RECYCLING AND REUSE OF PLASTICS CONTAINED IN WASTE …athens2014.biowaste.gr/pdf/triantou_pr.pdf ·...

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  • National Technical University of Athens

    School of Chemical Engineering

    Polymer Technology Lab.

    RECYCLING AND REUSE OF PLASTICS

    CONTAINED IN WASTE FROM

    ELECTRICAL AND ELECTRONIC EQUIPMENT

    Μ.Ι.Triantou, P.A.Tarantili, A.G. Andreopoulos

    2nd International Conference on Sustainable Solid Waste Management, Athens, Greece, 12-14 June, 2014

    http://www.google.com/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&docid=RpoYKoZ0RFadkM&tbnid=PtEgTBPz_WrxBM:&ved=0CAUQjRw&url=http://en.ecovitrum.eu/ver/177/Environmental-awareness-in-schools.html&ei=kxePU9nZO4K8Oe3xgcAG&bvm=bv.68235269,d.bGQ&psig=AFQjCNFeDAntQAi4urfISld73pfcZRnrhQ&ust=1401972697716184http://www.google.com/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&docid=RpoYKoZ0RFadkM&tbnid=PtEgTBPz_WrxBM:&ved=0CAUQjRw&url=http://en.ecovitrum.eu/ver/177/Environmental-awareness-in-schools.html&ei=kxePU9nZO4K8Oe3xgcAG&bvm=bv.68235269,d.bGQ&psig=AFQjCNFeDAntQAi4urfISld73pfcZRnrhQ&ust=1401972697716184

  • World plastics production 1950-2012Source: Plastics Europe-Plastics – The Facts 2013: An analysis of European latest plastics production, demand and waste data

    European plastics demand by segment 2012Source: Plastics Europe

    Plastics production and demand

    Global production of plastics in 2012 rose to 288 million tones – a 2.8% increase compared to 2011.

    In Europe, in line with the general economic situation, plastics production decreased by 3% from 2011 to 2012 reaching 57 million tones.

    In 2012: demand in Europe decreased by 2.5% and

    reached 45.9 million tones, the electrical and electronic equipment sector

    covered the 5.5% of the european plastics demand.

    2

  • Disposal, recycling and energy recovery

    of plastics in 2012 in Europe

    (Source: Plastics Europe)

    Waste management of plastics

    The total recovery of plastics increased by 4% in 2012 (mechanical recycling increased by 4.7%, energy recovery increased by 3.3%).

    At the same time, there was a reduction of 5.5% of landfilled plastics.

    Total plastics waste recycling and recovery 2006-2012 in Europe(Source: Plastics Europe)

    Treatment of post consumer plastics waste 2012 by

    EU-27+2 (Source: Plastics Europe)

    In Greece, recycling and energy

    recovery rates are still at low values.

    3

  • Waste management of EEE

    The waste coming from EEE represents an about 8% of the total municipal waste internationally.

    In European Union, 12-20 kg WEEE/habitant is produced each year and their overall, annual production varies between 6.5-7.5 million tones [Hellenic Solid Waste Management Association].

    In Greece, 170.000 tones WEEE are produced per year [Hellenic Solid Waste Management Association]. During 2005-2013 (1st semester), the 87.73% of EEE was treated, whereas the 12.27% was

    led to landfill in Greece [Appliances Recycling S.A.].

    Total exploitation of WEEE (tones) and separate collection WEEE from

    domestic sector (kg/habitant) during 2005-2012 in Greece

    (Source:eoan -Report of recycling in Greece, September 2013, Athens, 18-22)

    33411 tones

    exploited

    4

  • Composition of WEEE

    47,90%

    20.60%

    7%

    5,40%

    4,70%

    4,60%3,10%

    2,60% 2% 1% 0,90%

    iron-steel

    plasticscopper

    glass

    aluminium

    other

    circuits

    wood

    ceramics

    other metals

    rubberComposition of WEEE (Source: Hellenic Solid Waste Management Association)

    Packaging dominates the waste generated from plastics, covering 62.2% of the total. Other applications like building and construction, electrical and electronic products and agriculture count for 5 till 6% each [Plastics Europe] .

