1.
Biobased Chemicals
Presented by S.Rasoulinejad
Msc, Microbial Biotechnology
Winter 2013-2014

2.
introduction
Bio-based chemicals are derived from renewable feedstock, i.e. all biomass
derived from plants, animals or microorganisms (including biological
waste from households, agricultural residues, and waste from animals and
food/feed production), which can be used in part or as a whole as raw
materials for industrial production and energy generation.
is important to differentiate between 1st and 2nd
generation technology for the production of biofuels and
bio-based chemicals.
 First generations
 Second generations

3.
Analysis of markets for bio-based
products
There is a wide range of bio-based products which could eventually
acquire a substantial market acceptance:
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Fibre based materials (i.e. for construction sector or car industry);
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Bio-plastics and other bio-polymers;
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Surfactants;
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Bio-solvents;
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Bio-lubricants;
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Ethanol and other chemicals and chemical building blocks;
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Pharmaceutical products incl. vaccines;
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Enzymes;
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Cosmetics.

4.
bio-solvents, produced from vegetable oils and from starch
progressively replace petrochemical solvents. Solvents mainly part of
paintings, inks, varnishes, adhesives etc. Majority of solvents currently
petrochemical solvents.
Biopolymers, such as polysaccharides (carbohydrates – starch from
maize, wheat, and potatoes). Polylactic Acid (PLA), a plastic material
derived by fermentation (producing lactic acid) from starches or
glucose. Used for food packaging, bags, hygiene products, packaging
for biological waste, plant pots, etc. Also composite materials with
new qualities; textiles, etc.

5.
Surfactants lower surface tension of liquids and are used in
soaps, detergents, pharmaceuticals, food additives, etc. and for
the production of emulsions and foams. They are produced
largely from oils. Next generation "biosurfactants" can be
produced from algae or bacteria.
Biodegradable lubricants made from vegetable oils (and their
chemical derivatives) that are non toxic for soil or water. Used as
hydraulic oils in areas where high risk of pollution.

6.
The chemicals of interest are the ones that could potentially serve as
building blocks, platforms, for other chemicals and polymers.
Glycerol, a by-product of biodiesel production, was used as raw material for
the production of propionic acid, 3-hydroxypropionaldehyde (3HPA) and 3hydroxypropionic acid (3HP), while methacrylic acid (MA) was produced
from 2-methyl-1,3-propanediol, a by-product of butanediol production.
Lactobacillus reuteri was employed as a whole cell biocatalyst for the
conversion of glycerol to 3HPA and 3HP in aqueous solution.

7.
Potato juice, a by-product of potato starch processing, was
shown to be a promising, inexpensive nitrogen/vitamin
source for the growth of the organism and propionic acid
production

8.
Propionic Acid Production by
Microbial Fermentation of Glycerol
The main production route of propionic acid is the oxo-synthesis through
hydroformylation of ethylene with carbon monoxide yielding the
intermediate propionaldehyde, which gives propionic acid on oxidation.
It is also obtained as a by-product of the chemical production of acetic acid
by liquid phase oxidation of n-butanePresents the current status for
propionic acid production from glycerol using propionibacteria in
batch/fed-batch operations.

9.
oxo-synthesis
The process typically entails treatment of an alkene with high pressures
(between 10 to 100 atmospheres) of carbon monoxide and hydrogen at
temperatures between 40 and 200 C. Transition metal catalysts are
required)

10.
microorganisms can produce
propionic acid
-Veillonella (parvula and
alcalescens)
-Clostridium propionicum,
-Selenomonas (ruminantium
and sputigena)
-Megashaera
-Fusobacterium necrophorum
Among them, propionibacteria
have been mostly used as hosts
for propionic acid production
Fig. 3.1 Probionibacteria
SEM of P. acidipropionici
DSM 4900 grown on glycerolbased
medium.

11.
Fig. 3.2 Propionic acid fermentation pathway
The metabolic pathway for propionic acid production from different carbon sources,
showing the Wood-Werkman cycle, different intermediates and the metabolic end
products.
[1] Methylmalonyl-CoA transcarboxylase (pyruvate carboxytransphosphorylase)
[2] Malate dehydrogenase [3] Fumarase
[4] Succinate dehydrogenase [5]Propionyl-CoA:Succinate CoA transferase
[6] Methylmalonyl-CoA mutase (isomerase) [7] Methylmalonyl-CoA racemase
[8] Propionaldehyde dehydrogense (Predicted) [9] Alcohol dehydrogenase (Predicted)

12.
Bio-plastics
Existing and emerging bio-based bulk plastics are starch plastics, cellulosic
polymers,
polylactid acid (PLA),
polytrimethylene terephthalate (PTT) from bio-based 1,3-propanediol (PDO),
bio-based polyamides (nylon),
polyhydroxyalkanoates (PHAs),
bio-based polyethylene (PE),
polyvinyl chloride (PVC) from bio-based PE, other bio-based thermoplastics
(polybutylene terephthalate (PBT), polyphenylene sulphide (PBS), polyethylene
terephthalate (PET), polyethylene-co-isosorbide terephthalate polymer (PEIT),
further polyesters based on PDO),
polyurethane (PUR) from bio-based polyols and bio-based thermosets.

