Download - Biobased chemicals
Biobased Chemicals
Presented by S.RasoulinejadMsc, Microbial Biotechnology
Winter 2013-2014
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
introduction
Analysis of markets for bio-based products
Fibre based materials (i.e. for construction sector or car industry);
Bio-plastics and other bio-polymers;
Surfactants;
Bio-solvents;
Bio-lubricants;
Ethanol and other chemicals and chemical building blocks;
Pharmaceutical products incl. vaccines;
Enzymes;
Cosmetics.
There is a wide range of bio-based products which could eventually acquire a substantial market acceptance:
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.
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.
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 3-
hydroxypropionic 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.
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
Propionic Acid Production byMicrobial 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.
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)
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 ProbionibacteriaSEM of P. acidipropionici
DSM 4900 grown on glycerolbasedmedium.
Fig. 3.2 Propionic acid fermentation pathwayThe metabolic pathway for propionic acid production from different carbon sources,showing the Wood-Werkman cycle, different intermediates and the metabolic endproducts.[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)
Bio-plasticsExisting 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.
Bio-solvents 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. There are eight main solvent groups: aromatic hydrocarbons, petroleum-based solvents, alcohols, ketones, esters, ethers, glycol ethers, halogenated hydrocarbons and so-called special solvents.
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). Bio-
solvents 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.
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.
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.
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.
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.
Products/uses
intermediates Secondry chemicals
Building blocks
Intermediate
platform
Biomass feed stock
Industrialtransportation
Reagents-building unitFuel oxygenatesSolventsAminesPhenol-formaldehyde resinsPlasticizersPolyvinyl acetatePolyvinyl alcohol
Ammonia synthesis ,hydrogenation productsMethyl esters,Formaldehyde, Acetic acid, Dimethylether,Dimethylcarbonate, Methyl amines, MTBE, olefins ,
GasolineOlefinhydroformylationproducts: aldehydes, alcohols,
acids....
H2Methan
Higher alcoholMixed alcoholsOxo syntheseis
products.......
BiobasedSyn gas
starch
textiles Antifreeze and deicersEmulsifiers
Fermentation products, Propylene glycol, malonic, 1,3-PDO, diacids, propylalcohol, dialdehyde, epoxidesReagent, propionol,
acrylate....
GlycerolLactic
Propionic acid......
hemicellulose
Safe food supply
Green solventsPolypyrrolidonesPhthalate polyesters
THF, 1,4-Butanediolγ-butyrolactone, pyrrolidones, esters, diamines,4,4-Bionelle ,
HydroxybutyricacidButanediols, butenols.....
Fumaric acidAceton
Malic acid......
Sugers:GlucoseFructoseXyloseLactoseSucrosestarch
cellulose
Communicationenvironment
Resins, crosslinkersPolyethersPolyhydroxypolyestersSpecialty chemical intermediate
Methyl succinatederivatives (see above), unsaturated estersmany furan derivativesEG, PG, glycerol, lactate, hydroxyfurans, sugar
acids.....
FurfuralXylitol/
arabitolitaconic acidItaconic acid....
Lignin
Recreationhousing
PolyurethanesNylons (polyamides)PEIT polymer
1,5-pentanediol,itaconicderivatives, pyrrolidones, esters,Numerous furan derivatives, succinate, esters, levulinicacidGlycols (EG, PG), glycerol, lactate, isosorbideCaprolactam, diaminoalcohols, 1,5-diaminopentane
Citric/aconitic acidLysine
Sorbitol.....
oil
Health and hygience
Phenolics, food additives Gallic acidFerulic acid
protein
PoyaminoacidsPolysaccharidespolyhydroxyalkonoates
Direct polymers & gum
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.
In the case of bio plasticizers
reFlexTM 100
thermal stability,
and improved plasticization efficiency
butyl benzyl phthalate [BBP]
diisononylcyclohexane-1, 2 dicarboxylate (DINCH)
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.
Pathways to Building Blocks from Sugars
Health and hygience
recreation housing communication
environment Safe food supply
textiles transportation
industrial
Plastic eyeglasses,Cosmetics,Detergents,Pharmaceuticals,Suntan lotion,Medical-dental product,aspirin
Footgear,Protectives equipment,Camera and film,Bicycle parts & tires,Wet suits,Tapes-CD’s-DVD’s,Golf equipment,Camping gear,boats
Paints,Resins,Siding,Insulation,Cements,Coatings,Varnishes,Flame retardents,Adhesives,carpeting
Molded plastics,Computer casings,Optical fiber coating,liquid crystal displays, pens,pencils,inks,Dyes,Paper products
Water chemicals,Flocculants,Chelators,cleaners and detergents
Food packing,Presevatives,Fertilizers,Pesticides,beverage bottles,Appliances,Beverage can coating, vitamins
Carpets,Fibers,fabric,Coatings,Foam cushions,upholstery,drapes,Lycra,spandex
Fuels,Oxygenates,Anti-freeze,Wiper fluids molded plastics,Car seats,Belts hoses,Bumpers,corrosion inhibitors
Corrosion inhibitors,dust control,boiler water treatment,gas purification,emission abatement,specialty lubricants,hoses,seals
Figure 3 – Analogous Model of aBiobasedProduct Flow-chart for BiomassFeedstocks
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.
PBT )Polybutylene terephthalate and (PET )Polyethylene terephthalate (
Chemical Economics Handbook ® (CEH(
Companies Solazyme Codexis Gevo Amyris Cereplast NatureWorks Novamont Novozymes Johnson & Johnson Monsanto
BASF Nestlé
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.
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
Producing hydrogen from biomass
Hydrogen is a promising fuel for the future
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.
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.
Fermentations 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.
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%.
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