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PROSPECTUS

HANDBOOK OF
COMMERCIAL
BIO-BASED CHEMICALS

Furan
Dicarboxylic
SOME BIO-ROUTES TO
Acid CHEMICAL INTERMEDIATES
1,5-Pentanediamine

Levulinic Acid

Itaconic
Acid
1,6-hexanediol D-Glucose

Fumaric Succinic Acid


Acid
Pyruvic Acid
Malonic Acid

September 2016
HANDBOOK OF COMMERCIAL BIO-BASED CHEMICALS

INTRODUCTION
Tecnon OrbiChem has been producing monthly reports: “Bio-Materials
& Intermediates”, in the Chemical Business Focus series, since
September 2013. Each month we compile a profile on a particular
chemical, that can be produced by both conventional and metabolic
processes, comparing the different routes and commenting on the
potential commercial viability of the bio-processes. Each profile is
given the date of its compilation and readers should be aware that
there may have been developments since that date. Although current
low crude oil prices are delaying the time scale for the bio-processes
to become competitive, many companies with vision are preparing
for the days ahead when petroleum products return to their 2010-
2012 price levels, and penalties related to carbon emissions become
a serious burden on petro-products. This Handbook is a collection
of the Profiles that we have compiled over the past three years. We
hope it will serve the needs of people wishing to have an overview
of the progress towards a world where bio-based chemicals can
compete with and even supplant their petro-based homologues.

Some sample profiles now follow.....

2 Tecnon OrbiChem
HANDBOOK OF COMMERCIAL BIO-BASED CHEMICALS
CONTENTS of the handbook
Acetone
Acrylic acid
Adipic acid
BTX
Butadiene
1,4-Butanediol
n-Butanol
Epichlorohydrin
Ethylene
Ethylene oxide & MEG
Fatty acids
Fatty alcohols
Glycerol
5-HMF/FDCA
Hexamethylene diamine
Itaconic acid
Levulinic acid
Malonic acid
Methanol
Monoethyene glycol (MEG)
Monopropylene glycol (MPG)
1,5-Pentane diamine (PDA)
Polyamides
Polybutylene adipate terephthalate
Polybutylene succinate (PBS)
Polybutylene terephthalate (PBT)
Polycarbonate
Polyethylene
Polyethyene terephthalate (PET)
Polyhydroxyalkanoates (PHA)
Polylactic acid (PLA)
Polyols
Polystyrene
Polyurethanes
1,3-Propanediol
Propylene
PTA
Sebacic acid
Succinic acid

3 Tecnon OrbiChem
LEVULINIC ACID
Introduction

Levulinic acid (LVLA) is a non-toxic organic compound with the following formula:

It has two reactive functional groups, a carboxylic acid group and a keto group. It exists as a white
crystalline solid with a melting point of 33-35ºC. LVLA has been listed as one of the ‘Top Value Added
Chemicals From Biomass’ by the US Department of Energy (DOE) in 2004. The bifunctionality of the
keto and carboxylic acid groups makes levulinic acid a versatile chemical intermediate. It can also
be converted to many other useful chemical products such as solvents, pesticides, herbicides, polymer
resins, and cosmetics, and also to gasoline or diesel components.

Processing Technology

A significant amount of research has been conducted over the years to develop processes to manufacture
levulinic acid (LVLA) at a cost that is competitive with alternative synthetic materials. These efforts have
involved converting natural materials through the following five steps:

A. Breaking down biomass into lignin, cellulose and hemi-cellulose

B. Converting cellulose into glucose

C. Isomerising glucose to fructose

D. Converting fructose to 5-hydroxymethylfurfural (5-HMF)

E. Splitting 5-HMF into levulinic acid and formic acid

These steps are undertaken by chemical processes, not through the use of enzymes. The intermediates
are not isolated. Usually two or three of these steps are undertaken in a single process, and indeed in
some processes all five steps have been performed in a single reactor. In some test set-ups steps A and
B have been eliminated and the starting material used is a sugar, which is taken through steps C, D and
E. Figure 1 shows the chemical processes involved in steps C, D and E.

4 Tecnon OrbiChem
Figure 1

HO
HO
O
HO OH
OH
HO
O HO HO
HO HO
HO O O

Pyranose form Furanose form


Levulinic acid
Fructose
+
H
HO
O
O
HO O
Hydroxymethylfurfural
HO
HO
H
HO OH
Formic acid
O
Note: In solution fructose is
68% pyranose: 32% furanose
HO

Glucose

The use of a sugar entails an increase in cost that is not acceptable for a commercial process, however.
Consequently, the aim is to use low cost biomass, such as corncobs or sugar cane bagasse, or even
negative cost materials such as paper mill sludge. The first process to be used semi-commercially was
the Biofine Process, developed by chemical engineer Stephen Fitzpatrick in the 1990s, which reduces
the above five steps to a two-reactor process.

The Biofine process claims to convert essentially any ligno-cellulosic materials such as paper mill sludge,
municipal solid waste, paper and wood wastes, and agricultural residues to LVLA using high temperature
(150-220°C), dilute acid-catalysed hydrolysis in a continuous two-stage reactor system. In the first stage
biomass is converted to soluble sugar monomers, namely hexoses (mainly glucose) and pentoses, with
the hexoses immediately being converted to 5-hydroxymethyl-2-furfuraldehyde (5-HMF); in the second
stage the 5-HMF is further hydrolysed to levulinic acid. The first stage is very rapid, taking a mere 20
seconds, while the second stage takes only about 20 minutes. The conversion rate has been suggested
to be about 50% of the mass of 6-carbon sugars. Co-products include formic acid, furfural (coming
from the pentoses), and ligneous char. Formic acid is a valuable co-product and is mainly used as a
preservative and antibacterial agent in livestock feed as well as in the production of leather. Furfural is
used to make thermosetting resins among other uses.

