Bio-Based Chemical Feedstocks - Tecnon OrbiChem 2012/KICHEM2012_2... · o A polyester made from TPA...
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Bio-Based Chemical Feedstocks Darrel Collier Tecnon OrbiChem Seminar at KICHEM 2012 Seoul - 2 November, 2012
Transcript of Bio-Based Chemical Feedstocks - Tecnon OrbiChem 2012/KICHEM2012_2... · o A polyester made from TPA...
Bio-Based Chemical Feedstocks
Darrel Collier
Tecnon OrbiChem Seminar at KICHEM 2012Seoul - 2 November, 2012
KICHEM 2012
BIO-BASED CHEMICAL FEEDSTOCKS
• Discussion Topics
o Definition
o Common Myths
o Three Approaches to Bio-Based Materials
o Recent Commercial Successes
o New/Old Developments
o Conclusions
Source: Tecnon OrbiChem
• Definition
o Bio-Based is defined as a product that has been made from a biological (living) or renewable source (i.e. corn/sugar cane/cellulosics)
• Bio-based products use New Carbon vs Old
KICHEM 2012
BIO-BASED CHEMICAL FEEDSTOCKS
Source: Tecnon OrbiChem
CO2 Biomass/Bio-Organics
Fossil Fuels
›106
Years
Polymers, Chemicals & Fuels
Bio-Chemical Pr
ocesses
(months to a few ye
ars)
Source: Tecnon OrbiChem
KICHEM 2012
THE CARBON CYCLE – NEW vs OLD
KICHEM 2012
BIO-BASED CHEMICAL FEEDSTOCKS
• Discussion Topics
o Definition
o Common Myths
o Three Approaches to Bio-Based Materials
o Recent Commercial Successes
o New/Old Developments
o Conclusions
Source: Tecnon OrbiChem
• Bio-Based Materials Always Have a Lower Carbon Footprint
• Bio-Based Chemicals and Polymers are a Recent Development
• Bio-Based Materials Compete with Food Supply and Consume Needed Resources
• Bio-Based Products will Require Lengthy Development
• Consumers will Accept Lower Performance and Significantly Higher Prices for Bio-Based Products
KICHEM 2012
COMMON MYTHS
Source: Tecnon OrbiChem
KICHEM 2012
BIO-BASED CHEMICAL FEEDSTOCKS
• Discussion Topics
o Definition
o Common Myths
o Three Approaches to Bio-Based Materials
o Recent Commercial Successes
o New/Old Developments
o Conclusions
Source: Tecnon OrbiChem
Source: Tecnon OrbiChem
1. Build on Naturally Occurring Cellulose Polymeric Chains
o Done for over 100 years, chiefly via the rayon process, but this is highly polluting
o The Lyocell process reduces pollution by using a solvent in a closed loop spinning process
o Using eucalyptus trees, the yield per hectare is 10 times that of cotton
2. Develop Bio-Based Routes to Existing Intermediates
o Bio-based processes to make MEG, paraxylene, adipic acid, butadiene, caprolactam etc. are being developed; they are in varying stages of advancement - ‘drop in’ chemicals
3. Develop New Polymers/Fibres
o Completely new bio-based polymer products that demonstrate similar or improved properties as compared to existing commercial oil-base products.
KICHEM 2012
THREE APPROACHES TO BIO-BASED MATERIALS
KICHEM 2012
BIO-BASED CHEMICAL FEEDSTOCKS
• Discussion Topics
o Definition
o Common Myths
o Three Approaches to Bio-Based Materials
o Recent Commercial Successes
o New/Old Developments
o Conclusions
Source: Tecnon OrbiChem
Source: Tecnon OrbiChem
• PTT - Poly (Trimethylene Terephthalate)
o A polyester made from TPA and 1,3-propanediol
o 1,3-propanediol was first made synthetically, but now is also made by fermentation of corn sugar by DuPont Tate & Lyle BioProducts
o DuPont’s PTT polymer, Sorona®, contains 37% by weight renewable plant ingredients
o Sorona® polymer, which has characteristics between PET and nylon, is having great success in carpet applications and in apparel applications as diverse as crease-resistant suits, stretch swimwear, underwear and membranes
KICHEM 2012
COMMERCIAL SUCCESS (NEW POLYMER)
Source: Tecnon OrbiChem
• PLA – PolyLactic Acid
o Made from corn starch (in the US), tapioca products (mostly in Asia) or sugar cane or sugar beet (the rest of the world)
o Has had success as a packaging plastic due to its biodegradability and 100% bio-content
o Major producer is NatureWorks, a joint venture of Cargill and PTT Chemical, Thailand (since October 2011). One 140 ktpa plant in the USA. The next plant of NatureWorkswill be built in Thailand
