Plastics World Plastics Production 299 Million Tonnes/year EU - - PowerPoint PPT Presentation
FLEXI-PYROCAT T Pyrolysis-Catalysis of Waste Plastics to Fuels, Chemicals & Materials Research and Innovation Staff Exchange Project, Grant number: 643322-FLEXI-PYROCAT; as part of the Marie Sklodowska-Curie Action: H2020;
Research and Innovation Staff Exchange Project, Grant number: 643322-FLEXI-PYROCAT; as part of the Marie Sklodowska-Curie Action: H2020; H2020-MSCA-RISE-2014
Source : Plastics the Facts 2014/2015, Plastics Europe 2015
Consumer demand Post-consumer plastics waste Converter demand EU-27 Plastics Production 57 Mtonne 45.9 Mtonne 25.2 Mtonne Recovery 15.6 Mtonne Disposal 9.6 Mtonne Recycling 6.6 Mtonne Energy Recovery 8.9 Mtonne Import Import Import Export Export Export
Source : Plastics Europe 2014
Source: Velis, C., Global recycling markets - plastic waste: A story for one player - China. ISWA, International Solid Waste Association: Vienna, 2014
Annual volume of globally traded waste plastics is ~15 Million tonnes
Weight 1,000 Tonnes Contribution (%) Hong Kong 1,984 24.7 Thailand 802 10.0 Japan 737 9.2 Germany 669 8.3 Philippines 455 5.7 USA 426 5.3 Others 2,972 36.9 Total 8,042 100
Source: Velis, C., Global recycling markets - plastic waste: A story for one player - China. ISWA, International Solid Waste Association: Vienna, 2014
Sources of waste plastics imported into China
“European Strategy on Plastic Waste in the Environment” Members of the European Parliament noted;
significant global damage to human health and the environment”
and employment in the EU.”
Source:2013/2113(INI) – 14/01/2014 Text adopted by EU Parliament
heat transfer problems in the subsequent catalysis
can be easily controlled.
plastics remains in the pyrolysis unit.
and enables the reacted catalysts to be recycled and reused.
Source: Serrano D.P., et al. ACS Catalysis, 2, 1924-1941, 2012.
Waste Plastics Thermal Reactor Catalytic Reactor High Value Products
Hydrogen Carbon nanotubes Gasoline & chemicals
Pyrolysis Reactor
Waste Plastics
Hydrogen Gasoline Chemicals
Catalytic Reactor
Carbon nanotubes
High Value Products Reforming Catalysts Solid Acid Catalysts High Value Products
Two-stage processing with catalysts for higher value products
Depending on the type of catalyst used and the process conditions, high value products can be targeted. For example, the hydrocarbon pyrolysis products derived from the waste plastics can be steam reformed in the second stage catalytic reactor with nickel based catalysts at typical catalyst temperatures of ~800 °C to produce a hydrogen rich syngas. Alternatively, solid acid catalysts such as microporous Zeolites and mesoporous MCM-41 can be used in the second stage catalytic reactor at temperatures of ~500 °C to produce an upgraded oil product for use as premium grade fuels or chemicals.
Commercial catalytic methane steam reforming
Source: http://www.digipac.ca/chemical/; http://www.airproducts.com
Steam-methane reforming reaction CH4 + H2O → CO + 3H2 Water-gas shift reaction CO + H2O → CO2 + H2
Hydrogen is currently produced mostly (96%) from fossil fuels, the largest source being natural gas (methane). The process involves steam reforming of methane in the presence
to produce hydrogen and carbon monoxide. Further reaction of the carbon monoxide with steam using an iron oxide catalyst at ~350 °C produces enhanced hydrogen yields, but also carbon dioxide via the water gas shift reaction.
Reactions taking place during pyrolysis-catalytic steam reforming of waste plastics Waste plastics catalytic steam reforming
Pyrolysis Reactor Reforming/ Gasification Reactor Steam Plastic wastes Catalyst Hydrogen rich gas 500 °C 800 °C
Producing hydrogen from waste plastics would offer an alternative feedstock and also solve a major waste treatment problem.
Source: Czernik S., French R.J., (2006) Energy & Fuels, 20, 754-758.
Pyrolysis-Catalytic Steam Reforming of waste plastics
Commercial C11-NK nickel catalyst Pyrolysis 650 °C & catalytic steam reforming 850 °C
potential amount (0.429 g H2 g-1 polypropylene (i.e. if all of the polypropylene was completely converted to CO2 and H2)
H2, ~16 vol.% CO2, ~11 vol.% CO
a b c d e f g h i j k l 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Potential H2 production (wt.%) Catalyst
Source: Wu C., Williams P.T. (2009) Applied Catalysis B: Environmental, 90, 147-156.