The process has been developed and brought to a semi-commercial stage by the company Biofine
Technology LLC, initially with a mobile processing unit at Biofine’s demonstration plant in South Glens
Falls, New York, and later in a 1 ton of dry feedstock per day demonstration plant in Gorham, Maine,
USA. The process is said to be capable of using a wide range of types of biomass. In the case of
feedstock consisting of hard wood the yield per dry tonne is:

Levulinic acid 250 kg

Formic acid 100 kg

Furfural 125 kg (but variable according to market demand)

Ligneous char 525 kg (3% ash)

5 Tecnon OrbiChem
Formic acid and furfural are useful by-products, which have a market value. The ligneous char will
be used as in-plant fuel. More recently Biofine Technology’s interest has moved towards making ethyl
levulinate as a diesel fuel component, as the quickest route to a commercially viable product. The first
commercial plant is planned for New England, with an input capacity of 125 dry tons/day of waste
cardboard or forest products, producing 8.1 million gal/year of levulinate ester and formic acid.
CAPEX is expected to be $5.50 per annual gallon of liquid product (levulinic ester and formic acid),
while OPEX is estimated at $2.44/gal of liquid product.

Italian Green Future s.r.l. has been attempting to produce levulinic acid on a commercial scale in what
is claimed to be the world’s first commercial-scale plant in Caserta, Italy. According to Green Future,
the Caserta plant has an annual capacity of 8,500 tons. The production process uses glucose derived
from corn processing as feedstock. Glucose syrup is converted to levulinic acid and formic acid via
acid hydrolysis by boiling with dilute acid such as hydrochloric acid and sulphuric acid. Evidence
suggests that the Caserta plant was initially used as a demonstration site by Biofine Technology LLC to
produce LVLA from cellulose gleaned from local tobacco bagasse and paper mill sludge through the
Biofine Process, but major problems were encountered from clogging of the reactor by calcium salts
and humins deposition (tars). It is not clear that these problems have been overcome and the plant is
no longer in operation.

Segetis Inc. has been operating a pilot plant facility to produce levulinic acid in Golden Valley, Minnesota
since 2013, demonstrating the viability of its proprietary process to convert biomass to levulinic acid.
The pilot plant has a nameplate capacity of 80 metric tons/year and currently uses corn sugar as
feedstock, although the company says its process has broad capability and is intended to be used to
explore many other feedstocks as Segetis’s technology develops.

Segetis has been very active in the production and marketing of levulinic ketals. Prior to the start-up of its
own levulinc plant, Segetis had been sourcing levulinc acid from China to make ketals. Segetis produces
levulinic ketals using its highly selective process combining esters of levulinic acid with alcohols derived
from vegetable oils. The properties of levulinic ketals are modified and tailored through the R1 and R2
functionalities, allowing the compounds to be used alone or as a building block. Segetis currently has
a demonstration facility under toll manufacturing, which is capable of producing over 3m pounds/year
of levulinic ketals-based solvents and plasticizer products. Segetis also has a 250,000 lb/year pilot
plant that has been online since 2009 in Minneapolis that is used for process validation for its levulinic
ketals and derivatives. Segetis is planning for a commercial facility (most likely for levulinic ketals
and downstream derivatives) by around 2015/2016. The company’s portfolio of partners includes
Arkema, PolyOne, and Georgia Gulf in bio-based plasticizers, while DSM and SABIC are also Segetis
investors.

The companies mentioned above use dilute acid, usually hydrochloric acid, to promote the hydrolysis
reactions. However, there have been many studies on achieving higher conversions of cellulose
to levulinic acid by using other homogeneous catalysts (e.g. phosphoric acid), and also by using
heterogeneous catalysts. A heterogeneous catalyst that has been used by several research groups is
a macro-porous, cationic ion-exchange resin, such as Amberlyst 70, which has proved effective for
conversion of the water soluble sugars into HMF, levulinic acid and formic acid. Also the zeolite catalyst
ZSM-5 and the ionomer Nafion have been shown to give good results. Noble metal coordination
compounds have also been used as catalysts. A research group at Pisa University, Italy, has achieved
improved conversion of sugars to levulinic acid through the use of niobium phosphate. Heterogeneous
catalysts must be used with soluble sugars rather than cellulose, in order that the catalyst can be
recovered easily.

Pre-treatment of cellulose prior to thermal hydrolysis can improve yields. In the DIABNET programme,
coordinated by the University of Limerick, Eire, improved yields have been achieved by pre-treatment
of the cellulose with hydrogen peroxide, and also pre-treatment of cellulose with a commercial cellulase
enzyme mix has given better yields.

6 Tecnon OrbiChem
The maximum theoretical yield of levulinc acid obtainable from cellulose is 71.5%, and from hexoses is
64.5%. In practice yields are often less than half of this, and even under laboratory conditions yields
are rarely better than two-thirds. The main problem is the formation of black solids, called humins,
which cause clogging of the reactor. A number of commercial endeavours to produce levulinic acid
have been thwarted by the problem of build up humins in the reactor and also of tars formed by the
action of acid on the lignin.

Producers of Levulinic Acid

The production of levulinic acid has been almost entirely in the hands of small producers in China,
which has been the only significant source of product. Even Segetis has based its development work
on levulinic derivatives on imports of the acid from China. Companies in China that are producers are:

Jiangsu Yancheng China Flavor Chemicals Co.


Hebei Langfang Triple Well Chemicals Co. Ltd.
Shijiazhuang Pharmaceutical Group Ouyi Pharmaceutical Co Ltd.
Hebei Shijiazhuang Worldwide Furfural & Furfuryl Alcohol Funan Resin Co., Ltd
Tianjin Kailida Chemical

Total production in recent years is said to be around 3,000 tpa.

Biofine Technology LLC has a pilot plant in Old Town, Maine, which is currently operated for testing
feedstocks for process fine-tuning and yield confirmation. Levulinic acid capacity is around 250 kg/day
(90 tpa). Biofine had a plan for a commercial plant in New England to come on stream in Q4 2015
with a capacity to use 125 dry tpd waste cardboard, producing 8.1 million gal/year of levulinate ester
and formic acid, but there has been no recent news on this project.

Segetis Inc. has been operating a pilot plant facility to produce levulinic acid in Golden Valley, Minnesota
since 2013, used to optimise its proprietary process to convert biomass to levulinic acid. The pilot plant
has a nameplate capacity of 80 tpa. Segetis has been concentrating its research effort on levulinic
ketals, using a 250,000 lb/year pilot plant that has been online since 2009 in Minneapolis. Segetis
also has a demonstration facility, which is capable of producing over 3m pounds/year of levulinic
ketals-based solvents and plasticizer products. Segetis is planning to build a commercial facility (most
likely for levulinic ketals and downstream derivatives) by around 2015/2016.

Avantium has developed a tunable process to convert plant-based carbohydrates into high purity methyl
levulinate.

