Recycling used Hygienic Disposables

Marcello Somma, Sustainability Innovation Manager of Fater SpA (Italy) described the technical progress made on their 500kg/batch pilot plant developed to recycle diapers and other absorbent hygenic products (AHPs) .  He claimed it was achieving separation efficiencies of >95% without degrading the reclaimed materials which were produced sterile and at moisture contents below 20%.  Fater is a JV between Procter and Gamble and Angelini.

In Italy alone, 900,000 tonnes per year of used AHPs are landfilled or incinerated every year, and a system of segregation and collection of such waste already serves 7 million people.

The pilot plant looked like a very large drum washer/dryer which could discharge clean dry waste into a shredder/separator.  1 tonne of used diapers fed to the pilot plant contained about 50% body fluids and yielded 350kg of sterilised absorbent comprising fluff pulp and superabsorbent. 
 This recycled cellulose stream is being evaluated in pet-care absorbents, spill control products, compost, gas generation via digesters, paper mills, and even viscose production.  It also yields a recycled plastic stream comprising 150 kgs of white mixed PP/PE polymer chips which Fater claim can be fed to a wider range of processes than standard recycled plastic.

The process, when scaled up, will be good for citizens who will get a dedicated AHP collection service and cash savings (if the proposed pay-as-you-throw taxes are introduced).  Local councils will save money on landfill and increase their contribution to EU recycling and biodegradable waste targets.  Waste disposal companies will develop new business if they instal the Fater system and of course the environment will benefit from the negative C-footprint (-17kgs CO2/tonne) if Italy as a whole adopts the process.

The next step is to instal a larger continuous pilot plant with a capacity of 8000 tonnes/year in Veneto by the beginning of 2015.

Automotive Biopolymers

José Rodilla, Senior Product Development Engineer with Faurecia - the world’s 6^th largest supplier to the auto industry with a turnover of €16 billion - described their development of “NAFI Lean”, a composite of 80%PP and 20% hemp intended to replace their P/E copolymer in cockpits, door panels, instrument panels etc.  It’s lower density and reduced thickness compared with P/E copolymer or GRP are the key benefits with reduced fuel consumption being the USP for the auto industry.

Short-cut hemp is compounded with PP to make chips for injection mouldings.  Their use provides:

  ·         25% weight savings.

  ·         20% LCA Savings (CO₂).

  ·         Processability on existing machinery with a 6% reduction in cycle time.

  ·         A step on the road to 100% bio-composites.

It is more expensive than P/E copolymer but currently perceived as the best compromise between quality and weight.  It is now used in the Peugeot 308.  3000 tonnes are produced in the EU and a further 10000 tpa planned for  Asia.

Faurecia is also developing its own 100% bio-based polymer “Biomat”,  for non-visible auto parts.  Biomat is 100% poly-butylsuccinate made from tapioca starch using monomer technology from BioAmber and polycondensation technology from Mitsubishi Chemicals.

Biodegradable Gas Barrier Films

Domenico de Angelis of Nippon Gohsei (Japan) believes their Nichigo G-Polymer™ (PVOH) makes a better gas barrier film than EVOH and in dry atmospheres it can be 50x better.  So for dry foods in controlled storage at humidities below 60% RH PVOH will outperform EVOH to an extent that downgaging  and cost saving is possible.  

PVOH gives films with glass-like transparency which biodegrade like cellulose and are therefore fully compostable.  The packaging film used PVOH as the middle layer of a sandwich with PLA as the outer layers.  There were problems with adhesion and these had been solved using a special tie resin.  The 3-layer film could also be ground and recycled as PLA; the PVOH being water soluble could be washed away. A typical construction would be 20 microns of G-Polymer inside  30micron layers of PLA each bonded to the G-Polymer with 10microns of adhesive to give an oxygen transmission rate of 0.02 ccs/square metre/day at 23C and 50%RH.

