OVERVIEW OF WORLD BIOPLASTICS TECHNOLOGY AND MARKETS: FUTURE

DRIVERS, DEVELOPMENTS AND TRENDS FOR FLEXIBLE PACKAGING

Terence A. CooperARGO Group International

SPE FlexPackCon 2016, Memphis TN 2016-10-12

OUTLINE Basic definitions, classifications and drivers for

bioplastics Evolving feedstocks and biobased monomer

development and concept of platform chemicals Commercial and potential future biobased polymers for

packaging, “drop-in” versus new polymers and key producers

Biodegradable plastics for flexible packaging Some current flexible packaging markets and

applications, and bioplastics growth projections and market trends

“Green issues”, consumer and environmental concerns

CLASSIFICATIONS OF BIOPLASTICSBIOBASED OR RENEWABLE PLASTICS:

Organic plastics composed wholly or significantly of recently fixed (new) carbon from biological sources such as renewable plant, forestry, animal, algal or marine materials (based on C14 content measurement as defined by ASTM D6866) - USDA definition

Renewable within 1-2 years (vs. millions of years for petro-) via plant-biomass photosynthesis from CO2 (biological carbon cycle)

Focus is only on origin of carbon constituents

May be fully biobased or partially biobased

May be biodegradable or non-biodegradable. For non-biodegradables, end-of-life process is recycling or recovery

CLASSIFICATIONS OF BIOPLASTICSBIODEGRADABLE AND COMPOSTABLE PLASTICS:

Focus is only on disposal or “end-of-life” processes, independent of carbon sources

Biodegradability is determined by polymer structure, not carbon source

May be bio-based (renewable) or petro-(fossil-)-based

THESE TWO CLASSIFICATIONS, BIOBASED AND BIODEGRADABLE, ARE NOT MUTUALLY EXCLUSIVE

NB: BIOBASED DOES NOT NECESSARILY MEAN BIODEGRADABLE AND BIODEGRADABLE DOES NOT NECESSARILY MEAN BIOBASED

DRIVERS FOR BIOPLASTICS Growing legislative, regulatory, NGO and consumer concerns over

carbon footprint, climate change, environmental pollution and health; Paris Agreement (COP21)

Increasing government and consumer demands worldwide to reduce dependence on fossil fuels and feedstocks and convert to renewables

Conventional petrochemical plastics under attack, even though they use only about 2.5B barrels of oil annually (<3% of all oil used)

Increasing legislation globally restricting uses and disposal of petrochemical plastics and promoting bioplastics

Reduced production cost from agricultural/biomass feedstocks due to advances in catalysis, gasification, biotechnology and other processes to make cheaper, novel, improved-function materials

Renewables are increasingly being seen as a fundamental pillar of a coming bioeconomy where biological sources produce energy, chemicals and materials with lower carbon footprint

USDA “CERTIFIED BIOBASED PRODUCT LABELING PROGRAM”

• SETS MINIMUM THRESHOLD OF 25% NEW CARBON FOR PRODUCTS TO BE CONSIDERED BIOBASED

• FIRST “CERTIFIED BIOBASED PRODUCT” LABELS AWARDED MARCH 2011. NOW OVER 2700 CERTIFIED PRODUCTS

EUROPEAN COMMISSION LEAD MARKET INITIATIVE

Standards, labeling and certification

Legislation promoting market developmentProduct specific legislation and goals, e.g.

Packaging Waste Directives, Producer Responsibility and Plastic bag directive.

Innovation and legislation promoting development of biomass sources

Encouragement of Green Public Procurement

Financing and research funding

Circular economy package

EUROPEAN BIOBASED CERTIFICATION PROGRAMS• VINCOTTE “OK BIOBASED”

Certification marks for biobased content levels of:20-40% 40-60% 60-80% >80%

• DIN CERTCO Requires minimum organic material proportion of 50% and minimum biobased proportion of 20%Certification marks for biobased content levels of:20-50% 50-85% >85%

BIOBASED CHEMICALS, MONOMERS AND POLYMERS DEVELOPMENT Rapid development of biobased routes from renewable feedstocks to make

existing petrochemical-based monomers, polymers, plasticizers and chemicals, producing “drop-in” replacements from renewable sources

Many large chemical and petrochemical companies are now involved together with small companies and start-ups

Key factor in routes from lab to commercialization is partnering of groups of companies where each contributes different parts of the technologies and market knowledge required

Not possible 10 years ago. Necessary catalyst, biotechnology & synthetic biology knowhow now becoming available in tandem with current drivers e.g. volatile oil prices, fossil feedstock substitution, increasing focus on renewables, climate change (Paris agreement), sustainable development, circular economy, environmental concerns and consumer demands.