A potential producer of levulinic acid or levulinate esters in the USA is xF Technologies Inc. (formerly
Incitor, Inc.) based in Albuquerque, New Mexico. XF Technologies’ low-temperature chemical process
breaks down biomass to create chemicals and biofuel. XF Technologies appears to be concentrating
on the production of furaoate esters for fuel use at present.

In Italy, Green Future s.r.l. has been attempting to produce levulinic acid on a commercial scale since
2006 in what is claimed to be the world’s first commercial-scale plant in Caserta, Italy. According
to Green Future, the Caserta plant has an annual capacity of 8,500 tons. The plant has had many
operating problems and appears to be no longer in operation.

Market Fundamentals

Levulinc acid has a very small market for direct use. Levulinate salts like sodium levulinate are applied in
the cosmetics industry as preservative and skin conditioning agent, adding no colour or pH to products
like anti-aging creams. In the food industry levulinate salts are a known preservative of meats and

7 Tecnon OrbiChem
other foodstuffs, significantly reducing the growth of aerobic microorganisms. Calcium levulinate is a
pharmaceutical product used as a calcium supplement and food nutrition enhancer.

As a platform chemical, LVLA can be converted to a wide range of compounds that have the potential
to penetrate a number of large volume chemical markets.

Levulinate esters, mainly methyl-, ethyl- and butyl-levulinate have numerous potential applications. They
can be used as plasticisers for PVC, with use of the traditional phthalates becoming increasingly under
suspicion due to endocrine disruptor effects. Levulinate esters can be used as additives for diesel fuel
or gasoline. Levulinate esters can be made by esterification of levulinic acid with alcohols, using acid
catalysis, but better yields are obtained using solid catalysts such as zeolites or sulphated zirconia.
It is also possible to covert biomass or sugars directly to levulinate esters. Ethyl levulinate has been
proposed as a sustainable diesel fuel that is superior to fatty acid methyl esters (FAME). Levulinates
have lower cloud-point and a lower gel-point than FAME biodiesel, resulting in better general cold flow
properties. Levulinates have  greater miscibility with petrochemical fuels than either soy diesel or
ethanol.  Thus, unlike ethanol, mixtures of levulinate and gasoline can be pipelined instead of having
to be splash blended at the pump.

γ-Valerolactone (GVL) is produced by hydrogenation and dehydration of LVLA, aided by metal catalysts.
It is used as a perfume and food additive, giving a fresh fruit aroma. GVL is made by hydrogenation
and lactonisation of levulinic acid in a hydrogen atmosphere in presence of a heterogeneous noble
metal catalyst (e.g. Pd, Ni, Pt, Ru). By-products are also produced, namely angelica lactone and
2-methyltetrahydrofuran, as shown in the reaction scheme. It has been proposed to use formic acid
in the reactor mix as a source of hydrogen. GVL is used as a solvent for lacquers, insecticides and
adhesives, as shown in Figure 2. It has been proposed to use GVL, or valerate esters derived from it,
as sustainable liquids for energy storage and transportation fuel.

Figure 2

OH

OH

Reduction O
Dehydration
4-Hydroxypentanoic acid

O
O O
OH
Dehydration Reduction
O
Gamma-valerolactone
Levulinic acid Angelica lactone
Reduction

2-Methyltetrahydrofuran

8 Tecnon OrbiChem
α-Angelica lactone is a flavour chemical, used in oral care formulations to round out mint notes and in
coffee flavours.

Delta-amino levulinic acid (DALA) is a natural component of plants regulating the chlorophyll growth. It
can be used as a biodegradable herbicide with a large potential market if its production cost could be
reduced. DALA acts by accelerating the chlorophyll growth in plants to toxic levels, so it can be used as
a defoliant on plants prior to harvesting such as picking cotton and apples. DALA is applied in medical
applications as photosensitizing agents, for example in skin treatment for sunspots and is approved for
photodynamic therapy use for the treatment of skin cancer.

Diphenolic acid (DPA) or 4,4-bis-(4’-hydroxyphenyl)pentanoic acid is of particular interest as an


alternative to bisphenol A (BPA), which is used in polymers such as polycarbonates. The use of BPA
in plastics that come into contact with food is coming under increasing scrutiny, and indeed use of
polycarbonate resin has been prohibited for babies’ bottles. Substitution by DPA could permit the
manufacture of BPA-free polycarbonates.

MTHF (2-methyl tetrahydrofuran) is obtained through reduction of γ-valerolactone. Besides being


applicable as a fuel component, MTHF has attractive solvent properties. MTHF has a higher boiling
point and limited water miscibility compared to THF (tetrahydrofuran). These two attributes result in
higher reaction speeds, higher selectivity and better yields, making MTHF an attractive sustainable
alternative to THF as a solvent for use in chemical reactions.

Valeric Acid (Penatanoic Acid) can be obtained from conversion of levulinic acid. Valeric acid, usually
produced from valerian root extract, is a chemical intermediate applied in pharmaceuticals, fragrances,
aromas, plasticisers, crop protection and lubricants. 

Levulinic ketals based on levulinic acid esters have been developed by Segetis. These compounds are
claimed to have a wide range of applications such as non-toxic biodegradable solvents, phthalate-free
plasticizers and polyols for polyurethane foams. The solvent and plasticizer products are already being
sold on the market.

Other chemicals that can be made from levulinic acid include β-acetacrylic acid (used for new acrylate
polymers), 1,4-pentanediol (used for new polyesters), N-methyl pyrrolidone (NMP), and 2-methylindole-3-
acetic acid.

Derivatives that have potential for fuel use include methyl tetrahydrofuran (MTHF) and levulinate esters, which
can be used to address fuel markets as gasoline and biodiesel additives. These will, however, have to prove
competitive with ethanol production costs in order to penetrate the transportation fuel additive market.

Prices

According to Guangzhou CCM Chemicals, in 2008 the market price of LVLA was approximately
$3.50/kg. Today, levulinic acid supplied by Hebei Shijiazhuang Worldwide Furfural & Furfuryl Alcohol
Funan Resin Co., Ltd., is sold at Rmb38000/ton ($6180/ton) for orders above 100 tons on Alibaba.
Levulinic acid (99%), supplied by Tianjin Kailida Chemical, is sold at a similar price at Rmb33/kg
($5300/ton) for orders above 200 kg on Alibaba.