13.
Bio-solvents
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Solvents are liquids that possess the ability to dissolve, dilute or extract
other substances without modifying the chemical composition of the
extracted substances or of the solvent itself.
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There are eight main solvent groups:
aromatic hydrocarbons,
petroleum-based solvents,
alcohols, ketones,
esters,
ethers,
glycol ethers,
halogenated hydrocarbons
and so-called special solvents.

14.
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Base on their properties, solvents are used as
degreasing agents (cleaning of metals, textiles),
additives and diluting compounds (paints, varnishes, inks, glues,
pesticides),
stripping agents (paint, varnish, glue removers)
and extraction solvents (perfumes, pharmaceuticals). Biosolvents have applications:
plant-protection oils and wetting agents and biofluxing agents.
The vast majority of bio-based solvents do not emit volatile
organic compounds (VOC) which are harmful to human health.

15.
Bio-surfactants
Surfactants lower the surface tension of liquids, allowing chemicals to mix
more easily. Surfactants are usually organic compounds that are amphiphilic,
meaning they contain both hydrophobic groups (their tails) and hydrophilic
groups (their heads). Bio-surfactants are surfactants in which at least one of
the two groups (hydrophilic or hydrophobic) is obtained from plants: they
are therefore not necessarily 100% plant-derived.

16.
Application of bio-surfactants
Surfactants are used in many industries such as household detergents,
personal care, industrial cleaners, food processing, oleofield chemicals,
agricultural chemicals, textiles, emulsion polymerization, paints and
coatings, lubricant and fuel additives, metal working, mining
chemicals, pulp and paper production, leather processing, etc. The
largest end use market for surfactants is household cleaning detergents.

17.
Raw materials
Surfactants are made from oleochemical (bio-based) and/or petrochemical
(synthetic) raw materials. Oleochemical surfactants are commonly derived
from plant oils such as coconut and palm oils, from plant carbohydrates such
as sorbitol, sucrose and glucose or from animal fats such as tallow.
In a typical palm plantation, besides the oil and lignocellulosic biomass
sources, there is some activity to convert palm oil mill effluent (POME) to
high value chemicals and biogas.
In the case of corn wet mill and sugar cane plantations, biomass is converted
to fuel (mostly bio ethanol) and chemicals such as polyols, acids, and others.

18.
Platform chemicals
Sugars,
Oils
and other compounds in biomass can be converted into platform chemicals
or building blocks directly or as by-products from fuel production
processes analogous to the petrochemical industry today.

19.
Biomass
feed stock
Intermediat
e platform
Building blocks
Secondry
chemicals
starch
Biobased
Syn gas
H2
Methan
Higher alcohol
Mixed alcohols
Oxo syntheseis
products
.......
Ammonia synthesis,
hydrogenation products
Methyl esters,Formaldehyde,
Acetic acid, Dimethylether,
Dimethylcarbonate, Methyl
amines, MTBE, olefins,
Gasoline
Olefinhydroformylationproducts:
aldehydes, alcohols, acids....
Reagents-building unit
Fuel oxygenates
Solvents
Amines
Phenol-formaldehyde resins
Plasticizers
Polyvinyl acetate
Polyvinyl alcohol
Industrial
transportation
Glycerol
Lactic
Propionic acid
......
Fermentation products,
Propylene glycol, malonic, 1,3PDO, diacids, propylalcohol,
dialdehyde, epoxides
Reagent, propionol, acrylate....
Antifreeze and deicers
Emulsifiers
textiles
Fumaric acid
Aceton
Malic acid
......
THF, 1,4-Butanediol
γ-butyrolactone, pyrrolidones,
esters, diamines,4,4-Bionelle,
Hydroxybutyricacid
Butanediols, butenols.....
Green solvents
Polypyrrolidones
Phthalate polyesters
Safe food
supply
Furfural
Xylitol/arabitolitaconic
acid
Itaconic acid ....
Methyl succinatederivatives (see
above), unsaturated esters
many furan derivatives
EG, PG, glycerol, lactate,
hydroxyfurans, sugar acids.....
Resins, crosslinkers
Polyethers
Polyhydroxypolyesters
Specialty chemical intermediate
Communication
environment
Citric/aconitic acid
Lysine
Sorbitol
.....
1,5-pentanediol,
itaconicderivatives, pyrrolidones,
esters,
Numerous furan derivatives,
succinate, esters, levulinicacid
Glycols (EG, PG), glycerol, lactate,
isosorbide
Caprolactam, diaminoalcohols,
1,5-diaminopentane
hemicellul
ose
cellulose
Lignin
oil
protein
Sugers:
Glucose
Fructose
Xylose
Lactose
Sucrose
starch
Gallic acid
Ferulic acid
Direct polymers & gum
intermediates
Polyurethanes
Nylons (polyamides)
PEIT polymer
Products/uses
Recreation
housing
Health and
hygience
Phenolics, food additives
Poyaminoacids
Polysaccharides
polyhydroxyalkonoates

20.
Which Way to Go?
Various building block molecules such as 5-hydroxymethylfurfural (HMF),
derived from cellulosic biomass,
Startup companies such as Segetis: are developing novel chemicals based
on levulinic acid for use as replacement solvents and plasticizers.
Roquette :has been actively pursuing commercial scale production of
isosorbide from sugar feedstock useful in the development of
bioplasticizers and bisphenol free polycarobonate resins.