USDA: 2014, biobased products industry contributed $393 billion and 4.2 million jobs to US economy, displacing 300 Mgal petroleum and 10Mt CO2. Milken Institute/USDA study (2013): $720B opportunity for US renewables in next decade, equivalent to 20% of chemicals markets.

EVOLVING FEEDSTOCKS FOR BIOBASED POLYMERSFOOD CROPS, BY-PRODUCTS AND WASTES

Polysaccharides – starches (corn, potato, tapioca, rice, pea etc), sugars, pectin, chitosan, gums, alginates etc

Fats and Oils: Animal: fatty acid glycerides Vegetable: soy, castor, palm, waxes, triglycerides, etc Algal: oils

Proteins: Animal proteins: keratin, casein, whey, gelatin, collagen, spider

silk, meat, blood and bone meal Vegetable proteins: soy, zein, gluten Algal and fungal proteinsNON-FOOD CROPS AND WASTES

Lignocellulosic biomass– wood, straw, stover, bagasse, grasses Cellulosics – cotton, paper and paperboard Biomethane, carbon dioxide, carbon monoxide

CONCEPT OF PLATFORM CHEMICALSIMPORTANT CONCEPT

To make a renewably sourced material, it is only necessary to make the FIRST chemical or monomer in the synthesis chain from a renewably sourced feedstock

This first chemical or monomer is called a platform chemical or monomer and can be made from the renewable feedstock using biological, chemical, thermal, pyrolytic, supercritical, catalytic or other processes

All of the later synthetic steps can then be performed using standard chemical processes which have already been developed for petrochemical-based materials

For some materials such as copolymers, it may be necessary to have two or more platform chemicals, i.e. one for each monomer, to make them fully biobased, e.g. polyesters, polyamides, ethylene copolymers

BIOETHYLENE CHEMICAL PLATFORM

Ethylene Polyethylenes

Styrene Monomer

Ethylene Oxide/Glycol

EDC

Other

Polymers/Rubbers

Polyester

PVC

Alpha Olefins

PVA

Ethanol60%

7%

14%

12%

7%

Ethanol production ~ World Ethanol Production~ 70 million tonnes

World Ethylene Production ~ 110 million tonnes

Source: NNFCC

GEVO RENEWABLE ISOBUTYLENE PLATFORM

SOME BIOBASED MONOMERS AND CHEMICALS AT COMMERCIAL OR PILOT PLANT SCALE

OLEFINS: Ethylene – Braskem Isobutylene -- Gevo, Butamax, Lanxess, Global Bioenergies/Loreal, EnvergentACIDS AND DERIVATIVES: Lactic acid -- Cargill, Corbion, Myriant, Galactic-Total, Cellulac, etc Succinic acid -- DSM-Roquette (Reverdia), BioAmber-DNP, Mitsubishi, Mitsui, Myriant,

METEX, PTT, BASF-Corbion (Succinity), Showa Denko Adipic acid -- Verdezyne, Rennovia, Genomatica, BioAmber, Celexion 2,5-Furan dicarboxylic acid and esters – Avantium/BASF, Dupont/ADMGLYCOLS, POLYHYDRIC ALCOHOLS AND POLYOLS: Ethylene glycol -- India Glycols, Greencol, JBF, FENC, S2G, Liquid Light Propane 1,3 diol -- DuPont/Tate & Lyle, ADM, BASF/Oleon, METEX Butanediol – Novamont/Genomatica, DuPont/Tate & Lyle, Myriant, BioAmber, Mitsui,

LanzaTech Polyols -- Biobased Technologies, Cargill, Ford (from soybean oil); Covestro (from CO2)DIAMINES: Hexamethylene diamine – Verdezyne, Rennovia, Amyris Caprolactam -- Amyris C4 and C5 diamines -- DSM, Cathay Biotechnologies

SOME NON-BIODEGRADABLE BIOBASED PLASTICS FOR FLEXIBLE PACKAGING

Commercial: POLYOLEFINS - PE from bioethanol (totally biobased)

Polyolefin/starch blends (partially biobased) POLYAMIDES - PA 5,10; (totally biobased);

PA 4,10; 5,6; 6,10; 6,12; 10,10; 10,12 (partial bio) POLYESTERS - PET (PlantBottle®) – partially biobased

Developmental: POLYOLEFINS: Polypropylene, PVC POLYESTERS: PET (totally biobased)

PEF – polyethylene furanoatePTF – polytrimethylene furanoate

POLYAMIDES: PA 6,6

Mostly “conventional” rather than “new polymers”

ADVANTAGES OF RENEWABLE DROP-IN CONVENTIONAL MATERIALS

Current development largely for renewably-sourced conventional polymers rather than new polymers, since:

Market, supply chain and business infrastructure already developed (generally more difficult than science and technology)

Downstream conversion technology is understood and integrated manufacturing infrastructure available

Downstream products are identical to petrochemical products and fit existing conversion, applications and end-of-life infrastructure

Drop-in materials are chemically identical to petro-based materials and compete only on cost and quality

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SOME PRESENT AND POTENTIAL MANUFACTURERS OF BIOBASED NON-BIODEGRADABLE PACKAGING POLYMERS

Braskem, DSM, Solvay, Arkema, Sabic Polyethylene, PP, PVC

DuPont, Teijin, DSM, SK Chemicals, Toray, Indorama, M&G

Polyesters

BASF, DSM, Arkema, DuPont, Toray, Cathay Polyamides

Avantium/BASF, Dupont/ADM, Micromidas Furanoate polymers

GREEN POLYETHYLENE Braskem production in Brazil started 2010 using

ethylene from sugar cane ethanol, capacity 200 ktpa HDPE, LDPE and LLDPE grades available, identical

to petro-PE made by same polymerization process Currently higher cost than PE from shale gas

ethylene Advantageous carbon footprint and global warming

potential over petro-ethylene and provides green marketing credentials

Early packaging users have included Coca-Cola (Odwalla), P&G, Danone, J&J, Tetra Pak, Avery Dennison, Seventh Generation and Nestlé

COCA-COLA PLANTBOTTLE®

Coca-Cola PlantBottle® Current PlantBottle® PET bottles made with up to 30% by

weight (the ethylene glycol component) from sugarcane sources

This is up to 20% of renewable carbon

BIOBASED ROUTES TO TEREPHTHALIC ACID

isobutene p-xylene terephthalic acidVia p-Xylene Gevo: Fermentation of plant sugars (from lignocellulosic biomass) to

isobutanol, then chemical route to isobutene and p-xylene Virent (Tesoro)/Renmatix: Chemical catalytic BioForming® Platform

from plant sugars or cellulosic biomass to p-xylene. 10,000 gallon/yr pilot plant in operation. 100% biobased PET bottles exhibited with Coca-Cola at Milan Expo 2015-06-03.

Anellotech/Suntory/Toyota: Catalytic Fast Pyrolysis (BioT-Cat) route to convert biomass to aromatics (BTX). Pilot plant in Silsbee TX

Micromidas: Fermentation process from cellulosics to furanic intermediates to p-xylene

BioBTX bv (Holland): Catalytic pyrolysis from glycerol. Pilot plant 2017

BIOBASED VERSUS PETRO-BASED FEEDSTOCKS FOR TEREPHTHALIC ACID PRODUCTION

Petroleum is hydrogen-rich while biomass, cellulosics and glycerol are oxygen-rich and relatively hydrogen-poor

BTX (benzene-toluene-xylene) production from petroleum generates co-product hydrogen. Biomass conversion to BTX requires added hydrogen, causing additional cost or reduced raw material efficiency

p-Xylene must then be oxidized again to make TPA, removing the hydrogen just added

This leads to low overall terephthalic acid yields (<50%) based on plant sugars or (ligno)cellulosics and higher cost than petrochemical routes

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POLYETHYLENE FURANOATE (PEF) Avantium/BASF; Dupont/ADM; Micromidas; AVA Biochem; Corbion:

routes from plant sugars or cellulosics to furan-2,5-dicarboxylic acid (FDCA):

as alternative monomer to terephthalic acid

Potentially more favorable economics from plant sugars than terephthalic acid . No added hydrogen is needed. Requires less than half the mass of sugar to produce a kg of FDCA compared to purified TPA (A. Harlin, VTT, Finland data)

Produces PEF as alternative to PET with improved properties

FURANOATE POLYESTERSAVANTIUM – POLYETHYLENE FURANOATE (PEF): Pilot plant in operation in Geleen, Holland. Development with Coca Cola for beverage bottles,

Danone for food packaging, and ALPLA Werke. 2014 $50million consortium with Danone, Swire Pacific

and Coca-Cola to commercialize PEF for packaging 216 €20 million raised for commercial plant. Investors

include Coca-Cola, ALPLA and venture capital. BASF JV “Synvina” to build 50ktpa plant in Antwerp BE. Strategic partnerships with Mitsui and Toyobo for film,

sheet and fiber products in Asia. DuPont/ADM - POLYTRIMETHYLENE FURANOATE (PTF) Furane dicarboxylic acid methyl ester (FDME) 60tpa pilot

plant planned in Decatur, IL.