Research & Development

The production of levulinic acid from cellulose encounters problems from fouling of the equipment from
tars and humins. There is continuing effort to try to eliminate the hold-ups to production that result
from the need to stop the production process and clean the equipment. One approach is to produce
levulinate esters or levulinate ketals rather than levulinic acid, via processes that have a lower propensity
to build up of encrustations.

9 Tecnon OrbiChem
Many types of biomass have been tried as raw materials, often with success, but there is ongoing
research to identify suitable low cost or even negative cost organic materials, often discarded residues
from agricultural crops. Segetis is currently pursuing a number of paths to develop processes to convert
cost-effective feedstock such as woody biomass to levulinic acid.

An alternative approach is to use sugars rather than cellulose as the raw material, though clearly there
is an increase in cost which, it is hoped, will be mitigated by the absence of equipment fouling.

In a press release on 17 February, two companies in Italy, Bio-on SpA and Eridania Sadam SpA,
announced that they have agreed to work on a joint research programme to optimise the production
of levulinic acid. In this project, Bio-on will be researching new methods of producing levulinic acid on
an industrial scale. By-products of the sugar industry will be converted into levulinic acid, optimising
new innovative processes that are environmentally sustainable and cut down production costs. Eridania
Sadam plans to invest €1.8m in the joint venture.

US start-up company Reluceo/XL Terra, a spin-off from Segetis has developed a biomass-based polymer
called xylitol-levulinic polyester ketal (PXLK) as an alternative to polycarbonate and polymethacrylate.
PXLK is thermo-chemically produced by combining industrial grade xylitol and levulinic acid esters. It is
claimed to have superior tensile strength, heat deflection and thermostability characteristics compared
to existing bioplastics such as PLA and PHB. In addition, the increasing health concern regarding the
potential endocrine disruptor bisphenol A (BPA) and its recent ban on use in baby bottles by the FDA is
expected to make PXLK an attractive safe alternative.

PUBLISHED: 27TH FEBRUARY 2015

10 Tecnon OrbiChem
ADDENDUM TO THE PROFILE ON LEVULINIC ACID
The following information on levulinic acid has become available since publication of the February
issue of BioMaterials & Intermediates.

A New Company Aims for Commercial Production of Levulinic Acid

GFBiochemicals is the name of a new company whose first target is to start commercial production of
levulinic acid later this year. GFBiochemicals has assembled an experienced team of managers and
bio-engineers, some of whom have extensive prior experience of biomaterials production with DSM.
GFBiochemicals Group acquired Green Future s.r.l. in 2014.

According to a spokesman for GFBiochemicals, the company has retrofitted and adapted the existing
Green Future production facility in Caserta. The starting material will be corn-based biomass.
GFBiochemicals aims to switch to cellulosic biomass in 2016. GFBiochemicals has developed
a new process that is still based on catalysed thermo-chemical conversion of cellulose. However,
GFBiochemicals’ technology enables commercial-scale production of levulinic acid directly from biomass.
From the beginning, Green Future proposed and developed fundamentally different technology from
the original Biofine technology. GFBiochemicals’ new technology is significantly distanced from the
original process design. GFBiochemicals has retrofitted and adapted the existing production facility
and infrastructure in Caserta to test and demonstrate the new process and to produce levulinic acid
with its unique proprietary technology. The new technology will avoid the build-up of humins that
was one of the problems of the original plant at Caserta. Production was to begin in the summer of
2015. The commercial-scale plant has been retrofitted with new and modified conversion, recovery
and purification technology. Production capacity will initially be 2,000 tons per year of levulinic acid,
but the company aims to expand to the full capacity of the Caserta plant of 8 ktpa in due course.

Update on Levulinic Acid Capacity in China

There are four major levulinic acid producers in China, namely:

Langfang Triple Well Chemicals Co., Ltd.


Hebei Yanuo Chemical Industry Co., Ltd.
Shandong Zibo Shuangyu Chemical Co., Ltd.
Zibo Changlin Chemical Co., Ltd.

Chinese levulinic acid producers use the processing technology via furfuryl alcohol, either by outsourcing
furfuryl alcohol or producing furfuryl alcohol by themselves.  These producers have a similar capacity
for levulinic acid production of around 1,000 ton/year each, though their output is not fixed but
depends on the demand situation.  It is difficult to track the total output of levulinic acid in China, though
one market source mentions it may be less than 3,000 tons per year.

Current prices for levulinic acid in China are in a range of Rmb24,000– Rmb30,000/ton (99%
concentration), equivalent to $3275 – 4100/ton before VAT, with the high-end prices applying to
good quality material only.

It is understood that levulinic acid or levulinates applications in China have not yet been developed
very far.  The export market is quite important for some Chinese producers, who have regular overseas
customers. 

PUBLISHED: 30TH APRIL 2015

11 Tecnon OrbiChem
FURTHER ADDENDUM TO THE PROFILE ON LEVULINIC ACID
Levulinic acid updates: GFBiochemicals acquires Segetis

Italy-based levulinic acid producer, GFBiochemicals, announced this month that it has acquired all assets
and intellectual properties (IPs) of Minnesota, US-based levulinic acid derivatives producer, Segetis,
which will significantly expand GFBiochemicals’ levulinic acid applications portfolio.

Segetis is already producing and marketing levulinic ketals, a combination of levulinic acid esters and
alcohols derived from vegetable oils such as glycerol, under the brand JAVELIN™ for application such
as solvents and plasticisers. Segetis has a 113 tpa pilot plant in operation since 2009 in Golden Valley,
Minnesota, and has a 1.36 ktpa demonstration facility, which started in 2012 under toll manufacturing
also located in Minnesota. It was believed that Segetis has been sourcing its levulinic acid from China.

Segetis has been planning to build a commercial-scale plant in Hoyt Lakes, Minnesota, that would
produce levulinic acid and convert a portion of that output into plasticisers. The facility was expected
to have an annual levulinic acid capacity of 22 million lbs and 35 million lbs of plasticiser production
capacity.

Segetis’ portfolio of partners in developing bio-based plasticisers includes Arkema, PolyOne, and
Georgia Gulf. Its investors included DSM, Sabic, Malaysian Life Sciences Capital Fund, Khosla Ventures
and PNB Equity Resources Sdn Bhd.

Segetis is considered a premium levulinic acid derivatives producer with several proprietary applications
including fragrances, plasticisers for PVC & biopolymers, personal care, household & industrial
cleaners, agrochemicals formulations and coating/adhesive stripper industries – coming from years
of research and market development. GFBiochemicals said it will continue to look for further potential
acquisitions of levulinic acid’s derivative technologies, as well as creating high-value partnerships with
major companies.

