversion (as developed by Plaxica).
Table 9. Processes for lactic acid production from cereal residues (modified from Reineck
(2008))
Process Purpose
Pretreatment/liquefaction Thermal- and/or chemical-assisted modification of cereal grain structures
and carbohydrate-rich pockets
Saccharification Solubilisation and extraction of fermentable sugars from carbohydrate
polymers
Fermentation Microbial conversion of fermentable sugars to LA, addition of neutralising
agent to maintain pH in fermentor, and make lactate salts
Acidification Convert lactate salts to LA
Purification Separation of cells and nutrients, and residual sugars, to obtain LA
25
solution that needs purity requirements
Concentration Removal of water from LA solution to achieve required concentration
Pretreatment
The pretreatment step facilitates disruption of the cellulosic fibres to enable downstream
processing of the bound sugars. A wide variety of different pretreatment technologies exist,
although, frequently, the process will involve cooking the biomass in water at elevated
temperature and pressure (either with or without use of chemical agents).
Cellulosic raw materials often have specific requirements that have to be achieved before
pretreatments can be effective; depending on the chemical and structural composition of the
material. Cellulose tends to be more recalcitrant to physical, thermochemical and biological
pretreatment methods than starch-rich materials. For instance, arabinoxylans can be
solubilised and extracted by medium temperature water cooking, while cellulose requires
cooking in temperatures as high as 195°C and the use of harsh chemicals.
Consequently, the pretreatment technology of choice would depend upon the chemical and
structural composition of the milling residue.
Saccharification
After pretreatment, the sugars are mainly in the form of oligomers (shorter chain length
polymers) and therefore require further processing to form monomeric, fermentable sugars.
This process is known as saccharification and there are a wide variety of enzyme catalysts
tailored for this purpose. Saccharification is usually performed at temperatures in the 40–
80 °C range, and it is often combined with the subsequent fermentation stage.
LA fermentation
26
The technology behind LA fermentation from glucose is mature at commercial scales.
Globally, 95% of LA production is produced through fermentation using LA-producing
bacteria (LAB) such as Lactobacillus spp., a process used for centuries to produce yogurt.
Other bacteria and yeast can also be used to convert fermentable sugars to LA.
Fermentable sugars traditionally originate from materials such as sugar cane, wheat, corn,
or potato that have a high content of C6-sugars. However, new routes have been developed
utilising lignocellulosic biomass for the production of fermentable sugars. The carbohydrate
content of this ‘biomass’ generally contains:
There is a broad range of LAB strains that convert either C6 or C5 sugars (or both) into LA.
Known species include Lactobacillus, Bacillus, and Rhizopus spp. Strain selection depends
on many parameters including productivity, product yield, by-product formation, operating
temperature and pH, co-production of enzyme for starch saccharification and chiral purity.
A crucial parameter for LA fermentation is the composition of the fermentable sugars. This is
because a different set of reactions occur in the production of LA, depending on whether it is
C6 or C5 sugars being fermented. While C6 sugars are converted to LA entirely, with no co-
products, fermentation of C5 sugars results in the production of LA and acetic acid in a 3:2
stoichiometric ratio. Consequently, fermentation of sugars from lignocellulosic biomass will
result in a poorer LA yield than use of starch feedstock on account of its higher C5 sugar
content. However, the additional acetic acid produced can be utilised to develop further
valuable co-products that can be sold to improve the viability of the process.
Acidification
LA fermentation products are typically in lactate salt form, which needs to be converted to LA
via acidification. Acidification requires strong acids with (in the case of sulphuric acid)
gypsum being produced as the by-product which can be used as a fertiliser or component of
plaster.
Purification
Purification is one of the most expensive processes in LA production and therefore impacts
strongly on overall process viability. It is a multi-step process which involves removal of
27
microorganism cells and chemical impurities. In order to avoid excessively high purification
costs, addition of chemicals in upstream processing needs to be very selective.
In the initial stage of the process, microbial cells are removed from the product mix using
filtration or flocculation, depending on the size of the cells. LA solvent extraction or distillation
is then used to purify the product. LA can be purified further by use of activated carbon, and
ion-exchange resins. Other purification strategies include electrodialysis or purification via
intermediate ester formation.