o Other major producers are Purac (NL), Pyramid Bioplastics(Germany), and Zhejiang Highsun Biomaterials Co., Ltd., Taizhou (China)
o PLA fiber, such as NatureWorks’ Ingeo™ is used in nonwovens, such as spunbond roll goods, eg by CL Chemical fibers, China, in fibrefill, and apparel (especially next-to-the-skin applications)
KICHEM 2012
COMMERCIAL SUCCESS (NEW POLYMER)
Source: Tecnon OrbiChem
• Bio-based ethanol can be dehydrated to ethylene
o Has been done industrially for about 80 years --before naphtha cracking was invented -- especially in Russia and India
o Has been revived in the last few years, particularly in Brazil to make polyethylene
• Bio-ethylene can be converted to MEG
• Coca-Cola introduced ‘PlantBottle’ in late 2009
o Today this bottle contains 30% bio–MEG but 70% conventional PTA
o 10% of Coca-Cola’s bottles worldwide are PlantBottle today
o Coca-Cola targets that all its bottles will be 30% bio-based by 2020
• Several Fibre/Resin Programs selling commercial products
o Toyota Tsusho/KP Chemical/Honam Petrochemical among others
KICHEM 2012
COMMERCIAL SUCCESS (DROP IN INTERMEDIATE)
Bio Based MEG
KICHEM 2012
BIO-BASED CHEMICAL FEEDSTOCKS
• Discussion Topics
o Definition
o Common Myths
o Three Approaches to Bio-Based Materials
o Recent Commercial Successes
o New/Old Developments
o Conclusions
Source: Tecnon OrbiChem
Source: Tecnon OrbiChem
• De-oxygenation of carbohydrates
o Virent’s BioFormPX process starts from carbohydrates like sugars
o Sugars are converted to mono-oxygenated chemicals (alcohols, ketones), then to hydrocarbons, then aromatics
o Aromatics are separated by conventional means into benzene, toluene and xylenes
o Xylenes and then paraxylene are isolated using existing technology
o Virent has a small demonstration plant (30 tpa of bio-reformate) and plans commercial development
• Start from iso-butanol
� Gevo has a process to convert sugar fermentation units to produce isobutanol; large scale plant just started up
� Isobutanol can be dehydrated to iso-butene
� Iso-butene is dimerised to 2,4,4-trimethylpentene and converted to paraxylene(bioPX)
� Gevo is working with Toray to produce 100% bio-based PET
KICHEM 2012
NEW DEVELOPMENTS POLYESTERS(DROP IN PARAXYLENE)
Source: Tecnon OrbiChem
• Verdezyne (supported by BP and DSM)
o Pilot plant in operation in California, USA. Uses a metabolic (fermentation) methodology
o Various non-food feedstocks being experimented -- mostly vegetable oils
o Bio-based adipic acid is used to make PA66 polymer, carpet fibre and textile filament
• Rennovia
o Pilot plant in operation in California, USA. Uses chemo-catalytic technology
o Glucose (from biomass) is oxidised to glucaric acid and hydrogenated to adipic acid
• BioAmber (supported by Mitsui & Co.)
o First to market with bio-succinic acid, in a 2 ktpa plant in France
o BioAmber will adapt the bio-Succinic acid process to make adipic acid, with Celexion
• Other companies with plans to make bio-based adipic acid include DSM and Genomatica
KICHEM 2012
NEW DEVELOPMENTS POLYAMIDES(DROP IN ADIPIC ACID)
Source: Tecnon OrbiChem
High prices have revived interest in old Bio-based routes to butadiene
• Lebedev process, starting from ethanol
o Employs dehydration and dehydrogenation of ethanol. Used in Russia in the 1940s and operated until the 1970s
• Ostromislensky process, starting from ethanol
o Acetaldehyde, made from ethanol, is reacted with further ethanol. Used in the USA in the 1940s, and is used in some small plants in India and China
• Invista & LanzaTech joint venture
o LanzaTech, based in Chicago, 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
o LanzaTech is working to improve the process to dehydrate 2,3-butanediol to 1,3-butadiene, supported by Invista
• Versalis, Novamont and Genomatica joint venture
o Programme to produce butadiene from biomass, based on a biobased route being developed by Genomatica
KICHEM 2012
NEW DEVELOPMENTS POLYAMIDES(DROP IN BUTADIENE)
1,3-butadiene is the starting material for the process developed by DuPont and later Invista to make adiponitrile, the raw material for HMDA, which is combined with adipic acid to make nylon 6,6.