GFBiochemicals’ acquisition of Segetis will bring unique know-how and expertise, including over
250 patents applications worldwide. The company has acquired Segetis’ production plant based in
Minnesota, and will establish a direct presence in the US market under GFBiochemicals Americas.

GFBiochemicals started operations of its levulinic acid plant located in Caserta, Italy, in July 2015 using
cornstarch feedstock for now, but plans to switch to wood waste feedstock this year. The company’s
facility uses thermochemical conversion to produce levulinic acid. Biomass pre-treatment involves acid
hydrolysis for the conversion into C5 and C6 sugars. Co-products include formic acid, furfural and
char although there will be significantly less furfural production with the use of wood waste feedstock.
For the moment, GFBiochemicals does not recover and purify formic acid but there will be plans to do
this and sell it into the market in the future. The char is currently being used for energy. The process
runs continuously with an overall yield of between 45% and 65%, although the company is aiming for
a yield of 70%.

12 Tecnon OrbiChem
Current levulinic acid production capacity for the Caserta facility is at 1.2 ktpa with plans to
gradually increase to its full 10 ktpa capacity by 2017. A world-scale 50 ktpa plant is already
under discussion and is expected by around 2019 if all goes well with this market. According
to GFBiochemicals, the target markets for levulinic acid as a bio-based building block will not
be affected as much by the volatility of crude oil pricing as most of its applications are in low-
volume, high-value products in a variety of specialty chemicals markets such as in flavours and
fragrances, pharmaceutical, household and personal care, solvents, fuel additives, lubricants,
polymer additives/intermediates, agrochemicals, etc.

The challenge is the need for further market developments as current use of levulinic acid is limited
due to low commercial availability and high prices. GFBiochemicals would need to develop
application partnerships as soon as possible as product developments can take two years or
more. The company’s initial focus will be on food and flavours, polymer, resins, and coatings. The
company’s strategy is to add value to high-end markets such as resins and coatings rather than go
into lower value commodity markets.

For example, diphenolic acid based on levulinic acid derivatives can be used as a replacement for
bisphenol-A in epoxy resins. Methyl butanediol derived from levulinic acid can reportedly improve
the durability of polyester coatings, while levulinic esters can replace solvents of concern like
dimethylformamide (DMF) and N-methylpyrrolidone (NMP) in coatings. Phthalate-free ketal plasticisers
are biodegradable and can be used in flexible PVC applications.

For consumer products, levulinic acid has extensive applications for flavours, fragrances
and cosmetics. It has a creamy, buttery whiskey odour which offers a range of options in
fragrances. The chemical is also used in food compositions for maple and caramel flavours.
Levulinic acid also acts as a pH regulator for both food and cosmetics, which means it can
replace acidity regulators like acetic acid. Levulinic acid is an alternative to benzoic acid
or sorbic acid in preservation systems and its antimicrobial properties are already used in
perfumes and skin conditioning.

13 Tecnon OrbiChem
It also demonstrates a range of property opportunities for short and middle chain length
polyhydroxyalkanoates (PHA). This could enable durable PHBV products for film, fibre, injection
moulding and extrusion applications. Such PHBV products have advantages compared to PHB
such as improved fermentation yield, enhanced toughness and elongation properties. A wider
processing window is also possible due to the lower melt temperature and crystallinity control
enabled by levulinic acid.

The company is offering a more sustainably-produced and a much lower levulinic acid price
compared to incumbent products currently manufactured mostly in China. The global market
volume for levulinic acid is currently estimated at around 2-3 ktpa. Levulinic acid prices for product
from China are estimated at around $4-5/kg. Industry analysts expect GFBiochemicals to achieve
a cost of between $1.10-1.60/kg at full capacity.

Companies involved in levulinic acid

Company Location Status


Langfang Triple Well Chemicals Co. Ltd China Producer
Hebei Yanuo Chemical Industry Co. Ltd China Producer
Shandong Zibo Shuangyu Chemical Co. Ltd China Producer
Zibo Changlin Chemical Co. Ltd China Producer
Arzeda USA R&D
Biofine Technology USA R&D (demo plant)
Glucan Biorenewables USA R&D on furfurals
Mercurius Biorefining USA R&D
Reluceo/XL Terra USA R&D (levulinic derivatives)
Segetis USA Derivatives producer
GFBiochemicals Italy Producer
Bio-on SpA/Eridania Sadam SpA Italy R&D
DIBANET Project Ireland R&D (pilot plant)
LIFE + WALEVA Spain R&D (pilot plant to start in 2016)
Source: Tecnon OrbiChem

14 Tecnon OrbiChem
The market opportunity for levulinic acid is estimated at $30 billion, which could be attained within 10
years with expanded commercial production. GFBiochemicals expects its first commercial shipments
from the Caserta facility to start in the first quarter of 2016 using industry standard shipping via 2-litre
drum packaging. The company has no revenue at this point but it expects to break even by the time it
increases its capacity to 4.5 ktpa next year.

GFBiochemicals has also started discussions for commercial expansion with potential partners,
citing Brazil and Southeast Asia as possible locations. CAPEX needed for a greenfield 10 ktpa
facility is around $80-200 million, which is reportedly a typical investment required for this type of
chemical production. GFBiochemicals’ Caserta facility is previously owned by Green Future S.r.l.,
which has been also developing its own levulinic acid process. GFBiochemicals fully acquired the
Caserta facility in 2014, which lowered its CAPEX costs despite the required overhauling of the
plant in order to install GFBiochemicals’ much improved production process. Start-up problems
were also not as challenging as might have been expected since the Caserta facility is originally
geared toward levulinic acid production.

In terms of business strategies down the road, GFBiochemicals is not averse to licensing its technology,
although the company prefers a partnership approach in terms of production and downstream
applications.

PUBLISHED: 29TH FEBRUARY 2016

15 Tecnon OrbiChem
ETHYLENE OXIDE AND MEG
Introduction

Ethylene oxide (EO) is a reactive chemical that is a precursor to a number of derivatives, the most
important of which is mono ethylene glycol (MEG). EO reaches final markets in the form of these
derivatives, with only a small proportion being used directly, for example as a fumigant in grain storage
or as a sterilisation agent. The chemical structure contains an oxirane ring, which is easily opened by
chemicals with active hydrogen atoms, leading to a reaction that is usually highly exothermic.

