High Added Value Renewable Polymers

By:  Dr. Bernard Cooker,  Lee Enterprises Consulting

Summary

Biomass-based green polymer and monomer projects, as reported in Chemical and Engineering News and Chemical Engineering Progress in Q1, Q2 2017 are surveyed. The focus here is on combinations of low raw material cost, commercial scale operation and high added product value, to maximize the profit opportunity.

Introduction

The author has compiled a spreadsheet of every article on biomass-fed chemical processing projects in Chemical and Engineering News (CEN) and Chemical Engineering Progress (CEP) since 2013. Reviewing the 556 entry database of renewable chemicals, polymers made from biomass are increasingly prominent, more diverse and entering commercial production with greater frequency. This is driven by their higher added value relative to simpler molecules of narrower application and the need for financial investors to make an adequate profit. This article briefly surveys the biomass-fed biopolymer and monomer projects reported in the first half of 2017.

Succinic Acid

Succinic acid is a green straight chain C4 dicarboxylic acid and a candidate monomer for multiple polymers. Ref. 1 discloses three commercial succinic acid production projects: a 15,000 ton/yr unit by Myriant in the U.S., started in 2013, a second unit with 10,000 ton/yr capacity by Reverdia, a JV of Dutch State Mines and Roquette, which was started up in Italy in 2012, and Succinity’s 10,000 ton/yr plant in Spain, which was started up in 2014. Succinity is a partnership of BASF and Corbion. The two most recently disclosed commercial succinic acid projects are summarized in Table 1. The first is a 36,000 ton/yr unit in China, developed by BioAmber and CJ Cheiljedang, employing a converted amino acid plant and fermentation facility. Start up is projected for 2018. See refs. 2 – 4. The second such plant is by BioAmber and Mitsubishi in Canada, with a 30,000 ton/yr capacity and using yeast fermentation production technology, licensed from Cargill. See refs. 5 and 6 and Table 1.

Polybutylene Succinate (PBS)

A commercial polymer plant using succinic acid monomer was recently announced. See Table 1 and ref. 5. The polyester product combines butane diol and succinic acid and it is compostable and biodegradable. The plant is a JV of PTT and Mitsubishi Chemical, located in Thailand.

Epoxy Resins

AgroParis Tech of France recently reported separation of syringaresinol, a green monomer, from plant material, in the laboratory. They are targeting substitutes for bisphenol-A for epoxy resin manufacture. See Table 1 and ref. 7.

Polymers from Itaconic Acid

Itaconic acid is another monomer and renewable green chemical of interest, being an unsaturated C5 dicarboxylic acid, also known as methylene succinic acid. It is obtained from the fungal fermentation of carbohydrates and is non-toxic and readily biodegrades. See ref. 8. Ref. 9 discloses the laboratory scale work by Itaconix, a subsidiary of Revolymer, in the U.S., to make itaconic acid-incorporating polymers in collaboration with two partners. The first is Croda and the product is Zinador® 22L polymer, the prospective application being odor removal, and the second partner is AkzoNobel, making bio-based polymers for water quality, cleaning and hygiene applications. See Table 1.

2,5-Furandicarboxylic Acid

2,5-furandicarboxylic acid monomer is functionally somewhat equivalent to terephthalic acid in polymerizations, including polyester synthesis. A five member unsaturated C₄O furan ring substitutes for the aryl group of TA. Table 1 and refs. 10 and 11 outline the commercial 2,5-furandicarboxylic acid plant of 50,000 ton/yr capacity by Synovia, a Vanadium/BASF JV in Belgium. The monomer is synthesized from sugars. Avantium invested $80 million in capital in the project and $220 million came from BASF, according to refs. 10 and 11.

Polyethylene Furanoate (PEF)

Table 1 and ref. 10 summarize some previous development work by Avantium to produce polyethylene furanoate (PEF) from 2,5-furandicarboxylic acid and ethylene glycol monomers. Avantium has collaborated with Coca Cola to develop a green PEF beverage bottle and they have also worked with Danone, to develop a green food packaging polymer. Ref. 12 relates to Avantium’s PEF pilot program and their $110 million public offering. Synvina, the Avantium/BASF JV, has invested in a commercial PEF plant in Europe, using their captive 2,5-furandicarboxylic acid supply. See ref. 13, which also discloses that a European PET bottle group recently concluded that PEF can be recycled with the PET stream.

Polyhydroxyalkanoates (PHAs)

Commercial capacity for PHAs from non-food agricultural residues at 1,000 ton/yr has been built in Italy by Bio-on and Sadam. The capital cost of the investment was reported as $15 million. See Table 1 and ref. 14.

Polyols

BioBased Technologies, recently purchased by Cargill, announced commercial biomass conversion to polyols, which are CHO polymers with multiple hydroxyl groups, frequently used as a co-monomers in epoxies and urethanes. The US plant produces polyols for production of flexible foams with high bio-based content. See Table 1 and ref. 15.