Concentration
4.3 Summary
All cereal milling residues contain high levels of fermentable sugars that may feasibly be
converted to lactic acid (LA). However, these sugars are predominantly found in complex
polymer structures (cellulose, arabinoxylans, β-glucans etc.) and thus require intensive
processing over and above what is needed for starch-based feedstocks. The decomposition
of carbohydrate polymers prior to fermentation is generally performed through pretreatment
and saccharification. These steps are essential in achieving LA production from cellulosic
sugars.
28
5. Feasibility assessment
5.1 Feedstock requirements
In Section 3 it was demonstrated that the UK grain milling industry produces a range of by-
products, namely wheat bran, wheat germ, oat bran and oat husks/hulls, that could
potentially be utilised as feedstock for a lactic acid (LA) plant. Other potential feedstocks
produced from the grain industry also exist, such as starch and out-of-specification grains.
However, starch was discounted from further analysis on account that PLA production from
this feedstock has already been undertaken (Reineck, 2008). Meanwhile, production of out-
of specification grains is highly weather-dependent, with wet weather usually producing a
poorer quality harvest. This annual variability is expected to introduce too much uncertainty
into supply chain security and therefore, out-of-specification grains were also discounted
from further evaluation 26.
In order to determine the feasibility of using UK cereal milling by-products as feedstock for a
LA plant, it is essential to establish feedstock volumes required for development of a facility
of viable scale. It has previously been demonstrated that a 30,000 tpa PLA plant in the UK is
of appropriate scale for economic viability (Reineck, 2008). We have therefore provided
estimates in this study based upon a LA plant capable of supplying a 30,000 tpa PLA plant
(i.e. 37,500 tpa LA plant).
To determine required feedstock volumes, the amount of fermentable sugar in each milling
by-product was determined (Table 11) and conversion rates for the process outlined in
section 4.2 , established 27.
26
It should be noted that therein lies potential to use out-of-specification grains as an alternative to existing
feedstock for a LA plant –however, this fact should not be used for justification of a business case on account of
the high level of risk involved.
27
Conversion factors:
1.1 gram glucose is theoretically yielded from hydrolysis of 1 gram starch/cellulose/β-glucan; glucose yield from
pretreatment/hydrolysis of starch/sugar of 100%; glucose yield from pretreatment/hydrolysis of cellulose/ β-
glucan of 80% for wheat residues (Palmarola-Adrados et al.,2005) and 89% for oat residues(Perruzza, 2010); 1
gram glucose yields 0.90 grams lactic acid (in literature: 0.74-0.99 gram lactic acid(Martinez et al., 2013))
1.136 gram xylose/arabinose is theoretically yielded from hydrolysis of 1 gram arabinoxylan; xylose/arabinose
yield from pretreatment/hydrolysis of arabinoxylan of 80% for wheat residues(Palmarola-Adrados et al., 2005)
and 84% for oat residues(Perruzza, 2010); 1 gram xylose/arabinose yields 0.61 gram of lactic acid and 0.41 gram
acetic acid (theoretically 0.682 gram lactic acid and 0.455g acetic acid)(Martinez et al.,2013; Taskila and Ojamo,
2013)
1.2511 gram of LA is needed to produce 1 gram PLA.
29
Table 10. Chemical composition of cereal milling residues
Wheat Oat
28 Husks/hulls
Bran Germ Bran
(Kamm et al.,
(Saunders and (Šramková et (Kamm et
2010; Perruzza,
Walker, 1968) al., 2009) al.,2010)
2010)
Cellulose, % 22 37 34
Arabinoxylan, % 27 46 33
β-glucan, % 10
Sugars, % 5 17
Starch, % 9 20
Non-sugars (proteins, fats, ash, lignin),
27 40 9 28
%
Moisture content, % 10 14 12 5
The selection of feedstock has a strong impact on the design and the size of the LA
production plant. As a rule of thumb, the higher the sugar content of the feedstock, and the
greater the ratio of C6 to C5 sugars, the smaller the fermentation capacity of the LA
production plant needs to be. It should be further considered that while LA product yield is
lower for C5 sugar fermentation, acetic acid is formed as a co-product which could be sold
as a platform chemical – or used to produce other valuable products streams – to generate
further revenues for the plant.