Ethylene oxide is made by the chemical oxidation of ethylene. Because ethylene oxide is so reactive this
can not be achieved by biological processes. However ethylene can be made by bio-based processes,
so the ethylene oxide made from bio-ethylene can be considered as partially sustainable. This will
then apply, in reduced measure, to chemicals made with such ethylene oxide. In the case of the main
derivative, mono-ethylene glycol, there are other bio-routes that do not pass through ethylene oxide as
an intermediate, and can be considered to have a higher level of sustainability.

Processing Technology

The first industrial process to make EO proceeded by hydrochlorination of ethylene to produce ethylene
chlorohydrin as an intermediate, which was not isolated, but converted to ethylene oxide by heating
with lime water.

H2C=CH2 + Cl2 + H2O → HOCH2CH2Cl + HCl

2 HOCH2CH2Cl + Ca(OH)2 → 2 + 2 H2O

This process suffered from the loss of chlorine, to the point that it became uneconomic and has been
abandoned.

16 Tecnon OrbiChem
Today, EO is made by the oxidation of ethylene. This can be done using air as the source of oxygen,
or else pure oxygen. In either case the catalyst used is based on silver. The main reaction is partial
oxidation of ethylene:

H2C=CH2 + ½ O2 →

But there are two subsidiary reactions, namely the complete combustion of ethylene and further oxidation
of EO:

H2C=CH2 + 3 O2 → 2 CO2 + 2 H2O

+ 2.5 O2 → 2 CO2 + 2 H2O

Industrial processes achieve a selectivity to ethylene of 65--75% with the air oxidation process and
70--80% with the oxygen oxidation process. Because of the mode of action of the silver catalyst the
maximum selectivity is 80%, so ultimately 20% of the ethylene is converted to carbon dioxide and lost
to the desired reaction. There have been many attempts to avoid this problem. No other catalyst other
than silver has proved successful. However, success has been achieved by adding rubidium or cesium
halides as co-catalysts, which alter the reaction mechanism, allowing selectivity of over 80% to be
achieved, with even 94% having been reported.

Because of the better conversion rates with the use of oxygen, this has become the main process used.
Typical reaction conditions are 10-20 bar and 250-300 oC.

Bio-based Processes to Make EO and MEG

Companies wishing to make bio-based EO must concentrate their activities in making ethylene from
renewable resources, since the conversion of ethylene to EO is inevitably an industrial chemical process.

Ethylene can be made sustainably by dehydrogenation of ethanol that has been roduced by a
fermentation process. This was one of the first ways of making ethylene, but it has been replaced in
industrial countries by the cracking of hydrocarbon feedstocks. However, dehydration of fermenatation
ethanol has continued to be used in developing countries with rich agriculature resources, such as
Brazil, India and China, and has been given a boost in recent years by the use of such bio-ethylene to
make MEG, which is then used to make PET resin of claimed 30% renewable content.

Ethanol is catalytically dehydrated to produce ethylene according to the following chemical reaction:

C2 H5OH ↔ C2 H4 + H2O

Traditionally the agent used for the dehydrogenation was sulphuric acid, but later solid catalysts were
developed, such as aluminium oxide or molecular sieves. The reaction is endothermic. Also the reaction
is reversible with the equilibrium being favoured by higher temperatures and hindered by higher
pressures and water vapour in the feed. As recovery of unconverted ethanol for recycle is energy and
capital intensive, reaction conditions enabling 99% + conversion of ethanol are usually preferred.

17 Tecnon OrbiChem
Production Process and Feedstock

The first step in bio-ethylene production is the creation of bio-ethanol from biomass feedstock. This is a
well known process as bio-ethanol is extensively used as a transportation fuel. Three types of biomass
can be used: sucrose, starchy biomass and lignocellulosic feedstock.

Sucrose, which can be derived from sugarcane, sugar beets and sweet sorghum, is relatively easy to
break down as sucrose is a disaccharide, which can be directly fermented into bio-ethanol by yeast.
Starchy biomass, such as wheat, corn and barley, contains cellulose polysaccharides (i.e. long chains
of D-glucose monomers), which must first be converted into a glucose syrup by either enzymatic or
acidic hydrolysis. Glucose is then fermented and distilled into bio-ethanol. Currently, most starch-based
bio-ethanol is produced in the United States, from corn (maize). Ligno-cellulosic biomass, such as
wood, straw, and grasses, consists mostly of three natural polymers: cellulose, hemicelluloses and lignin.
Ligno-cellulosic biomass forms the largest potential source of bio-ethanol because it is widespread and
largely available at low cost. It can also be grown as a perennial crop on low-quality land. However,
the conversion of ligno-cellulosic feedstock into bio-ethanol is difficult and costly. Lignin forms highly
branched structures that are strongly bound to cellulose and are hard to break down by microbial
systems. This makes the hydrolysis process and the final bio-ethanol relatively expensive.

Once bio-ethanol has been produced and purified to chemical grade, it is converted to bio-ethylene by
an alumina or zeolite (silica-alumina) catalyst. One ton of bio-ethylene requires 1.74 tons of (hydrated)
bio-ethanol. Conversion yields of 99% with 97% selectivity to ethylene are claimed. The reaction is
endothermic and requires a minimum theoretical energy use of 1.6 GJ per ton of bio-ethylene. While the
ethanol-to-ethylene (ETE) process is relatively simple, it is competitive only if the bio-ethanol is available
cheaply. The current production capacity is about 535 ktpa, of which 200 ktpa are used for producing
bio-PE, 60 ktpa to produce VCM/PVC and 275 ktpa for producing bio-based ethylene glycols (EG).

The bio-ethylene used to make EG is first converted to ethylene oxide (EO) by the industrial chemical
processes described earlier. The EO is not isolated, but is converted to EG on site.

EG results from the addition of water to EO, with the main product (90%) being mono-ethylene glycol,
but also 9% of diethylene glycol (DEG) and 1% of triethylene glycol (TEG) are formed.

+ H2O → HOCH2CH2OH → HO(CH2CH2 O)2 H → HO(CH2CH2O)2H


EO EO
MEG DEG TEG

Reaction conditions are normal pressure and 50--70 oC if an acidic catalyst is used (e.g. 1% H2SO4)
or 20—40 bar and 140--230 oC in absence of catalyst, the latter being preferred as subsequent
purification is simpler.