Nippon Gohsei make 70,000 tonnes/year of PVOH in Japan.  Nichigo G-Polymer™ is the world’s first amorphous PVOH and combines the strengths of regular PVOH and EVOH.

Certification of Biopolymers

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Miriam Lübbecke of DIN Certco (Germany) specialises in biopolymer certification using a scheme which is totally transparent with all details publically available on their website.  When a manufacturer applies for a certificate, DIN Certco assesses the relevant literature and decides how to test the product.  It uses appropriate independent test laboratories chosen from its list of 130 accredited and contracted testing partners, issues a report on the results,  and if appropriate, the certificate of conformance and permission to use the logo.  “Biobased” certificates cover three levels, 20-50%, 50-85% and >85% biobased according to ASTM D 6866 methods which requires a total organic carbon of >50% and a C14 content above 20%.  Testing is required every second year.

“Compostable” certificates can include 4 logos, “the seedling” for industrial compostability, and 3 “DIN-Gepruft” logos covering industrial, home composting and additive content. ASTM D6400 is among the approved tests, but only the Australian standard AS 5810 is used for home composting certification.  The tests include ultimate biodegradability, disintegration, plant toxicity, EN 13432 chemical analysis and, for home composting the ASTM E 1676 earthworm toxicity test.

“Recycled Content” is determined by DIN EN ISO 14021 and audits of the manufacturing site to determine traceability under DIN EN 15343.  A new “All-in-one” DIN Certco logo covering all 4 properties is now available.

Biocomposites from Starch, Natural Fibres and Polymers

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Leon Mentik of Roquette (France) explained how they bought maize, potatoes, wheat, tapioca and peas for processing and used the extracted starches to make bioplastics.  After cellulose, starch was the second most abundant polymer on the planet with 1.3 billion tonnes being produced annually in plants.  6% of this (80 million tonnes/year) is extracted very easily, the by-products being proteins and fibre for use as food.  Starch is highly reactive and easily grafted or alloyed with other materials to add desirable functionalities.  It can be used directly to make starch-based plastics, either as blends with other polymers or in the form of durable thermoplastic starch.  It can also be easily hydrolysed to glucose to provide the starting point for the whole range of bio-based or bacterially produced polymers.

Gaialene® is Roquette’s durable, i.e non-compostable, starch-based plastic which has been certified against ISO 14040/44 by Price Waterhouse Coopers with a carbon footprint of 0.74 kg CO₂ eq./kg resin or ~1/3^rd that of PP.  It has applications in replacing polyolefins in  films, injection moulding and foams, to produce  shopping bags (for recycling or incineration), multilayer shrink wrap, moulded paint containers, fabric coatings, mud-guards, sound insulation and packaging foams.  It is fully recyclable, GMO-free and does not compete with food crops.

Sergio Fita of Aimplas provided another comprehensive overview of the Technological Institute and its work on composites for those who joined the conference late.  He reiterated the variability issue which arises because natural fibres are inherently variable and moisture sensitive and said AIMPLAS was working to overcome this deficiency.  Examples of successes were the woven Flax/Jute battery case which used an epoxidised acrylate soybean-oil resin (ASEO); the Roadside Grit Box using wet compression moulded Flax/biobased unsaturated PET resin (thermoset); the woven flax/PLA tractor door, the Cayley project honeycombs based on FR-treated bio-resins and natural fibres and the Ecoplast project for automotive parts made by extruding PHB polymer onto flax fabrics, calendaring to impregnate and then moulding to shape.

Biopolymer Waste in Spain

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Francesc Giró of the Catalonia Waste Agency was concerned that the desertification now occurring in southern Europe needed to be corrected by adding massive amounts of organic matter to the soil, and this required more composting infrastructure.  In reality 70% of waste organic matter in the region is still land-filled or incinerated and action was needed to allow this to be collected separately and composted.  The target is to compost 50% of organic matter by 2020 and in Catalonia a tax on landfill and incineration is encouraging movement in this direction.