    Source: WRAP, 2009

    Generation of post-consumer plastics

    waste by application (Source: Plastics Recyclers Europe)

    ACR

    6%

    PA

    4%

    PEP

    3%

    HIPS

    2%PET

    2%POM

    2%

    PE

    2%PVC

    2%Άλλα

    4%

    DMPS

    3%

    PB

    3%

    PC/ABS

    3%

    ABS

    20%

    PP

    10%

    PS

    12%PC

    11%

    SAN

    10% 5

  • Materials

    ABSABS

    PPPCCl30B Cl30B

    Poly(acrylonitrile-butadiene-styrene) terpolymer, ABS (Terluran GP-35, BASF)

    Polycarbonate, PC (Makrolon 2805, Bayer)

    Polypropylene, PP

    Cloisite 30B (OMMT) (Rockwood Clay Additives GmbH)

    2 phr

    100/0

    70/30

    50/50

    30/70

    0/100

    2 phr

    ABS PC Cloisite 30B

    Organic modification

    of Cloisite 30B

    PP 6

    contributes to the

    improvement of

    properties of blends

    acts as a compatibilizer

    between the

    components of blend

    a low-cost, ecological additive

  • Experimental procedure

    Pre-mixture

    Melt intercalation (co-rotating, twin screw extruder)

    Granulation Injection

    Melt Flow Index

    (MFI)

    Thermogravimetric

    Analisis (TGA)

    Gross Calorific

    Value (GCV)

    Tensile

    testDynamic Mechanical

    Analisis (DMA)

    7

  • Melt Flow Index (MFI)

    The incorporation of organoclay into the ABS/PC blends results in a decrease of the MFI, maybe due to the confinement of polymer chains motion, caused by organoclay platelets and tactoids, and the interactions between the polar groups of ABS and oxygen containing groups of Cloisite 30B.

    The MFI of ABS/PP blend tends to be decreased by incorporating OMMT.

    70/30 50/50 30/700

    2

    4

    6

    8

    10

    12

    14

    16

    18

    MF

    I (g

    /10

    min

    )

    ABS/PC (w/w)

    0 phr Cl30B

    2 phr Cl30B

    PC

    100/0 70/30 50/50 30/70 0/1000

    1

    6

    8

    10

    12

    14

    16

    MF

    I (g

    /10

    min

    )

    ABS/PP (w/w)

    0 phr Cl30B

    2 phr Cl30B

    8

    The ABS/PC blends exhibit higher MFI than that of PC.

    ABS exhibits lower MFI than PP and ABS/PP blends presents melt behavior closer to that of PP.

    Blending of polymers is the key for the improvement of their processability.

  • Tensile test

    The tensile strength of ABS is increased by the addition of PC, whereas it is decreased significantly by the addition of PP.

    In ABS/PC blends, the tensile strength seems to follow the rule of mixture. In ABS/PP blends, the tensile strength is closer to that of pure PP. The incorporation of organoclay in ABS/PC blends seems to cause a slight increase in the

    tensile strength.

    In ABS/PC blends, a synergic action between the two polymers is observed for Young’s modulus.

    In ABS/PP blends, the Young’s modulus is decreased as the PP concentration is increased. The addition of organoclay significantly improves the Young’s modulus of the examined

    blends. The enhancement of stiffness is interpreted by the higher modulus of organically modified

    clay and by the low deformability of polymeric chains penetrating the silicate galleries.