Recent developments are aimed at eliminating the co-production of DEG and TEG. This is achieved by
reacting EO with carbon dioxide to produce ethylene carbonate. This is then hydrolysed to produce
MEG with no DEG or TEG, together with the release of carbon dioxide. The yield approaches 100%.
The industrial process, developed by Shell, has been named OMEGA. However this process has not
been used with EO produced from bio-ethylene so far.

Other developments seek to eliminate the use of EO as an intermediate. The most successful has been
developed by Ube Industries, whereby methanol is carbonylated to dimethyl oxalate, which is then
hydrogenated and hydrolysed to MEG. The methanol is recovered and recycled, so essentially this is a
process to convert carbon monoxide to MEG. This process has been widely adopted in China, using

18 Tecnon OrbiChem
carbon monoxide derived from coal. However, there would be the possibility of generating the carbon
monoxide from biomass in future.

Producers of Bio-derived EO and MEG

Producers of bio-derived EG are the following:

Company Location Capacity(ktpa) Status


India Glycol India 125 In Operation
Greencol Taiwan Taiwan 130 In Operation
Global Biochem China 30 In Operation
Jilin Zhongxin Chemical Group China 90 Start-up Q4 2014
Jiaozuo Heyang Alcohol Industry China [90] Cancelled
M&G Chemicals China 200 Start-up in 2017
JBF Industries Brazil 500 Postponed
JBF Industries USA 150 Initial planning

Ethylene has been produced from ethanol on a small scale in India for decades. The main producer
today is India Glycols, which was the first company in the world to make ethylene oxide from ethanol,
using it to make a range of derivatives. India Glycols has been producing EG using ethylene derived
from bio-ethanol since 1989. The plant uses standard technology from Scientific Design, producing
MEG, DEG and TEG in the usual proportions. The MEG is of 99.5% purity and is used to produce
polyester fibres and PET resin. Also produced are ethoxylates and PEGs, performance chemicals,
glycol ethers and acetates. The feedstock used is molasses derived from sugar cane. The capacity to
make EG is 175 ktpa.

Greencol Taiwan Corporation (GTC) operates a plant to manufacture bio-monoethylene glycol (bio-
MEG) of 100 ktpa capacity at Kaohsiung, Taiwan since 2012. GTC is a 50:50 joint venture between
Nagoya-based Toyota Tsusho Corporation (TTC) and Taipei-based China Man-made Fiber Corporation.
Bio-MEG is used to produce PET on a tolling basis, which is marketed in Europe, Japan and the USA. The
plant uses Petron Scientific’s ethanol to bio-ethylene technology (see below). The bio-ethanol feedstock
is supplied by Petrobras, which signed a ten-year supply agreement with TTC in October 2010. Under
the agreement, Petrobras will supply 143,000m³ of ethanol annually. The supply agreement is worth
$820m.

Petrobras uses ethanol itself to make ethylene, but does not make MEG. Braskem inaugurated its bio-
ethylene plant in the Triunfo Petrochemical Complex in Rio Grande do Sul state in September 2010. The
plant uses ethanol produced from sugarcane as the feedstock. With the capacity to produce 200,000
tpa, Braskem claims that it is the first commercial-scale green ethylene plant in the world. The ethylene is
converted into equivalent polyethylene (PE) resin. Braskem invested approximately R$500m ($278m)
on the plant. The plant consumes about 462 million litres of ethanol annually to produce the resin. The
ethanol is initially being sourced from major Brazilian producers in the Minas Gerais, Paraná and São
Paulo states.

Global BioChem is the leading corn processor in China, producing amino acids and glycols from corn.
It is headquartered in Hong Kong and its production facilities are based in Changchun and Dehui
in Jilin province, China. The company was established in 1994 and listed on the Hong Kong Stock
Exchange in 2001. Production at the 200 ktpa glycols plant began in 2007. Capacity for bio-MEG
is 30 ktpa; it is being used to make polyester fibre and resin. Also made is bio-MPG, which is being
used in Unsaturated Polyester Resins, Heat Transfer Fluids, and solvent applications. It is believed that
this plant is not operating at present.

In 2010, Jilin Zhongxin Chemical Group Co. Ltd. (JZC) awarded a contract to Petron Scientech to build
a 90 ktpa ETE facility in Jilin, China, which will be integrated to a bio-EO production facility with a

19 Tecnon OrbiChem
capacity of 120 ktpa, and producing bio-MEG as a by-product. The facilities uses waste corn cobs for
feedstock in the production of bio-ethanol.

UK-based specialty chemicals company, Croda, announced early this year its plans to build a bio-
based ethylene oxide (EO) production facility near to its Atlas Point manufacturing site in New Castle,
Delaware, US. Some industry players in the surfactants market were distinctly puzzled, doubting
the ability of higher-priced EO from bioethanol to compete with petro-EO based on cheap ethylene
feedstock in the US. Croda did not disclose any capacity figures but noted that it will be small enough
to fulfil its surfactants requirements in the USA. The facility will use corn-based ethanol for feedstock that
will be delivered via railcars or tank trucks. It is expected to start operation by 2017. In an interview,
Croda confirmed that it will not produce any ethanol-based MEG at the facility. The project will provide
for on-site production of EO that will replace the company’s current purchases of EO. Croda pointed
out that it is getting harder and harder for EO consumers who are not near the Gulf Coast to source
EO supply via railcars because of the hazards associated with transporting it. A number of surfactants
players not vertically integrated with EO production have announced plans to move their surfactant
operations to the Gulf Coast where several EO producers have announced investment plans for new/
additional capacity led by cheaper shale gas-based ethylene feedstock.

There are a number of projects for bio-EO and bio-MEG which, however, may well be slowed down or
cancelled as a result of the recent fall in hydrocarbon and energy costs.

M&G Chemicals, a unit of Italy’s Gruppo Mossi & Ghisolfi, plans to build a $500 million biorefinery
in China to make ethanol and MEG from biomass. The facility in Fuyang, Anhui Province, China, is
being built in a joint venture, with M&G holding 70% and the Guozhen Group, a Chinese energy and
real estate conglomerate, holding 30%. The total joint venture investment is estimated to be around
US$325 million, and will be the largest cellulosic (i.e. using non food biomass) bio-refinery in the
world. The Fuyang refinery, which will use PROESA technology from Beta Renewables, will convert
970-1,300 ktpa of agricultural residues into cellulosic ethanol, glycols and by-products such as lignin.
The biomass will be supplied by Guozhen and the enzymes for the conversion of the biomass will be
supplied by Novozymes. Beta Renewables was established at the end of 2011 as a joint venture
between Biochemtex, a company of the Mossi Ghisolfi Group, and the U.S. fund TPG (Texas Pacific
Group) with a total investment of 250 million Euro (350 million dollars at that time); Novozymes later
became a shareholder.