Of all cereal milling residues assessed, the greatest volumes of wheat germ would be
required to provide 37,500 tpa LA (Table 11), estimated at 84,200 tpa. This is largely on
account of the comparatively low carbohydrate content of wheat germ. This required volume
would represent almost half of total UK production, suggesting that use of this feedstock
would unlikely be feasible given the distributed nature of wheat milling in the UK and
consequential challenges in regards to transport logistics.
Meanwhile, 78,200 tonnes of wheat bran would be required to supply sufficient LA for a
30,000 tpa PLA plant, a figure close to that of wheat germ. However, almost 1 million tonnes
of wheat bran is produced in the UK every year. Wheat bran requirement would therefore
represent only 8% of UK production, suggesting that sufficient volumes of this feedstock
would be available to supply a UK LA plant.
28
Chemical composition of wheat middlings assumed to be equivalent to that of bran.
30
Slightly lower volumes of oat bran and oat hulls/husks would be required than wheat milling
by-products to supply a LA plant, with estimates at 73,000 tpa and 60,000 tpa, respectively
(Table 11). However, availability of oat bran is low with UK production at less than 90,000
tpa, suggesting that use of this feedstock would encounter logistical difficulties in supplying a
UK based world-scale LA plant. Availability of oat husks/hulls is higher at 182,000 tpa. A LA
plant based on oat husks/hulls would therefore require just over a third of UK production.
While this might appear ambitious, a representative from industry confirmed the existence of
at least one facility in the UK producing 60,000 tpa of husks/hulls from oat milling, a quantity
that alone is almost sufficient to supply a 37,500 tpa LA plant.
Table 11. Carbon mass balances for converting fermentable sugar constituents of cereal
milling residues to LA (results are given on an ‘as received’ basis)
For 30,000 Tonnes PLA production capacity, the plant requires as feedstock:
either 78,200 Tonnes milling wheat bran
or 84,200 Tonnes milling wheat germ
or 60,000 Tonnes milling oat bran
or 73,000 Tonnes milling oat husks/hulls
On account of these estimates of relative availabilities, wheat bran and oat husks/hulls can
be considered the most feasible milling by-products for use as feedstock for a UK LA plant.
Therefore, it is these that were taken forward for assessment of economic viability.
To determine the potential of developing effective values chain from conversion of cereal
milling residues to LA, an economic assessment of LA production from wheat bran, wheat
middlings and oat husks/hulls was undertaken, utilising a range of scenarios to account for
varying cost prices for each feedstock. Again, the analysis has assumed production of
37,500 tpa LA, sufficient to supply a 30,000 tpa PLA.
A full techno-economic analysis of each feedstock is outside the scope of this study. Instead,
the exercise concentrated on determining value added to feedstock, based on the buying
price of the feedstock and the selling price of the LA, to determine whether an attractive
value chain could be developed i.e. the analysis did not include feedstock logistics, capital
costs, other purchasing costs, manpower, or operational expenditure.
Selling price ranges for wheat and oat milling by-products (as gathered from literary
references and communication with industry representatives) are shown in Table 12.
31
Table 12. UK prices of cereal milling by-products
For the purpose of this analysis, it is assumed that LLA, rather than DLA, is manufactured by
the plant. This is because the technology production of LLA is more mature and,
consequently, the vast majority of LA available on the market is LLA (with pricings more
readily available).
In 2007, the price of LLA in the market ranged from $1.38/kg for 50% purity to $1.54/kg for
88% purity (£856–£955 per tonne) (Martinez et al.,2013). However, recent discussions with
industry indicate that current price for LLA to be between €1.30 and €2.30 per tonne
(£1005–£1860 per tonne) (figures from communication with an industry representative). For
the purpose of this study we used a mid-price estimate of £1400 per tonne LLA. Potential
sales of co-products of the LA production process, e.g. acetic acid derivatives, were not
included in the analysis.
When accounting for these price assumptions it is evident that effective value chains can be
developed from production of LLA from cereal milling residues; value added estimates for all
by-products ranged from £38 million for wheat bran under a high cost price scenario to £48.1
million for wheat bran under a low cost price scenario (Table 13).
