APIC2014 03 Charles Fryer - OrbiChem 2014/APIC2014_03... · Hydrogenation Fermentation Catalytic process ... • Michelin & Tereos jv plus Axens & IFP Energies Nouvelles ......

Bio-Based Chemicals

Dr Charles Fryer

Tecnon OrbiChem Marketing Seminar at APIC 2014

Pattaya, 15 May 2014

APIC 2014

SUSTAINABILITY, BIODEGRADABILITY, RECYCLING

Source: Tecnon OrbiChem

• Sustainability

� The ability to maintain an activity indefinitely over time� Sustainable activities do not exhaust the planet’s resources

upon which they depend

• Renewables

� Chemicals made from plants and bio-feedstocks� Can be identical to today’s petro-chemicals (“drop-ins”), or new

products offering new opportunities� Enable a company to achieve instant public recognition of its

commitment to sustainability� Witness: The success story of DuPont’s Sorona® fibre, having

37% renewable content, Mohawk’s SmartStrand® carpets, and CocaCola’s PlantBottle


• Biodegradability�The ability for a substance to be easily degraded to small molecules by bacteria, in

nature or in a controlled environment�Some petrochemicals are easily degradable, such as fatty alcohols

• Recyclability�Chemicals or plastics, whose waste can be re-used in a similar way to prior

processing�Wastes can be in-factory discards, but more important if material recovered from

manufactured articles at the end of their use by consumers�Post-consumer waste recycling is challenging, because of the need for collection,

recovery, identification and sorting�Some plastics are easily recycled (e.g. PET bottles), some need special equipment

(e.g.PA-6 carpet facings), some are intractable (e.g. UPR)

• Sustainability, Biodegradability, Recyclability- Which Comes First?�Sustainability is the highest objective, but if this is too difficult, we need to strive at

least for biodegradability or recyclability �Bio-materials offer sustainability - can be undermined by processing or logistics costs

APIC 2014

SUSTAINABILITY, BIODEGRADABILITY, RECYCLING

APIC 2014

PETRO-CHEMICALS ARE BUILT UP FROMSMALL MOLECULES

Naphtha

Ethylene

Polyethylene Ethylene Glycol 1,4-Butanediol

[ ]n


APIC 2014

BIO-MATERIALS PRODUCTION STARTS PREFERABLY FROM C5 OR C6 PRE-BUILT CARBON CHAINS


Alpha-D-Glucose D-Glucose Itaconic Acid

AspergillusTerreus

=

APIC 2014

BETTER STILL ARE C10 OR C11 STRAIGHT CHAINS- GOOD FOR POLYAMIDES


Undecylenic Acid (C11)

Alkali

280ºC

Polyamide 6,10&

Polyamide 5,10Sebacic Acid (C10)

Polyamide 11

Pyrolysis300ºC

Ricinoleic Acidfrom

Castor Oil

APIC 2014

TWO ROUTES TO 1,3-PROPANDIOL- THE BIO-ROUTE HAS PREVAILED


Corn Syrup

CO

Ethylene Oxide

Genetically modified E. coli

1,3-Propandiol

3-Hydroxypropanal

Hydroformylation

H2Hydration

=

APIC 2014

POLY LACTIC ACID (PLA)- AN ECO-FRIENDLY POLYESTER

Lactic Acid(From fermentation of glucose)

Lactide

Lactic acid exists in L- and D- forms. They give rise to different polymers. The poly (L-lactic acid) is the common form, usually called PLA. A blend of this form with poly (D-lactic acid) has superior properties.

PLA


APIC 2014

PETRO- vs BIO-ROUTES TO SUCCINIC ACID


Butane(C4)

Maleic Anhydride(C4)

CO2 waste(yield loss)

Succinic Acid(C4)

Glucose(C6)

Pyruvic Acid(C3)

Fumaric Acid(C4)

37ºC

(1atm)

CO2 sequestered (yield increase)

PETRO ROUTE

MYRIANT’S BIO ROUTE

Succinic Acid(C4)

Corn

CrudeOil Cat.