• ·         Door to door collection of food waste is required.
• ·         Compostable bags need to be used for this collection.
• ·         Disposable nappies were a huge problem, accounting for 2.5% of all waste.
• ·         Compostable diapers could make a large contribution to compost production, but they were currently twice the price of the petro-diapers.

Judit Janasa of TOMRA Sorting and Recycling commented on the difficulties of separating mixtures of plastics containing biopolymers but concluded that their sorting machines would soon be able to remove compostable bioplastics from the recycling stream.  They have installed 3470 sorting machines worldwide, mostly in the Iberian peninsula.  These machines use electromagnets, high intensity visible light, infra-red both transmitted and reflected, X-ray, atomic density, and laser fluorescence sensors to identify different materials.

The machines are tuned to the key wavelengths reflected or transmitted by each polymer and digital images taken at these wavelegths are analysed pixel-by-pixel so that for a bottle for example, the cap, label and body polymers are identified and recorded.  Problems arise with black polymers (no reflection), and labels made of paper prevent the underlying polymer being seen.  PLA and PET bottles which look identical can be separated easily.  The software in use can be updated for every new polymer once samples have been tested.

Asked how multilayer bottles or films would be treated, Ms Janasa said the majority polymer would take precedence.

Biopolymers from waste and Compostable Packaging

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Mercedes Villa-Carvajal, a biotechnology researcher at the Ainia Technology Centre (Spain) described the use of waste liquor from the orange juice processing industry to produce poly-hydroxybutyrate for bottle production.  The PHB was compounded with cellulose fibres and fillers and injection moulded to make the bottles. (“Phbottle”)

Pretreatments prepared the raw material to receive an inoculation of microorganisms.  Bioprocessing involved fermentation and separation of the required monomer.  Post treatment involved polymerisation.

In principle, any carbon source (e.g. food waste) could be pretreated to receive any one of a range of microorganisms, patented or unpatented, GMO or not, provided with oxygen, and fermentation would result.

Jordi Simon and Matthias Klausmann of BASF (Germany) used the term BioCom to refer to their compostable polymer recommended for use where organic matter is left behind after the food has been taken out of the packaging.  BioCom in fact appeared to be being used as a term of the biodegradable and compostable properties of their Ecoflex® polymers which could be made either from petro- or bio-based sources as required. Ecovio® is their blend of Ecoflex® and PLA.

Ecovio® is finding applications as an agricultural mulch film and as a bag for food waste intended for composting.  A new application was demonstrated at the conference, a 100% biodegradable coffee capsule designed to allow coffee and its carrier to be added to the compostable waste stream.  The capsules packaging was also a 3 layer compostable film.  The system had yet to be adopted by any of the major coffee capsule makers and appeared to be a unique design using a permeable tea-bag nonwoven top cover rather than air-tight foil.

Customised Bioplastics

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Chelo Escrig of AIMPLAS ran through a range of bioplastics developments underway at AIMPLAS. A new extrudable polyvinyl alcohol had been developed and this allowed production of a 3-layer oxygen and moisture barrier film comprising polyvinyl alcohol sandwiched between layers of PLA (“C-Calpe” and “Bio4map”).  It could also be co- injection moulded with polyethylene. PVOH was unique among polymers in that it was not polymerised in that form.  Vinyl acetate was polymerised to PVAc and then hydrolysed back to PVOH.

PLApack was a highly plasticised version of PLA film which had low modulus and hence suitable for a wider range of packaging films.
Hydrus was a PLA tubing suitable for micro-irrigation with an operating temperature range up to 103^oC.
Biopolyim A was a soft PLA containing newly developed plascticisers based on lactic acid oligomers.
Innorex was PLA produced without metal catalysts using ring-opening polymerisation of a lactide in a reactive extrusion process.  The lactide was fed into an extruder with laser, microwave and ultrasound being shown as the initiators of the polymerisation.
BioBottle was injection moulded from PLA with supercritical CO₂ injected into the first of two extruders.  The resulting volatiles were vented from the second extruder which delivered odour-free PLA to the mould.

