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%.

About Wageningen UR

Thanks for you attention