400ºC

(150 kPa)

130ºC

(30 MPa)

Polyester Polyols6.2% PBS, PBST

9.0%

Other18.5%

Plasticizers4.0%

Solvents & Lubricants

4.0%Food

12.6%

Pharmacy15.1%

Cosmetic5.3%

De-icer Solutions1.0%

Resins, Coating, Pigments19.3%

BDO4.8%

Total = 40,000 Metric Tons

APIC 2014

SUCCINIC ACID MARKET SHARE BY END-USE 2011

Source: BioConsepT Report 2013, Weastra

APIC 2014

SUCCINIC ACID

Four companies are producing succinic acid by biological methods

� BioAmber, first to market via a small plant in France, now building a 30 ktpaplant in Canada in a jv with Mitsui, due to come on stream in Q1 2015.

� Myriant, owned 47% by PTT Chemical, started production in a 14 ktpa plant in Louisiana, USA in June 2013, will reach full production in Q2 2014

� Reverdia, a jv of DSM and Roquette, started production at a 10 ktpa plant in Italy in December 2012, sales started in late 2013

� Succinity GmbH, a jv of BASF and Corbian Purac, started production in February 2014 in a 10 ktpa plant in Spain

Three companies in China are planning to produce succinic acid by biological methods

� Shandong Landian Biotech, started a small pilot plant at end 2013

� Sinopec Yangzi Petrochemical, with a 1,000 tpa pilot plant at Nanjing

� Bluestar, planning to build a 100 ktpa plant in association with JM Davy


Established Petro-Routes• Reppe process, starting from acetylene

Developed in the 1940s but still new plants are being built in China• Mitsubishi process, starting from butadiene

Volatile butadiene pricing has inhibited wider use of this technology• Davy process, starts from maleic anhydride (from butane or butenes)

Proceeds via conversion of MA to its ester, and hydrogenation• LyondellBasell process, starting from propylene oxide (PO)

PO is converted to allyl alcohol, which is then hydroformylated

Bio-Routes Under Development• Succinic acid, made from sugars, is hydrogenated to BDO• Metabolic conversion of sugars to 1,4-BDO • Direct conversion of biomass to 1,4-BDO • Conversion of poly-4-hydroxybutyrate to GBL and then BDO

World market for 1,4-BDO is about 2 million tons per year.

APIC 2014

ROUTES TO 1,4-BUTANEDIOL


APIC 2014

BIO-BASED ROUTES TO 1,4-BUTANEDIOL


Genomatica

Sugar

BDO

SuccinicAcid

Sugar Sugar or other Agricultural Products?

Poly-4-Hydroxybutyrate

(P4HB)

GBL

Biomass

BASFPurac Myriant

BioAmberMitsui

Reverdia(DSM/

Roquette)

Fermentation

ConventionalHydrogenation

Fermentation

Catalytic process

Metabolix

APIC 2014

FDCA - FURAN-2,5-DICARBOXYLIC ACID

Avantium’s YXY process converts biomass into alkoxy-methyfurfural (RMF) in a dehydration process in the presence of alcohols (R-OH) and catalysts. The alkoxy-methylfurfural (RMF) is then oxidised to furandicarboxylic acid (FDCA).

Furandicarboxylic acid (FDCA) is condensed with ethylene glycol (EG) to form polyethylene furanoate (PEF) polymer, a high performance engineering thermoplastic.PEF based on FDCA is similar to PET based on PTA.


APIC 2014

FDCA – A NEW DI-CARBOXYLIC ACID


•FDCA - 2,5-Furan Dicarboxylic Acid

� Can be made by bio-catalytic oxidation of hexanoses (glucose, fructose)

� Products using PTA can be reformulated with FDCA, leading to ….

� … new polyesters, polyamides etc., with different properties

� Produced by Avantium using its proprietary YXY® technology

Image Source: Avantium

APIC 2014FDCA PROMISES NEW POLYMERS, NEW FIBRES

• PEF - Poly (ethylene Furanoate)� Similar to PET, able to replace it in many

applications, but PEF can be 100% bio-based (if made with bio-MEG)

� Avantium plans to start commercial production of FDCA and PEF in 2016 through a 50,000 tons/year plant

Avantium’s 100% biobased T-shirtsfrom recycled PEF bottles

� Avantium has cooperation agreements with Coca-Cola, Danone and ALPLA for the development of PEF bottles, as well as with Wifag-Polytype for the development of thermoformed PEF