    100/0 70/30 50/50 30/70 0/10025

    30

    35

    45

    50

    55

    60

    65

    70

    Ten

    sile

    str

    en

    gth

    (M

    Pa)

    (w/w)

    0 phr Cl30B/ABS/PC

    2 phr Cl30B/ABS/PC

    0 phr Cl30B/ABS/PP

    2 phr Cl30B/ABS/PP

    100/0 70/30 50/50 30/70 0/1001250

    1500

    1750

    2000

    2250

    2500

    2750

    Yo

    un

    g's

    mo

    du

    lus

    (MP

    a)

    (w/w)

    0 phr Cl30B/ABS/PC

    2 phr Cl30B/ABS/PC

    0 phr Cl30B/ABS/PP

    2 phr Cl30B/ABS/PP

    9

    + 4-13.5%: ABS/PC

    + 14-23.5%: ABS/PP

  • Dynamic Mechanical Analysis (DMA)

    -100 -50 0 50 100 150 2000.00E+000

    5.00E+008

    1.00E+009

    1.50E+009

    2.00E+009

    2.50E+009

    3.00E+009

    Sto

    rag

    e m

    od

    ulu

    s (P

    a)

    T (oC)

    100/0 ABS/PC

    70/30 ABS/PC

    50/50 ABS/PC

    30/70 ABS/PC

    0/100 ABS/PC

    -120 -90 -60 -30 0 30 60 90 120 1500.00E+000

    5.00E+008

    1.00E+009

    1.50E+009

    2.00E+009

    Sto

    ra

    ge m

    od

    ulu

    s (P

    a)

    T (o

    C)

    100/0 ABS/PP

    70/30 ABS/PP

    50/50 ABS/PP

    30/70 ABS/PP

    0/100 ABS/PP

    -120 -90 -60 -30 0 30 60 90 120 1500.00E+000

    5.00E+008

    1.00E+009

    1.50E+009

    2.00E+009

    2.50E+009

    3.00E+009

    Sto

    ra

    ge m

    od

    ulu

    s (M

    Pa

    )

    T (o

    C)

    30/70 ABS/PC

    2 phr Cl30B/30/70 ABS/PC

    30/70 ABS/PP

    2 phr Cl30B/30/70 ABS/PP

    A synergistic effect is observed for ABS/PC blends and the greatest value is recorded for 50/50 w/w composition.

    Below 10 oC, the ABS/PP blends present higher storage modulus than that of neat ABS and lower than or equal to that of neat PP. On the contrary, over 10 oC, the Gʹ of ABS/PP blends is higher than that of neat PP and lower than that of neat ABS.

    The ABS/PC blends present higher storage modulus than that of ABS/PP blends.

    The incorporation of organoclay leads to an impressive increase of storage modulus, in comparison with this corresponding to unreinforced blends.

    10

    PC

    ABS blends

    25 oC

    ABS

    PP

  • Thermogravimetric Analysis (TGA)

    250 300 350 400 450 500 550 600 650-0.025

    -0.020

    -0.015

    -0.010

    -0.005

    0.000

    Deriv

    ati

    ve o

    f w

    eig

    ht

    ch

    an

    ge (

    %/o

    C)

    T (oC)

    100/0 ABS/PC

    70/30 ABS/PC

    50/50 ABS/PC

    30/70 ABS/PC

    0/100 ABS/PC

    300 350 400 450 500 550 600-0.020

    -0.015

    -0.010

    -0.005

    0.000

    Deriv

    ati

    ve o

    f w

    eig

    ht

    ch

    an

    ge (

    %/o

    C)

    T (oC)

    50/50 ABS/PC

    2 phr Cl30B/50/50 ABS/PC

    30/70 ABS/PC

    2 phr Cl30B/30/70 ABS/PC

    The thermal stability increases with the following order: ABS

  • Gross Calorific Value (GCV)

    ABS/PC ABS/PP8000

    8200

    8400

    8600

    9800

    10000

    10200

    10400

    GC

    V (

    cal/

    /g o

    rgan

    ic m

    ate

    ria

    l)

    50/50 w/w

    0 phr Cl30B

    2 phr Cl30B

    100/0 70/30 50/50 30/707500

    7750

    8000

    8250

    8500

    9000

    9250

    9500

    9750

    10000

    10250

    10500G

    CV

    (cal/

    g o

    rgan

    ic m

    ate

    ria

    l)

    ABS/PC (w/w)

    0 phr Cl30B

    2 phr Cl30B

    As the PC content in ABS/PC blends increases, a reduction of GCV is observed, due to the poor burning characteristics of PC as compared with ABS.