Table 13. Value analysis of scenarios comparing purchasing costs of required feedstocks
per year with product revenues from sales of 37,500 tpa LLA
32
Low price Medium price High price
In the event that production pathways for DLA become better established, therein lies
potential for improving these value chains further. As discussed in Section 2, new varieties of
PLA containing high DLA content often demonstrate improved properties over conventional
PLA. A higher price can therefore be demanded for these new polymer varieties, and
likewise for the DLA itself; industry representatives suggest DLA could command a price of
between £3,000 and £4,000 per tonne. However, due to the nascence of the DLA market
there will inevitably be technical challenges involved in large-scale DLA manufacture, such
as the scaling-up of fermentation processes that involve engineered microbial strains.
Therefore, while the potential rewards of DLA production can be expected to be higher than
for LLA manufacture, the level of risk involved is higher as well.
This analysis demonstrates that therein lies potential for developing effective value chains in
the UK based on production of LA from cereal milling residues. However, it should be
reminded that the information provided in this analysis is alone insufficient to give
confirmation of feasibility. A wide range of other factors require further consideration, such
as transport logistics, capital and operational costs etc.
6. Conclusions
On account of climate change and oil price volatility concerns, current EU policies and
regulations strongly incentivise the development of bio-based alternatives to fossil materials,
chemicals and fuels. As a consequence, the market for biopolymers can be expected to
grow significantly in the near future, this includes PLA. New varieties of PLA with improved
properties (e.g. with high heat distortion temperatures) are undergoing development. This
can be expected to increase the number of available applications of the polymer, and thus
the overall PLA and LA markets, while also creating further opportunities for developing
improved value chains.
By analysing the technologies and production pathways needed for production of LA from
cereal residues, we found little prior research or activity in the utilisation of milling co-
products. However, we did establish several relevant technologies that would be suitable for
33
such processes and consequently demonstrated a theoretical processing pathway for
conversion of milling by-products to LA.
This study also demonstrated that there is good potential in the UK for developing value
chains based on production of LLA from cereal milling residues, notably wheat
bran/middlings and oat husks/hulls, in sufficient volumes to supply a 37,500 tpa LA plant
(equivalent to the feedstock requirement of a 30,000 tpa PLA). Most encouragingly, it was
discovered that a single oat milling facility exists in the UK which alone produces almost
sufficient residue volumes to supply a facility of this scale. Improvements upon the value
chains discussed here could be realised in the event that DLA is provided as the output to
the LA plant. However, this can be expected to increase the level of risk involved.
The main observations from the analyses are summarised in Table 14.
Table 14. Cumulative results scheme from feasibility analysis for production of PLA from
cereal milling residues in UK
Wheat Oat
Waste wheat Wheat Wheat Residual Oat
middlings husks/
milled grain bran germ starch bran
(wheatfeed) hulls
Abundance/
High High Low High Low Low High
availability
Total carbohydrate 80%
63% 47% 63% Up to 90% 83% 67%
content (wet basis) (endosperm)
Industrial Food/ Food/ Food/ Food/ Feed/
Competitive uses Feed
(periodic) feed feed industrial feed energy
Technological 1G/ 2G/ 1G/ 2G/ 2G/
2G/ 1G/
feasibility/ C6 C6+C5 C6+C5 C6+C5 C6+C5
C6+C5 Ferm C6 Ferm
maturity Fermentation Ferm Ferm Ferm Ferm
Economic
Good Good N/A Good Good N/A Good
competitiveness
Water content
(transportation/ 20% 10% 14% 10% Very low 12% 5%
storage)
Overall
Low High Low High Low Low High
attractiveness
Ultimately, this study demonstrates that there is a strong and growing market for LA, the
production pathways from cellulosic feedstocks are becoming commercialised and therein
lies potential to develop value chains from cereal milling residues in the UK. However, little
work has been done to date regarding the manufacture of LA from milling residues, and
34
therefore this opportunity can be expected to have significant risks, especially in regards to
technical feasibility without further research.