Adhesives, Lignin

Use of lignin, which has historically been consumed in the boilers of the pulp and paper mills where it is produced as a byproduct, as a low value fuel, is being upgraded to higher value products. All lignocellulosic biomass, including wood, contains 20 to 35% lignin on a dry basis. The upgrade is driven by the world wide decline in paper sales and consequent need by manufacturers to find new products from their feedstock and develop applications for them, including the lignin. Table 1 and ref. 16 disclose two projects at Stora Enso, the Finnish pulp and paper manufacturer to add biorefineries to their existing mills to accomplish this.

The company is piloting conversion of lignin, a tough, branched, high MW polymer, containing aryl rings and CHO-based functional groups, to adhesive for use in manufactured wood products, such as particle board and plywood. Stora Enso has also announced a 50,000 ton/yr lignin plant, the 95% pure product to yield phenol substitutes in manufactured wood composites. See ref. 16.

Methylene Diphenyl Diisocyanate and Pentamethylene Diisocyanate Monomers

Table 1 and ref. 17 disclose a potentially important development in processes for diisocyanate monomers. Covestro and collaborators University of Stuttgart, CAT Catalytic Center at RWTH Aachen University and Bayer, in Germany, have converted sugar and ammonia in the laboratory to aniline, via an intermediate. Aniline is a precursor to methylene diphenyldiisocyanate, a monomer in polyurethanes. Covestro is piloting the conversion of biomass to pentamethylenediisocyanate, another monomer, used as a polyurethane coatings hardener. See ref. 17.

Conclusions

Investors in the bioeconomy increasingly seek high value added green products from efficient commercial plants because the combination of low raw material costs, lower conversion cost at scale and high product added value maximize profit potential. A growing proportion of new bio-projects are not in ethanol, biofuels or other low MW products with limited properties. This article has illustrated the high added value trend regarding green monomers and polymers. Highlights include the recent progress in commercial (low value) lignin conversion to useful polymeric products of added value and the conversion of non-food agricultural waste to PEF, which can now be comingled with a European PET recycle stream.

Dr. Cooker is a consultant affiliated with Lee Enterprises Consulting Inc., the world’s premier bioeconomy consulting group. LEC provides technical and business expertise in bioenergy, biofuels and renewable chemicals, through its 100+ members, worldwide.

Table 1. Added Value Renewable Polymer Projects, Q1 – Q2, 2017, Chemical and Engineering News, Chemical Engineering Progress. L – laboratory, P – pilot plant, C – commercial

#	Product	Raw materials	Scale (ton/yr)	Company, institution	Notes
1	Succinic acid	Biomass	C, 36,000	BioAmber, CJ Cheiljedang	China
2	Succinic acid	Biomass	C, 30,000	BioAmber, Mitsubishi	Canada
3	Polybutylene succinate	Succinic acid	C	PTT/Mitsubishi JV	Thailand
4	Epoxy resins	Syringaresinol	L	AgroParis Tech	France, green monomer
5	Zinador® 22L polymer, biobased polymers	Itaconic acid	L	Itaconix	U.S.
6	2,5-Furandicarboxylic acid	Sugars	C, 50,000	Synvina, Avantium/BASF JV	Belgium
7	Polyethylene furanoate	Biomass	P	Avantium, Coca Cola, Danone	Green bottles, packaging
8	Polyethylene furanoate	2,5- Furandicarboxylic acid	C	Synvina, Avantium/BASF JV	Europe, recycled PEF/PET mix OK
9	Polyhydroxyalkanoates	Nonfood ag residues	C, 1,000	Bio-on, Sadam	Italy
10	Polyols	Biomass	C	BioBased Technologies, Cargill	U.S.
11	Adhesive	Lignin	P	Stora Enso	Sweden
12	Lignin	Wood	C, 50,000	Stora Enso	Finland
13	Methylene diphenyl diisocyanate, via aniline	Sugar, ammonia	L	Covestro, Bayer, academia	Germany
14	Pentamethylene diisocyanate	Biomass	P	Covestro	Germany

 

References

1. Chemical and Engineering News, 2/13/17, p. 22
2. Ibid, 1/2/17, p. 13
3. Ibid, 1/9/17, p. 30
4. Ibid, 2/13/17, p. 23
5. Ibid, 2/13/17, p. 22
6. Ibid, 3/27/17, p. 12
7. Ibid, 1/30/17, p. 9
8. Itaconic acid, Wikipedia, 6/19/17
9. Chemical and Engineering News, 2/6/17, p. 12
10. Ibid, 2/20/17, p. 13
11. Ibid, 5/29/17, p. 15
12. Ibid, 3/20/17, p. 13
13. Ibid, 5/29/17, p. 15
14. Ibid, 3/20/17, p. 12
15. Ibid, 5/22/17, p. 15
16. Ibid, 5/29/17, p. 28
17. Ibid, 6/8/17, p. 10

About the Author: Bernard Cooker is a member of Lee Enterprises Consulting, the world’s premier bioeconomy consulting group, with more than 100 consultants and experts worldwide who collaborate on interdisciplinary projects, including the types discussed in this article.  The opinions expressed herein are those of the author, and do not necessarily express the views of Lee Enterprises Consulting.