Best available and emerging
technologies for PVC production,
processing and disposal
A Sevenster
Fourth Andean Conference on PVC Sustainability
Bogota, Colombia, September 28, 2010
Contents of the presentation
● Best available and emerging technologies for PVC
– Production and processing
– End of life
● Additives
– Status of core additives
– Developments
● New PVC carbon footprinting & sustainability tool
● (Optional background slides) Eco-profiles, LCA and
EPD
BAT in PVC manufacturing and processing
THREE PILLARS
● Voluntary
commitments
● Good Practices
Responsible manufacturing
Health
Environment
Safety
Some voluntary commitments
● Australia
– Industry Product Stewardship commitment
launched in October 2002
– Some of the commitments
● Residual VCM in finished resin < 1 ppm:
ACHIEVED
● VCM emissions not greater than 50g/tonne PVC:
ACHIEVED
● Phase out of cadmium stabilisers by 2003: ACHIEVED
● Phase out of lead stabilisers by 2010: ON TRACK
● Europe (next slide)
● South America
– Brazilian pipes and fittings producers committed to replace lead
stabilisers by calcium/zinc
● USA
– Industry initiatives to phase out lead
Voluntary commitments in Europe
● ECVM industry Charters
– Voluntary commitments to reduce environmental impact of manufacturing
activities
● Target setting for emission limits, essentially EDC and VCM
● Apply Best Available Techniques (associated BAT documents)
● Reviews by an independent third party
– VCM and S-PVC (1994), E-PVC (1998)
– 3rd verification of VCM/S-PVC Charter and 2nd verification of E-PVC Charter
currently in progress
– More information on www.pvc.org
● Vinyl 2010
– Refer to presentation by Helmuth Leitner, but as reminder:
● Phase out of cadmium
● Progressive phase out of lead, complete by 2015
● Phase out of Bisphenol A in polymerisation
● Risk assessments on all phthalates
● Development of recycling
Good Practices
● ECVM Annual Health, Safety and Environment
Conference
– 30 - 40 participants, typically production managerial staff. All
companies represented
– One and a half day
– Review of accidents, incidents and near misses (“True
confessions”)
– Exchange of information on HSE issues related to manufacturing
● US companies also meet regularly to discuss safety in
manufacturing
Emerging technologies for PVC production
● Incremental improvements of the
established processes
– For example recovery of process water
● Environmental impact of current acetylene
process worse than ethylene process
– Could it become sustainable?
● Raw materials can be obtained from
renewable resources
– Ethylene from bio-based ethanol (Brazil) or
from methanol synthesized from waste
(“Methanol to Olefin” processes)
– Chlorine obtained from sea salt with
electricity from renewable sources
BAT for end of life treatment of PVC
● Landfilling to be avoided wherever possible
– Unsustainable “solution”, waste of space and resources
● Recycling to be favoured, because it’s best for saving resources and energy
but
– Collection of sufficiently homogeneous waste streams is an (essentially economic)
issue
– It can be hampered by standards, regulations (e.g. REACH) and public
acceptance
● Energy recovery is an option, but PVC has disadvantages compared to e.g.