21.
In the case of bio plasticizers

reFlexTM 100

thermal stability,

and improved plasticization efficiency

butyl benzyl phthalate [BBP]

diisononylcyclohexane-1, 2 dicarboxylate (DINCH)

22.
This is very true for bio products such as bio ethylene derived from sugar
cane or bio 1, 3 propane diol that are targeted to replace corresponding
petroleum derived products.

23.
Pathways to Building Blocks from Sugars

24.
industrial
Corrosion
inhibitors,
dust control,
boiler water
treatment,
gas
purification,
emission
abatement,
specialty
lubricants,
hoses,
seals
transportation
Fuels,
Oxygenates,
Anti-freeze,
Wiper fluids
molded
plastics,
Car seats,
Belts hoses,
Bumpers,
corrosion
inhibitors
textiles
Carpets,
Fibers,fabric,
Coatings,
Foam
cushions,uphols
tery,drapes,
Lycra,
spandex
Safe food
supply
Food packing,
Presevatives,
Fertilizers,
Pesticides,
beverage
bottles,
Appliances,
Beverage can
coating,
vitamins
environment
communication
Water chemicals,
Flocculants,
Chelators,
cleaners and
detergents
Molded plastics,
Computer
casings,
Optical fiber
coating,liquid
crystal displays,
pens,
pencils,
inks,
Dyes,
Paper products
housing
Paints,
Resins,
Siding,
Insulation,
Cements,
Coatings,
Varnishes,
Flame
retardents,
Adhesives,
carpeting
recreation
Health and
hygience
Footgear,
Protectives
equipment,
Camera and
film,
Bicycle parts
& tires,
Wet suits,
Tapes-CD’sDVD’s,
Golf
equipment,
Camping
gear,boats
Plastic
eyeglasses,
Cosmetics,
Detergents,
Pharmaceuticals
,
Suntan lotion,
Medical-dental
product,
aspirin
Figure 3 – Analogous Model of aBiobasedProduct Flow-chart for BiomassFeedstocks

25.
Sugar-based platform.
Platforms based on sugars (Werpy, et al., 2004) have been deployed to
create acids such as succinic acid and convert the acid to high value
chemicals such as:
 2- pyrrolidone,
 1, 4 butane diol,
 tetra hydrofuran and others.

26.
Polyethylene terephthalate PET Polybutylene terephthalate and PBT

27.
Chemical Economics Handbook® (CEH)

28.
Companies
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Solazyme
Codexis
Gevo
Amyris
Cereplast
NatureWorks
Novamont
Novozymes
Johnson & Johnson
Monsanto
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BASF
Nestlé

29.
Solar cells for sustainable production of methanol from
CO2
In the BIOCOMET project,
The researchers simulate the photosynthesis process in plant cells by
manufacturing biomethanol on a large-scale, using solar cells for the
purpose.
(Bio)methanol is used as a raw material for making plastics (including
bioplastics) and also in fuels (for biodiesel and for the fuel additive MTBE).
This project is part of the BioSolar Cells programme and enables
Wageningen UR Food & Biobased Research to contribute to the Biobased
Economy.

30.
Tulip compounds for production of biobased
polymers
Tulips produce tulipaline and tuliposides. These compounds play a role in
the protective mechanisms of the plant and also fight bacteria, fungi and
insects. Also, the compounds are suitable as building blocks for the
production of plastics

31.
Producing hydrogen from biomass
Hydrogen is a promising fuel for the future
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biomass may be used as a raw material, the conversion to electricity is
extremely efficient, and hydrogen does not contribute to the production of
CO2.
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Up to the present, residual materials from the food industry, potato
steam peels, molasses, wheat bran, and barley straw have all been
studied for their potential as biomass. Eventually, cultivated biomass
such as sugar beets and sweet sorghum will also be added to this list.

32.
Fermentations

About Wageningen UR
The core of biochemical hydrogen production consists of two consecutive
fermentations : During the first fermentation, when they reach 70ºC,
thermophilic (heat-loving) bacteria convert the substrate to hydrogen, CO2
and organic acids.
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During the following fermentation, with the aid of light energy,
bacteria convert the organic acids to hydrogen and CO2.
This makes it possible to raise the efficiency level of the hydrogen
production as high as 75%.

33.
Thanks for you attention