� PEF has better performance than PET as regards barrier properties (to oxygen and CO2), heat resistance and light weighting

• Nylons and Aramids using adipic acid (e.g. PA6,6) can be reformulated with FDCA, leading to new polyamides


APIC 2014

CONVERTING NAPHTHA TO USEFUL CHEMICALS


SBR ABS NBR etc

Naphtha

Ethylene

Cyclododecatriene

+

+

Propylene

Butadiene

HMDA

H3CCH3 Ethane

• Invista, Arzeda & LanzaTech jv� LanzaTech has a fermentation process to convert CO (carbon monoxide) to

ethanol, and then to 2,3-butanediol, operated in a pilot plant in New Zealand� LanzaTech is working with Orochem Technologies to improve the process to

dehydrate 2,3-butanediol to 1,3-butadiene, supported by Invista� Lanzatec has a jv with SK Innovation to improve the process for dehydration of 2,3-

butanediol to 1,3-butadiene• Versalis, Novamont and Genomatica jv

� Programme to produce butadiene from biomass, based on a bio-based route being developed by Genomatica

• Braskem & Genomatica jv� Similar to the above?

• Michelin & Tereos jv plus Axens & IFP Energies Nouvelles� Developing the “BioButterfly” process, to make cost competitive bio-butadiene from

sugar, to prepare for a bio-sourced synthetic rubber industry• Others

� Lanzatech and SK Innovation, also via 2,3-BDO starting from carbon monoxide� Cobalt Technologies and two Asian companies, from biomass via butanol?� Global Bioenergies with Synthos, a direct metabolic route� Amyris and Kuraray, alternative route to butadiene polymers

APIC 2014

BIO-BASED ROUTES TO BUTADIENE


Hydrogenation, Oxidation,

Ring-opening oxidation

Cyclododecatriene

Dodecandioic Acid (C12)

Micro-organism Route Employed by Cathay Biotech

Dodecane

APIC 2014

ALTERNATIVE ROUTES TO STRAIGHT CHAIN DI-ACID


APIC 2014

CONVERTING NAPHTHA TO USEFUL CHEMICALS

Naphtha

Benzene

Hydrogen +

Cyclohexane

Adipic Acid HexamethyleneDiamine (HMDA)

1,5-Pentanediamine


=

Alpha-D-Glucose D-Glucose 1,5-Pentanediamine

Micro-Organism

APIC 2014

NEW BIO-ROUTE TO A POLYAMIDE PRECURSOR


1,5-PD - 1,5-Pentanediamine

� PA5,6 fibre, made by combining 1,5-PD with adipic acid, has similar properties to PA 6,6 but is softer and has higher moisture absorption

� PA5,10 is made by combining 1,5-PD with with sebacic acid (made from castor oil) to give a 100% renewable polyamide

APIC 2014

CONCLUSIONS

• Companies in all manner of industrial activities will come underincreasing pressure to demonstrate that they are improving theirenvironmental awareness, by reducing their carbon footprint and raising the sustainability of their operations

• One of the clearest ways to demonstrate that action is being taken is by employing bio-based materials

• The choice of bio-based monomers and polymers is limited at present, but is widening rapidly.

• Success in bio-based monomers will probably come mostly in the area of C4 and C5 chemicals, like:

� Succinic acid� Butadiene� 1,5-Pentanediamine� 1,4-Butanediol� 2,5-Furandicarboxylic acid


APIC 2014

CONCLUSIONS

• New polymers (e.g. polyethylene furanoate) will have to undergo lengthy testing before they will be accepted

• Companies introducing bio-based monomers will have to demonstrate:

� That their operations do not reduce the food supply

� That a direct replacement (“drop in”) monomer costs the same as its synthetic equivalent -- or maybe 10-20% more if it allows the end user to boast of his environmental friendliness

� That a new monomer gives rise to a new polymer that has as good or better performance than existing polymers


…..your source of expert chemical industry knowledge

APIC2014 03 Charles Fryer - OrbiChem 2014/APIC2014_03... · Hydrogenation Fermentation Catalytic process ... • Michelin & Tereos jv plus Axens & IFP Energies Nouvelles ......

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