    The incorporation of OMMT to ABS/PC or ABS/PP blends does not have a significant effect.

    Emissions from hazardous substances in WEEE (heavy metals, halogens, organic components like brominated and chlorinated flame retardants) complicates the technical aspects of energy recovery.

    The GCV increases with the following order: PC < ABS < PP.

    12

  • Conclusions

    The addition of PC in ABS matrix improves its thermomechanical properties, whereas the addition of ABS in PC matrix makes feasible its processing at lower temperatures.

    The addition of PP in ABS matrix increases its thermal stability, whereas the addition of ABS in PP matrix improves its mechanical behavior.

    The incorporation of OMMT to ABS/PC or ABS/PP blends leads to an increase of their melt viscosity, improves significantly the Young’s modulus and the storage modulus and protects the PC phase during the thermal decomposition of PC-rich, ABS/PC blends.

    The blending of polymers used in WEEE is an appropriate procedure for their common management, which eliminates the time consuming and costly phase of sorting.

    The incorporation of organoclay to polymer blends is a low-cost and environmentally friendly alternative technique for the upgrading of their performance during their mechanical recycling.

    13

  • Future Research

    14

    Thorough investigation capability of Cloisite 30B to improved compatibility and performance of ABS/PC and ABS/PP blends.

    Extension of the study to other polymeric blends with various components (e.g. PC/SAN).

    Upgrading of the examined plastic blends by the incorporation of the appropriate amount of additives (e.g. carbon nanotubes, graphene) as advanced technology reinforcing fillers.

  • National Technical University of Athens

    School of Chemical Engineering

    Polymer Technology Lab.

    RECYCLING AND REUSE OF PLASTICS CONTAINED IN

    WASTE FROM ELECTRICAL AND ELECTRONIC

    EQUIPMENT

    Μ.Ι.Triantou*, P.A.Tarantili, A.G.Andreopoulos

    2nd International Conference on Sustainable Solid Waste Management, Athens, Greece, 12-14 June, 2014

    Thank you very much

    for your attention

    *e-mail: [email protected]

  • 16

    Temperature at six zones of extruder (oC)

    1st 2nd 3rd 4th 5th Die

    (100/0 w/w) ABS/PC 210 200 200 195 195 190

    (100/0 w/w) ABS/PC* 190 195 195 200 200 205

    (70/30 w/w) ABS/PC 230 215 215 210 210 205

    (50/50 w/w) ABS/PC 240 235 235 230 230 225

    (30/70 w/w) ABS/PC 260 255 255 250 250 245

    PC 290 280 275 270 265 260

    Temperature at six zones of extruder (oC)

    1η 2η 3η 4η 5η Die

    0/100 ABS/PP 180 180 185 185 190 190

    30/70 ABS/PP 190 190 195 195 200 200

    50/50 ABS/PP 190 190 195 195 200 200

    70/30 ABS/PP 190 190 195 195 200 200

    100/0 ABS/PP 190 195 195 200 200 205

    Screw speed:200 rpm

    ABS is composed of :44% acrylonitrile42% styrene14% butadiene

  • 17

    50/50 ABS/PC nanocomposite

    According to SEM this nanocompositeconsists of a continuous ABS phase and a dispersed PC phase.

    Clay tactoids are arranged mainly on the ABS/PC interphase and in the ABS phase

    It is possible the formation of a physical crosslinking network structure composed of clay particles and polymeric chains which limitates the chains’ motion and protects them during the thermal degradation.

    The heat barrier effect could also provide superheated conditions inside the polymer melt leading to extensive random scission of polymer chain and evolution of numerous chemical species which, trapped between clay layers, have more opportunity to undergo secondary reactions. As a result, some degradation pathways could be promoted leading to enhanced charring.

    The clay may permit radical recombination reactions, exerting thus a stabilization effect in the ABS/PC/layered silicate nanocomposite.

    The dispersion of organoclay layers leads to the formation of a tortuous path which inhibits the passage of volatile degradation products during the initiation of thermal degradation (labyrinth effect).