David Bertomeu of FKUR reviewed their range of compounds for use in food packaging.  They buy PLA, PHA, PBAT, PBS and Cellulose Acetate and compound them in different ways to make Bioflex®, Biograde®, and Fibrolon®  for use in agricultural mulch films and flower-pots. For the catering industry they make a complete range of compostable plastic cups, plates, cutlery and disposal bags to that the entire table setting and any food waste can be gathered for delivery to the composter.  They also buy biobased PE and make Terralene™ blends to get a range of properties which allow substitution of the full range of polyethylenes from LDPE to HDPE.

Bio-based Polyamides

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Pep Catalan, Sales Manager – Speciality Polyamides for Arkema (France) said they intended to continue to lead the field in production of high performance polyamides based on castor oil chemistry.  Their Rilsan® process, established in the 1950’s as a way of avoiding the Dupont nylon patents, did not compete with food, avoided deforestation and used a crop which could be grown in semi-arid areas.  It was now a high-performance, high temperature resistance bio-plastic for engineering applications.

Compared with the petro-polyamides, on a cradle to factory gate basis, it reduced global warming potential by up to 52%, saving 4.7 tonnes CO₂ emissions for every tonne of polymer produced.

A new elastomeric version, a PA/polyether block copolymer called “Pebax”, is now available.  Here the PA is bio-based but the polyether isn’t.  “Pebax Rnew” is however based on 95% renewable carbon and has high energy absorbtion and recovery.  This springy polymer is being developed for running shoes and ski-boots.

“Rilsan Clear” is a cycloaliphatic PA, now also bio-based. It has glass-like transparency.

A New Engineering Bio-Composite

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Frank Steinbrecher of Mitsubishi Chemicals (Germany) introduced Durabio®, a renewable durable polycarbonate-like bio-polymer based on isosorbide made from sorbitol which in turn came from glucose made from starch.  

The technology had been developed by Roquette.  In 2010 the Durabio® capacity was 300 tpa and last year it was 5000 tpa.  The injection moulding grade has high hardness and the end-products are positioned between PMMA and PC for transparency. Compared with PC, Durabio® also performs better on weathering but is slightly worse for tensile strength.  It is being used to make high-gloss coatings for mobile phones by injection moulding and as glass-replacements in roadside sound barriers by extrusion.  Automotive parts are also made by extrusion and have proved to have the necessary optical, chemical and safety characteristics for interior trim.  It is less flammable than either PMMA or PC.  Asked if it was weldable to ABS like PC is, Mr Steinbecher thought it was, in principle, but Mitsubishi would be happy to test this.

Mitsubishi’s GS Pla was their biodegradable polymer originally made from petrochemicals and now available from bio-succinic acid.  Despite its name it is a polybutyl succinate and not a PLA.

Biopolymers in Nestlé

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Carlos de la Cruz, the Head of Regulatory Affairs for Nespresso Capsules criticised the industry for confusing consumers with too many eco-claims and argued that the packaging was the key to improvement.  It not only protected the product and kept it fresh but could also be used to communicate with and educate the consumer.  Communications had to be based on comprehensive life-cycle assessments of the food and its pack from farm to fork.  Bioplastics made from foodcrops can improve the environment but crops do need fertilisers and pesticides.  These are based on fossil carbon and have additional adverse impacts on the ecology per se.  Irrigation if needed is a further negative impact in LCA terms.  Furthermore, bioplastics food packs must protect the food from spoilage to the same extent as petro-polymers or the resulting extra wastage will easily nullify any benefits. 

Examples of successful packaging using biopolymers where the benefits were explained on the packs included Purina One Beyond dog food, PLA twist wrap for sweets on Quality Street in the UK, Herta Sweet Ham using a 20% bio-sourced wrap in France, the Davy Milk carton bioplastic cap and “Vittel” water bottles using 30% biosourced PET in France.  