7. Further recommendations
The use of wheat bran or oat husks need further investigation to be verified as competitive
feedstocks for LA production in UK. First, further research and development is needed from
a scientific point of view to confirm: 1) practical suitability of the suggested processing
pathway for conversion of milling by-products to LA; 2) scalability of the processes through
experimental investigation from bench to pilot scale; and 3) LCA analysis of PLA production
from wheat bran and oat hulls/husks in UK. Moreover, system integration and a full techno-
economic analysis is also essential for further investigation for confirming feasibility (El
Mekawy et al.,2013; Kazi et al.,2010)
Other feedstocks that were out of scope for investigation in this report, but represent
promising feedstock for a UK LA plant, include rapeseed press cake, wheat straw, barley
straw, and rape straw (Martinez et al.,2013) These feedstocks are regarded as attractive
opportunities because they have high sugar content, are abundant and available at low cost
in the UK, are non-food residues and processing technologies are already available to
convert them to LA. It is therefore recommended that these feedstocks are also investigated
in the future due to their competitive value and characteristics.
35
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LA is chiral, existing as D- and L- optical isomers (enantiomers), termed DLA and LLA,
respectively. The L- enantiomer is produced by enzymes in animals and microorganisms,
such as yeasts, produce (racemic) mixtures of LLA and DLA. However, CORBION uses
proprietary microorganisms to produce LLA essentially free of DLA and can also produce
DLA essentially free of LLA.
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As described in the text, there are also three forms of PLA. Most of the PLA which is
commercially available currently is the polymer of L-/L- lactide and mesolactide.
Enantiomeric PLLA (the polymer of L-/L- lactide) and PDLA (the polymer of D-/D- lactide)
have been developed and are expected to be commercially available in the near future. The
molecular structure of PLA determines its properties as a thermoplastic.
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Appendix 2 – PLA characteristics and considerations
Physical Properties
Physical properties which are inherent to all grades of PLA are as follows:
Low density of 1.25 g/cm3 (meaning lower part weight compared to PET and PVC >1.35)
High tensile strength (meaning thickness can be reduced)
Stiffness (similar to polystyrene)
High transparency (haze of 2.1%, only slightly less transparent than PS or PET; although
not immediately visible, PLA has a marked yellow colouring and a slight milkiness)
High moisture vapour permeability (MVP) (an issue for most packages whose function is
to keep water out)
High permeability to gases
Biorenewability
Biodegradable in industrial composting or anaerobic digestion (but not home
compostable)
Low UV absorbance (meaning that package would not protect contents from certain
wavelengths of UV radiation)
Good printability (meaning excellent results can be obtained with various ink blends and
printing systems)
Easily embossable (which is of great interest for thermoformed sheet applications)
Excellent dead-fold (and twist effect ~ 25% better than that of Cellophane) (meaning it is
possible to produce transparent packages by folding PLA film or sheet, much as with
paperboard)
Good crease resistance (same as with Cellophane, but approx. 20% better than all other
films currently on the market)
Flavour and odour barrier (excellent resistance vis-à-vis most of the oils and fats found in
foodstuffs)
Heat sealability (processing temperature: 80° C, heat seal strength: > 0.13 bar) (however
this might be considered low versus processing temperatures for other filmic materials)
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For First Generation PLA:
Impact resistance of 20–25 J/m is far too low for engineering applications
Heat distortion temperature (HDT) of 50–55 ºC means poor resistance to heat which
shows up as deformation of items such as trays and cups during transport and use. Also,
lumping of pellets during transport, storage and processing has been an issue.
Gas barrier properties are an issue for many types of packaging (not only carbonated
drinks)
For Second Generation PLA (polymers are based on PLLA and PDLA as an additive):
For Third Generation PLA (polymers are sc-PLA based on 1:1 PLLA-PDLA blends, with
HDT = >180°C):
Target applications for sc-PLA would require HDT 80–160°C and Izod impact strength
up to 140 J/m, replacing standard and engineering plastics such as polyethylene
terephthalate (PET) and polycarbonate (PC)
Targeting these development markets will require plastics technology including alloys,
additives, fillers, compounds and nano-composites
PLA can be solid stated (similar to PET) to increase molecular weight and crystallinity: this is
done now in biomedical applications.
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NNFCC
NNFCC is a leading international consultancy with expertise on the conversion of
biomass to bioenergy, biofuels and bio-based products.
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