In our July 9, 2012 post we discussed the initiative driven by Coca Cola to develop bio-based plastics for beverage containers. The first phase of this massive project has resulted in the Plant BottleTM which is made using bio-PET where the ethylene glycol starting monomer is made from renewable sources. The Plant Bottle contains approximately 30% bio-based carbon. But the project doesn’t stop there. Coca Cola has established three R&D partners (Virent, Gevo, and Avantium) to drive to a 100% biobased PlantBottle.TM As you recall, the Plant BottleTM used bio-based ethyleye glycol (EG) to make PET. The next piece of the puzzle is to find a synthetic route to bio-based terephthalic acid (PTA). The Virent approach uses soluble carbohydrate starting materials and the Gevo approach uses fermentable sugars to produce bio-terephthalic acid (bio-PTA). The Avantium YXY approach uses C6 sugars to produce furanics, then furandicarboxylic acid , which when polymerized with bio-EG will form bio PEF, a totally new, 100% biobased polymer. YXY is a trademark of Avantium (www.avantium.com) of the Netherlands. The following figure provides a graphical summary:
This post will focus on the Avantium approach to a fully bio-based polyethylene furanoate (PEF). Avantium has discovered and patented a revolutionary chemical, catalytic process that allows for the economic production of furanics based on a wide range of carbohydrates. The YXY process converts biomass from various sources into the building blocks of alkoxy-methyfurfural (RMF) using a dehydration process in the presence of alcohols (R-OH) and catalysts:
The process then converts the alkoxy-methylfurfural (RMF) to furandicarboxylic acid (FDCA) via an oxidation process:
The overall process can be summarized as follows:
Furandicarboxylic acid FDCA is polymerized in the presence of ethylene glycol (EG) forming polyethylene furanoate (PEF) yielding a high performance engineering thermoplastic capable of multiple applications. The difference in PET and PEF can be seen in the following graphic:
The Avantium product line called YXY PEF can be used to produce:
Fibers spun on commercial fiber lines
Films processed on commercial film extruder equipment
Another driving force behind PEF is not only the potential to have a high performance polymer made from 100 renewable sources, but PEF will compete on performance. Specifically PEF has very good barrier properties (hard to achieve with most bio-based polymers)
- O2 barrier – 6 times greater than PET
- CO2 barrier – 3 times better than PET
- H2O barrier – 2 times better than PET
PEF also has interesting mechanical properties compared to PET
- Higher Tg (glass transition temperature)
- Lower Tm (melting point)
- Higher modulus
Avantium currently has a pilot plant operational with capacity of 40 tons per year in Geleen, the Netherlands, and has plans for a commercial plant to come onstream in 2015 (40-50 kilo tons per year) and a full-scale industrial plant becoming operational in 2017-2018 (300-500 kilo tons per year). Avantium has made significant investments in R&D (especially catalyst development), pilot plant operations and has plans in place for large-scale commercial production.
1) Images from “Latest Advancements in Biobased Materials and Partnerships; YXY Green from Within, by Peter Magnus, Avantium; presented at the Bioplastics Conference in San Francisco, June 2012.
2) Furfural chemistry images from “Acid catalysed alcoholysis of lignocellulose; Towards second generation furan-derivatives,” by Ruud J.H. Grisel (ECN), Jan Kees van der Waal (Avantium), Ed de Jong (Avantium) and Wouter J.J. Huijgen (ECN); presented at COST Action CM0903 (UBIOCHEM), 3rd workshop, Thessaloniki (Greece), November 1-3, 2012.