polyolefins
– Constraints on incinerator design/operations to keep corrosion manageable; it is
feasible up to a chlorine content of 5-6%
– Generation of neutriaisation residues
● Cooperation of the value chain is essential for success
Global Warming potential reduction through recycling
●
●
●
●
Recent study by PE International
The figure depicts the results in terms of Global Warming Potential
The diagram clearly demonstrates that incineration carries much higher
burdens (3-4kg CO2-eq.) than mechanical recycling
“System expansion” refers to the inclusion of new production of PVC with additives
(which are different for cable and rigid PVC)
Emerging technologies for end-of-life PVC
● Mechanical recycling
– Vinyloop/Texyloop (See Vinyl 2010 presentation)
– Progress in sorting and separation technologies, allowing to recycle more
“difficult PVC waste”: For example Autovinyle in France
http://www.autovinyle.com/en_index.html
●
Feedstock recycling
– Lots of laboratory studies on gasification and pyrolysis, but very few
commercially demonstrated processes
– High investments
● Energy recovery from waste on PVC production sites
– Energy and sometimes HCl recovery
● Recovery of incineration residues
– Neutrec (developed by Solvay)
– Halosep (developed by Watech/RGS90/Stena with
the support of Vinyl 2010)
Autovinyle
process
Manufacturing products from PVC recyclate
for dismantled
parts
(Autovinyle)
ELV
Collection of
PVC parts
Densification
and
micronisation
 Pévéchouc ®
Calendering
or injection
The Neutrec ® process (Solvay)
● The Flue Gas Cleaning
Residues collected in the
bag filter are mixed with
hydraulic binders, then
placed in an aqueous
solution with certain
additives
● The suspension is filtered
● The insoluble part contains
in particular most of the
heavy metals. They are
solidified into inert matter
● The brine is further purified
and reused in the
manufacture of sodium
carbonate
● See www.neutrec.com
The Halosep ® process
● Recovers 98-99 % of the chlorine from
incineration flue gas waste residues in
the form of salts
● Applicable to Semi-Dry and Wet
incineration processes
● Reduces by 50–75 % the amount of
neutralisation waste to be disposed to
landfills and improves its leaching
properties
● The treated waste complies with the
leaching limit criteria for heavy metals
for non-hazardous waste
● The main product is a salt brine free
from dioxins, furans and heavy metals
● Cadmium, zinc and lead can be
extracted in various amounts
Additives
● Status of core additives
– Plasticisers
– Stabilisers
● Developments in plasticisers
Plasticisers – three main groups:
Products
LOW molecular
weight phthalates
SVHC *
• DEHP
• BBP
• DBP
• DIBP
HIGH molecular
weight phthalates
non-SVHC
Other plasticisers
• DINP
• DIDP
• DPHP
• DIUP
• DTDP
• Adipates
• Benzoates
• Citrates
• DINCH
• Others
There are ~ 100 plasticisers on the market but Phthalates represent ~ 90% of the WE
plasticiser market
15
Plasticisers are mostly used in
Flexible PVC products
LOW molecular
weight phthalates
HIGH molecular
weight phthalates
• Medical (DEHP)
• General purpose PVC
applications (DEHP)
• Adhesives (DIBP)
• Cosmetics
(DBP/DIBP)
• PVC Wire & cable
• PVC Flooring & wall
covering
• PVC Film & sheet
• PVC Synthetic leather
• PVC Coated fabrics
• Automotive
Other plasticisers
•Toys
•Food contact
•Sealants
•Medical
•Niche applications
16
Worldwide Plasticiser
Consumption
Other
Other
Other
Other
Other
DINP/DIDP
DINP/DIDP
DINP/DIDP
DINP/DIDP
DEHP
DEHP
DEHP
DEHP
DEHP represents 50% of the
phthalates used Worldwide…
1)
2)
…but only 17% of the phthalates
used in Europe
Notes :
Other Plasticisers include Adipates, Trimelliatates, Benzoates, DINCH & Citrates
2) Other Phthalates include Linears, DPHP, DIUP, DTDP, DOTP, DIBP, DBP
Source: 2007 Chemical Economics Handbook – SRI Consulting
17
Evolution of Plasticiser Consumption
in Europe
80%
70%
DINP/DIDP/DPHP
60%
Ongoing substitution
of classified LMW
by non-classified HMW
plasticisers
50%
40%
30%
DEHP
20%
10%
0%
2001
2002
2003
share of DINP/DIDP/DPHP in total plast.