The India-based producer JBF, working with US -based Cooper River Partners, has plans for a new
bio-PET facility to produce 438 ktpa of consumer grade PET , which is expected to consume around
151 ktpa of MEG that will also be produced at the site. The MEG facility will use sugarcane ethanol
as feedstock for an ETE unit. The MEG production will proceed via EO, some of which might go into
storage for subsequent shipment offsite. JBF had a bio-MEG project in Brazil but this has been dropped.

Another project in China that planned to use Petron Scientech’s ETE technology is a 90 ktpa bio-EO /
MEG plant announced by Jiaozuo Heyang Alcohol Industry Co. Ltd. in 2010. The company is engaged
in the production of food-grade ethanol. However, the ETE and EGs project has been cancelled.

Technology Providers

US -based engineering, licensing and processing technology firm Petron Scientech has been involved in
R&D of ETE technology in the last 15 years, and claims to be the only licensor with proven technology
that provides integration to the downstream applications such as EO and MEG. Netherlands-based
Global Industrial Dynamics has been collaborating with Petron Scientech, in promoting Petron’s Ethanol-
to-Ethylene (ETE ) technology worldwide and is the exclusive representative of Petron Scientech in Europe,
some parts of Asia, Middle East and Australia.

20 Tecnon OrbiChem
Petron Scientech and G.I. Dynamics are currently working on an ongoing ETE /bio-MEG project with
a capacity of between 300-500 ktpa in an undisclosed location. An industry source points India-based
JBF Industries as the most probable company involved in this project given that Petron Scientech had
been contracted by JBF Industries for its planned 500 ktpa bio-MEG facility in Brazil, which, hower, has
been postponed until further notice. JBF is also looking at a site in South Carolina, USA, for a possible
bio-MEG production facility.

Petron’s ETE technology available in the market usually has a 99.9% conversion rate and 99% selectivity
of the main-ethylene derived bio-products produced.

Chematur Engineering Group, Sweden, has a long history in providing ETE technology. The capacities
designed cover the range of 5 to 200 ktpa. The first plant was designed and built for Electro Cloro (a
subsidiary of the Solvay group of Brazil). It was designed to produce 20 MT/day (about 6700 tpa)
of vinyl chloride monomer grade ethylene. Since the start of operations in 1960 the plant has been
expanded and the ethylene produced has also been used as feed to a polyethylene plant.

Other companies currently offering their own ETE technology include Scientific Design; BP, which
recently announced the offering of its new Hummingbird™ ethanol dehydration technology; and the
collaboration between Total Petrochemicals, IFP Energies Nouvelles (IFPEN ) and Axens on their Atol™
advanced ethanol dehydration technology.

Technology to convert ethylene to EO and EGs has been offered by many years by Shell and Scientific
Design and most plants in the world use these technologies. Dow offers similar technology, which was
the originator of silver catalysed conversion through its Union Carbide subsidiary, and recently Dow
has been offering its improved METEOR technology. A development of recent years has been Shell’s
OMEGA process, involving conversion of EO to MEG alone, through use of ethylene carbonate as an
intermediate.

Market Fundamentals

Beverage maker Coca-Cola has introduced bio-material into packaging with the development of
renewably-sourced bottles, among them its PlantBottle™ packaging made from PET incorporating bio-
MEG. Coca-Cola currently buys ethanol-based ethylene glycol from India Glycols to make this PET.
bottle. Coca-Cola has formed a partnership with India’s JBF Industries to build a 500 ktpa bio-ethylene
glycol plant in Brazil, but this project is on hold.

Coca-Cola clearly believes that some customers will be attracted by its environmentally friendly
approach. However, many packaging producers believe that most consumers are unwilling to pay
higher costs for bioplastics compared to petro-based materials.

At the same time, there is a slew of new ethylene and derivatives plants that are planned in the USA
based on low-cost natural gas, including some EG units. The potential competition from low cost petro-
MEG is causing some rethinking about the viability of bio-MEG, certainly in the USA, but also in China.
In fact even the M&G project in China appears to have slowed down.

JBF and Coca-Cola announced their partnership in September 2012 for the supply of bio-MEG for use
in Coca-Cola’s PlantBottle™ packaging. Coca-Cola’s only current source of bio-MEG is India Glycols,
which has a capacity to produce 125 ktpa of sugarcane ethanol-based MEG in Garakhpur, India, for
Coca-Cola’s use. Bio-MEG from India Glycols is sent directly to the USA , Taiwan, the U.K., Mexico,
and Indonesia.

21 Tecnon OrbiChem
Prices

According to a report by the International Renewable Energy Agency (IRENA) in 2012, the production
costs of sugarcane bio-ethylene are very low in Brazil and India (i.e. around USD 1,200/t bio-ethylene).
Chinese production based on sweet sorghum is estimated at about USD 1,700/t. Higher costs are
reported in the United States (from corn) and in the European Union (from sugar beets) at about USD
2,000/t and USD 2,600/t, respectively. At present, the cost of ligno-cellulose-based production is
estimated at USD 1,900-2,000/t in the U.S. In comparison, the cost of petrochemical ethylene is
substantially lower (i.e. USD 600-1,300/t), depending on the region with a global average of USD
1,100/t. The current production cost of bio-ethylene is between 1.1-2.3 times higher than the global
average petrochemical ethylene, but ligno-cellulosic bio-ethylene is expected to reduce the gap in the
near future. The disadvantage of bio-ethylene is likely to have increased today, given the fall in costs of
naphtha, as well as the on-going low cost of ethane in the Middle East and the USA.

This inevitably means high costs and prices for bio-MEG. It is not possible to obtain pricing for bio-
MEG, since it is being bought by so few consumers. We estimate that its price is considerably higher
than petro-MEG, but buyers such as Coca-Cola are willing to pay higher prices for a certain period as
an investment in building up a base of loyal supporters who will prioritize enviromental issues in the
longer term.

PUBLISHED: 29TH MAY 2015

22 Tecnon OrbiChem
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