Source: Tecnon OrbiChem
• FDCA - 2,5-Furan dicarboxylic acid
o Can be made by bio-catalytic oxidation of hexanoses (glucose, fructose)
o Products using PTA can be reformulated with FDCA, leading to ….
o … new polyesters, polyamides etc., with different properties
• PEF – Poly (ethylene furanoate)
o Similar to PET, able to replace it in many applications, but PEF can be 100% bio-based (if made with bio-MEG)
o Avantium has a 40 tons per year pilot PEF plant in the Netherlands
o Avantium has cooperation agreements with Coca-Cola and with Danone for the development of PEF bottles
o PEF has better performance than PET as regards barrier properties (to oxygen and CO2), heat resistance and light weighting
o PEF’s potential for fibres is uncertain -- melting point is high
KICHEM 2012
NEW POLYMER DEVELOPMENTS
Source: Tecnon OrbiChem
• 1,5-PD - 1,5-Pentanediamine
o Lysine is produced by fermentation of plant materials; it can bedecarboxylated to 1,5-PD
o Ajinomoto, a producer of lysine, and Toray have an agreement to produce 1,5-PD and from it the polyamide PA 5,6
o PA5,6 fibre has similar properties to PA 6,6 but is softer and has higher moisture absorbtion
o PA 5,6 is made by combining 1,5-PD with adipic acid -- which can be replaced with sebacic acid (made from castor oil) to make PA 5,10 or by other dicarboxylic acids
KICHEM 2012
NEW POLYMER DEVELOPMENTS POLYAMIDES
Source: Tecnon OrbiChem
• Condensation Polyamides PA X,Y have the general formula
--[-HN(CH2)XNHCO(CH2)Y-2CO-]n-- and are made from diamines H2N(CH2)XNH2
and dicarboxylic acids HOOC(CH2)Y-2COOH
• Diamines (Bio-based)
o Old X = 6 or 4 (synthetic), or 10 (natural, made from castor oil)
o New X = 5 (natural) made from lysine
• Dicarboxylic acids (Bio-based)
o Old Y = 6 (synthetic from benzene) or 12 (synthetic from butadiene)
o New Y = 6 (natural, bio-based made from sugars etc.)
o Y = 12 (natural), made by Cathay Industrial Biotech
o Old Y = 10 (natural sebacic acid, made from castor oil, by Evonik and by Arkema and its subsidiary Casda Biomaterials (China), with Suzhou Hipro Polymers (China) making PA 10,10;
o Old Y = 9 (natural based azelaic acid, made from oleic acid, derived e.g. from olive oil)
Many of these polyamides can be used as fibres, though when Y is larger than 6 the main use is as monofilaments and as engineering resins
KICHEM 2012
NEW/OLD POLYMER DEVELOPMENTSPOLYAMIDES
• Several companies are building plants to make succinic acid by biological methods
o BioAmber, first to market with a small plant in France
o Myriant, to start production in Q4
o Reverdia, a jv of DSM and Roquette, to start production in October
o BASF and Purac, to start production in 2013
• Succinic acid can be converted to BDO (1,4-butanediol)
• BDO from this route can be used to make bio-based polymers and fibres such as PBT
• Other routes to BDO
• Metabolic conversion of sugars to 1,4-BDO has been achieved by Genomatica and will be used in a 20 ktpa plant being converted in Italy in a joint venture with Novamont, and in a plant in California, both starting up in 2013
• Genomatica is cooperating with Beta Renewables (a jv of Chemtex and TPG) to develop a direct process from biomass to 1,4-BDO
Source: Tecnon OrbiChem
KICHEM 2012
NEW MONOMER/POLYMER DEVELOPMENTS
KICHEM 2012
BIO-BASED CHEMICAL FEEDSTOCKS
• Discussion Topics
o Definition
o Common Myths
o Three Approaches to Bio-Based Materials
o Recent Commercial Successes
o New/Old Developments
o Conclusions
Source: Tecnon OrbiChem
• Companies will come under increasing pressure to demonstrate that they are improving their environmental awareness, by reducing their carbon footprint and raising the sustainability of their operations
• Many companies around the world are working to develop bio-based monomers, using both biological and chemical methods of converting natural raw materials
• Quickest commercialisation and largest opportunities will likelyinvolve ‘drop in’ monomers/polymers that take advantage of existing industry infrastructure
• Commercial success have involved partnering as different technologies and skill sets are needed to come together
Source: Tecnon OrbiChem
KICHEM 2012
CONCLUSIONS
• Companies introducing bio-based monomers will ultimately have to demonstrate:
o That their operations do not reduce the food supply
o 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
o That a new monomer gives rise to a new polymer that has as good or better performance than existing polymers
• Existing polymers/fibres (PET, PA6,6 etc) made with bio-based monomers will be greatly welcomed by the textile and packaging industry, provided there is no loss of performance due to impurities
Source: Tecnon OrbiChem
KICHEM 2012
CONCLUSIONS
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