2004
2005
2006
share of DEHP in total plasticisers
2007
2008
2009
share of non-phth in total plasticisers
Source: ECPI 2010
Source: ECPI, 2008
18
Stabilisers
● Cadmium
– Not used on EU market anymore (Vinyl 2010)
– 100 ppm limit likely to become mandatory for ALL applications
– Recycling issue: Hope for a 1000 ppm limit for cadmium originating from
recycling, in rigid building applications excluding drinking water pipes
● Tin
– Regulatory restrictions for di-butyltin in EU as from 2012
– Industry has anticipated
● Lead
– Phase out ahead of Vinyl 2010 schedule
– Will be also an issue in recycling
● Lead replaced by calcium/zinc – calcium/organic stabilisers
Alternatives to phthalates
● Some commercial non-phthalate options for general purpose use in PVC
– Epoxidised Oils (e.g. epoxidised soybean oil): Long term compatibility problems and
processability issues
– Citrates: Currently limited availability and higher costs. Performance lacking in
permanence
– Polyesters: Poor processability, higher costs
– Terephthalates
– Cyclohexanoate diesters: DINCH®
– Polyol esters: Danisco’s Grindsted® Soft-N-Safe
● Comparison with phthalates (presentation by D. Naert
(ExxonMobil Chemical) on behalf of ECPI at the
“PVC Formulation 2009” conference on 16 – 18 March 2009
– Phthalates like DEHP,DINP,DIDP have proven
track records of meeting GP plasticiser performance
– Main difference between phthalates: level of permanency
and processability
– Base set for a “General Purpose phthalate” with
a maximum index of 10 for each of the 5 key parameters
Terephthalates
Cyclohexanoate diesters (DINCH®)
Polyol esters: Danisco Grindsted®
Soft-N-Safe
PVC sustainability tool
● Developed by Adisa Azapagic, Haruna Gujba, Anthony
Morgan and Heinz Stichnothe
– School of Chemical Engineering and Analytical Science, The
University of Manchester
● Enables calculations of carbon footprint of different PVC
products and processes on a life cycle basis
– Cradle to gate
– Cradle to grave
● Calculates other environmental impacts
● Calculates value added along supply chains
● Includes case studies and a range of databases
New tool to assess PVC sustainability
● Questions explored within the PVC sustainability tool
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What is the carbon intensity of a PVC supply chain/process/product?
Where are the ‘hot spots’?
What are the low-carbon options for reducing the carbon intensity?
What would be the cost? And value added?
How would other environmental impacts change?
● Main features of the tool
–
–
–
–
–
Tailored for the PVC industry/supply chains
Free of charge
Simple to use
Integrated case studies
Includes data bases
●
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Materials
Energy
Transport
Packaging
Waste management
– Enables ‘what if’ scenario analysis
Built-in case studies and examples
Top-level view of the tool
Data shown for illustration only
Identifying carbon ‘hot spots’
Data shown for illustration only
Other environmental impacts
● Acidification
● Eutrophication
● Ozone depletion
● Photochemical
smog
● Human toxicity
Data shown for illustration only
Background slides (optional)
● LCAs remain the basis for scientific assessments of
environmental impacts
● High quality data available for plastic resins in general, and
PVC in particular
Eco-profiles
● Cradle-to-gate Life Cycle Inventories
● Benefits
– Essential basis for LCA studies of products
– Possibility of environmental benchmarking
● Encouraging environmental improvements in manufacturing
● PlasticsEurope eco-profiles
– Average representing the majority of European production
– Publicly available at http://lca.plasticseurope.org
– Included in the International Reference Life Cycle Data System (ILCD)
● Eco-profiles of PVC resin
– 92 % coverage of Western European industry
– Collected and calculated in 2005 by IFEU
● Eco-profiles of PVC conversion processes published in 2010
– Pipes and profiles extrusion, sheet calendering and coating, injection molding
Results of eco-profiles of PVC resin
EPD of PVC resin
● Environmental Product Declarations are socalled ‘Type III environmental declarations’
– Quantified environmental data for a product
using predetermined parameters, based on
ISO 14040 series
– The environmental data may be
supplemented by other quantitative and
qualitative environmental information
● The PVC EPD were the first to be published
under a new EPD programme launched by
PlasticsEurope
– Defined “Product Category Rules”, i.e. “Set of
specific rules, requirements, and guidelines
for developing Type III environmental
declarations for one or more product
categories”
– Essentially based on the eco-profiles
http://lca.plasticseurope.org
EPD results for 1 kg of PVC
●
represents the European PVC resin producing companies
and is a division of PlasticsEurope. Its membership includes the 13
European PVC resin producers which together account for 100 % of EU
27
production. ECVM is also a leading partner of Vinyl 2010 - the
organisation implementing the Voluntary Commitment of the PVC
Industry - together
with ESPA - representing the stabiliser producers, ECPI - representing
the plasticiser producers and EuPC - representing the PVC converters.