BIODEGRADABILITY Biodegradable - undergoes enzymatic fragmentation and

degradation by microorganisms to form water, CO2 (aerobic) and methane (anaerobic)

Very imprecise term – no defined criteria, environments, products or time limits. Biodegradability under one set of conditions does not necessarily imply biodegradability under other conditions

COMPOSTABILITY Meets specific requirements of industrial compostability (eg

ASTM D6400, EN13432 or JIS K6950 ) or home compostability standards (Vincotte OK Home Compost) – aerobic processes

Certification covers a product, not just a material, and includes determining the maximum thickness of material which can be degraded within one composting cycle

Not all biodegradable materials are biobased and not all biobased materials are biodegradable.

NOT a license to litter.

MAJOR COMPOSTABLE CERTIFICATION PROGRAMS

• VINCOTTE “OK Compost” and “OK Compost HOME”EN13432

• Association for Organics Recycling (AfOR)UK.• DIN CERTCO

Japan Green Pla

Biodegradable Product Institute (BPI) US ASTM D-6400

BIODEGRADABLE AND COMPOSTABLE PLASTICSMajor current commercial types are:

Polylactic acid (PLA) – biosourced lactic acid monomer from starches or biomethane, then ring-opening chemical polymerization

Polyhydroxyalkanoates (PHAs; PHB, PHBV, PHBH etc)- direct fermentation of starch, plant-based fatty acids or biomethane

Aliphatic and aliphatic/aromatic copolyesters (PBS, PBSA, PBAT, PCL) – mostly petro-based but becoming biobased

Starch blends and derivatized starch blends

Cellulose and some derivatives and blends

Under development: Protein-based materials, e.g. keratin-, zein-, casein-, whey and soy-

based (e.g. whey-based barrier layers) Bacterial-, algal- and fungal-based materials

SOME CURRENT LEADERS IN BIODEGRADABLE PLASTICS Primary Polymer Producers

PLA NatureWorks-PTT, Corbion, Hisun PHAs From starches: - Kaneka, CJ CheilJedang,

Ecomann, Tianjin BioGreen/DSM, Tianan, Bio-On

From sucrose: Biomer

From plant oils: MHG

From biomethane: Newlight (Ikea), Mango Materials Aliphatic/Aromatic Polyesters (PBAT)

BASF, Jinhui Zhaolong, Kingfa, Xinfu

Aliphatic Polyesters (PBS, PBSA etc) Kingfa, Xinfu, Sinoven, DSM, Mitsubishi, Showa Denko, Hexing, Novamont, SK Chemical

Polycaprolactone Perstorp, Daicel, BASF

PROJECTED GLOBAL BIOPLASTIC CAPACITY

BIOPLASTICS PRODUCTION CAPACITY BY POLYMER TYPE

Polymer Type 2014 Volume Ktpa 2019 Projected Ktpa

Bio-Polyethylene 201 196

Partially-biobased PET 602 6005

Polylactic acid 207 440

Starch blends 170 188Biodegradable polyesters 221 518

Polyhydroxyalkanoates 34 102

GLOBAL BIOPLASTICS CAPACITY BY MARKET

MAJOR CONCERNS WITH BIOBASED POLYMERS Use of foodstuff feedstocks. Major work on routes from

non-food biomass to avoid competition with food Land and water availability and competition for these

with foodstuffs and other uses Whether bioplastics really have lower carbon footprints

than petroleum-based materials, given agricultural and fuel inputs to grow the crop feedstocks

Not all chemical and polymer production will become bio-based.

BIOPOLYMERS WILL ONLY BE SUCCESSFUL IF:1. Equal product functionality is delivered at the same or lower cost2. New functionality is provided at acceptable cost3. The carbon footprint in the value chain is improved

FUTURE GROWTH OF BIOPLASTICS IN PACKAGINGThis will depend on:

Future trends in oil prices and impact of shale gas

Continuing transition from petro-based to biobased feedstocks and improvements in bioplastics pricing, carbon footprint and performance

Development of economic production routes from non-food feedstocks of biobased monomers and polymers identical to existing petrochemical counterparts which are drop-ins for existing processes, manufacturing facilities and recycling infrastructure

Increasing deployment of recycling, recovery and disposal (composting, anaerobic digestion) infrastructure to aid sustainability

How well the use of bioplastics addresses future environmental, societal, political and economic issues

THANK YOU FOR YOUR INTERESTDR. TERENCE A. COOPER

ARGO GROUP INTERNATIONAL

US Phone: +1 302 366 8764; +1 302 420 9467UK Phone: +44 (0) 203 286 0930; +44 (0) 7857 273 105

tacooper@post.com www.pcn.org/Cooper.htm

Specialist consultancy services in:Water-soluble, biodegradable and compostable plasticsBiobased and renewably-sourced plasticsMaterials and formulation development and selectionMarket and applications development and analysis

Member of the Plastics Consultancy Network and the Chemical Consultants Network