The Bioplastic Feedstock Alliance had been formed this year and brought together companies such as Nestlé, P&G, Unilever, Coca Cola, Heinz, Nike and Ford among others.  The next generation of bioplastics (Gen 3) would be derived from non-food sources such as wood, waste, drought resistant plants and algae.  (Gen 1 was PLA, described as food-based and unsuitable for widespread use in packaging.  Gen 2 were the “drop-in” polymers suitable for widespread use but expensive and made from sugar via ethanol.)

Green and Sustainable Composites

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Kerry Kirwan of Warwick University (UK) has re-evaluated the use of jute, flax and hemp in composite reinforcement.  These materials have been used mainly in electric cars where weight reduction c.f steel or GRP is a virtuous circle, and where, unlike the money-no-object F1 cars, carbon fibre is too expensive.  Unfortunately the variability of tensile properties from these natural product prevents them from performing as well as might be expected, so Warwick has been looking at their energy absorbtion properties with applications in crash-structures in mind.

Surprisingly, woven hemp or flax crash cones in a biobased resin matrix worked better than aerospace grade carbon fibre in epoxy resin.  These biocomposites  have now been incorporated into a Lola F3 car.

Marta Pascual of DSM Composite Resins (Holland) listed the challenges facing the EU composites industry:

• ·         Replacement of styrene due to its problems of flammability, toxicity and odour.
• ·         Replacement of the catalysts used for hardening: cobalt salts and tertiary aromatic amines.
• ·         Reducing dependence on fossil carbon sources and their price volatility.

One of their key products was in fact that contradiction in terms, the thermostable thermoplastic, an unsaturated polyester resin used in automotive applications (“Palapreg”) and artificial marble (“Synolite”).

Beyone™ (201-A-01) was a  40% renewable, cobalt-free, styrene-free resin used in the manufacture of wind-turbine blades by DSM/Siemens.  Coupled with Blucure™ curing technology, it had won the JEC Innovation award (2012).

Sustainability as a business strategy: Ecodesign

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Miguel Sibila of the Department of Sustainability and Industrial Valorisation at AIMPLAS observed that our environmental problems were the natural consequence of unrestrained economic growth.  This had been recognised as long ago as 1987 when the Brundtland Report made the case for capitalism giving social and environmental issues equal weight with economic issues.

The resulting sustainability movement began with prevention of pollution, moved to a focus on the environmental impacts of industrial processes and now encompassed the entire global environment.  In fact the production of green products had become one of the main economic drivers, and all consumers would now choose lower carbon footprint products in the absence of any price/quality disadvantages.  40% of consumers are willing to pay a premium.

Mr Sibila made the case for Eco-design or basing a product’s design on LCA,  because 80% of environmental impacts are fixed during the design phase.  

Ecodesign would involve:

• ·         Minimising raw material use
• ·         Improving energy efficiency and optimisation of any transportation needs
• ·         Using natural products, recycled materials and biopolymers rather than petro-polymers.
• ·         Making biopolymers from organic waste rather than foodcrops.
• ·         Reducing waste by optimising packaging and its recycling
• ·         Altering production processes to suit environmentally friendly materials

...and finally using certification and eco-labels to communicate with the consumer.

Bio-polyethylene Life-Cycle Analysis

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Martin Clemesha of Braskem (Brazil) reminded us that Brazil had the world’s best climate for growing sugar cane and was therefore the best place for producing biofuels and biopolymers.  Once again the land-use issue was dealt with thoroughly. 1 hectare of land can produce 77 tonnes of cane which can make 6700 liters of ethanol or 3 tonnes of ethylene or polyethylene per year.  Braskem’s capacity for PE, now 200,000 tonnes/year represented 2% of Brazil’s total ethylene production or 0.02% of Brazilian arable land.

On a cradle to factory gate basis, the “I’m green” PE had a negative Global Warming Potential of -2.15kgs CO₂/kg PE.  The by-products of ethanol production, vinasse liquor and bagasse solids, both contribute to this benefit. The vinasse liquor (13 litres per litre of ethanol produced) is phosphorous-rich and used for irrigation, replacing some petro-fertilisers which would otherwise be needed.  The bagasse (cane minus the sugar) is burnt in the power station providing more than enough electricity for the process.  Overall, the process uses 1/5th of the fossil carbon used for petro-PE production.

Bio-LDPE is now available alongside the linear-low and high density grades.  Illustrations of new applications included Huggies diapers in Asia.

Asked about the costs of the bio-PE Mr Clemesha said it would be a long time before they could compete with petro-PE.  They had made massive investments and “I’m Green” would be a premium product for a long time. He could not say how much more expensive it would be but commented that it could well be the cheapest bio-plastic.  Could the bagasse be used in composites?  No, it was susceptible to rotting.

Horizon 2020: Opportunities for Biopolymers

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José Manuel Gonzalez, the Spanish Delegate and Contact Point at the Ministry of Economy and Competitiveness, International Programmes Directorate, European Programs Division (Spain) enthused about the EU’s Bioeconomy objectives for 2020 without getting bogged down in anything too specific.  

The objectives included:

• ·         Discovering and exploiting new terrestrial and aquatic biomass resources to minimise environmental impacts.  Marine biomass could yield many new molecules.
• ·         Developing integrated second and third generation bio-refineries.  (First generation refineries used food-crops as raw material.  2^nd generation will use forestry, 3^rd generation will use waste products.)
• ·         The work programme for 2014-15 (€486M) will focus on Sustainable Food Security, Blue Growth (Seas and Oceans), and Innovative Sustainable Inclusive Bioeconomics (!).
• ·         Specifically the “Value Chains” of bio-based industries would be more important. E.g.

         o   Biofuels, biochemicals and biomaterials from lignocellulosic feedstocks.
         o   Utilisation of the next generation of forest-based value chains for new added value products.
         o   Utilisation of the next generation of agro-based value chains to realise the highest sustainability and added value from improved agricultural production.  New oil crops would be sought.
         o   Realising sustainable bio-energy production by backwards integration with bio-refineries making high added value materials.

• ·         Research on converting atmospheric carbon dioxide into useful chemicals would be encouraged.
• ·         “Waste” would be redefined as an attractive source of raw materials.

In summing up, Mr Gonzalez said EU programmes (and hopefully the Job Titles. Ed.) would become less R&D oriented and more applied.

Bioplastic Opportunities and Challenges

Summaries of the papers given at the Bioplastics and Sustainable Composites conference at AIMPLAS, Valencia in March 2014 are being posted here...

Constance Brükerl, Environmental Affairs Manager at the European Bioplastics Association reviewed how the market for bioplastics was developing, making it clear that the Association which had been set up with biodegradable plastics in mind was now heavily involved with non-degradable materials i.e. conventional polymers produced from non-fossilized biomass.  These were now referred to as bio-based or durable bioplastics.

·         The Durable bioplastics market would grow seven-fold in the 5 years from 2012 to reach 5,000,000 tonnes by 2017, this growth being driven by PET30, a bottle polymer blend of 70% PET and 30% bio-PET.  (Clearly only 30% of the PET30 blend in this statistic is bio-PET)

• ·         Bio-polyethylene would grow steadily and by 2017 “drop-in” bioversions of  PA, PU, PC, PVC, PP and durable starch blends would all be available.
• ·         Use of foodcrops to make durable bioplastics was described as negligible: stopping it would confer no benefit to society.
• 
  

·         Biodegradable plastics would grow from 600,000 tonnes in 2012 to a million tonnes in 2017, with half of this growth being driven by PLA expansion.

• ·         75% of this market was in packaging, catering and agriculture.  Regenerated cellulose, presumably cellophane and acetate packaging film was included.