Potential Hydrogen Production (%)
Potential H2 production from pyrolysis- gasification of polypropylene with different catalysts
influence on H2
a: Ni-Al (1:4) b: Ni-Al (1:2) c: Ni-Al (1:1) d: Ni-Mg-Al (1:4:1) e: Ni-Mg-Al (1:1:2) f: Ni-Mg-Al (1:1:1) g: Ni-Cu-Al (1:1:2) h: Ni-Cu-Mg-Al (1:1:1:3) (a-h are calcined at 750 °C) i: Ni-Al (1:4) j: Ni-Al (1:1) k: Ni-Al-Mg (1:1:4) l: Ni-Mg-Al (1:1:1) (i-l are calcined at 850 °C) a b c d e
Catalyst
f g h i j k l
Type of catalyst and catalyst preparation procedure influence catalyst activity and therefore H2 production
Catalyst support
Source: Wu C. and Williams P.T. (2009), Applied Catalysis B: Environmental, 87, 152-161.; Wu C, Williams P.T. (2009) Energy & Fuels, 23, 5055-5061; Wu C. Williams P.T. (2008) Energy & Fuels, 22, 4125-4132.
Ni/CeO2/Al2O3 Ni/ZSM-5 Ni/Al2O3 Ni/CeO2 Ni/MgO Ni-Mg-Al Ni-Al
Potential Hydrogen Production (%)
60 50 40 30 20 10
Catalyst
2 4 6 8 10 12 14 16 10 20 30 40 50 60 70 10 20 30 40 50 60 70
Potential H2 production (Wt.%) CO H2 CO2 CH4 C2-C4 Gas composition (Vol.%) Water flow rate (g h
Steam input Catalyst temperature
Potential H2 production (%) Potential H2 production (%)
Catalyst
preparation influence H2 yield
followed by saturation
yield; but can sinter the catalyst
Catalyst Temperature (°C) Potential H2 production (%) Gas composition (vol.%)
Polypropylene
Catalyst Temperature (°C) H2 production (g/g plastic) Gas composition (vol.%)
Wu C, Williams P.T., (2010), Int. J. Hydrogen Energy, 35, 949-957 Wu C., Williams P.T. (2010) Fuel, 89, 3022-3032.
PP PS HDPE Waste Plastic Mixed Plastics 5 10 15 20 25 30 35 40 45 50 55 60 65 70 Gas composition (Vol.%) CO H2 CO2 CH4 C2-C4
Gas composition (vol.%)
Plastic type
Mixed plastic Waste plastic HDPE PP PS
1 2 3 4 5 6 7 8 9 10 15 20 25 30 35 40 45 50 55 60 65 70
Gas concentration (Vol.%) Reaction Time (h) H2 CO CO2
Effect of extended continuous reaction time Screw Kiln
Post-consumer waste plastics
Source: Park Y., et al. (2010) Fuel Processing Technology, 91, 951-957. Namioka T., et al. Applied Energy, 88, 2019-2026, 2011.
Source: He M., et al. International Journal of Hydrogen Energy, 34, 1342-1348, 2009.
Pyrolysis steam reforming of waste polyethylene at 900 °C with a NiO/γ-Al2O3 catalyst
Flowchart of experimental apparatus. 1. steam generator, 2. valve, 3. piezometer, 4. steam flow meter, 5. motor, 6. screw feeder, 7. hopper, 8. fixed bed gasifier, 9. porous ceramic, 10. catalyst, 11. electric furnaces, 12. temperature controller, 13. cyclone, 14. condenser, 15. flask, 16. filter, 17. gas meter, 18. silica gel, 19. air pump, 20. gas sample bag
DTG-TPO
Temperature °C Derivative Mass (°C-1)
100 200 300 400 500 600 700 800
0.0000 0.0002 0.0004 900 Layered Carbon Filamentous Carbon
Carbons Catalyst Temperature programmed oxidation Focused Ion Beam (FIB)/ Scanning Electron Microscope (SEM)
Layered type carbon deposits Filamenteous carbon deposits
Source: Wu C., Williams P.T. Appl. Catal. B-Environ., 96, 198-207, 2010 Argyle M.D., Bartholomew C.H., (2015) Catalysts, 5, 145-269
Catalyst metal particle sintering
Source: Martins-Júnior P.A. et al. J DENT RES 2013;0022034513490957
Single wall carbon nanotubes (SWCNT)
Multi wall carbon nanotubes (MWCNT)
Properties
Applications
Chemical vapour deposition (CVD) for carbon nanotubes production
Hydrocarbon precursors: methane, ethylene, acetylene, benzene, xylene and carbon monoxide. Temperatures: 700 – 1200 C Catalysts: Fe, Co, Ni, nano-particles; Solid organometallocenes (ferrocene, cobaltocene, nickelocene
Source: Kumar M. in Yellampalli S., Carbon nanotubes,- Synthesis, characterisation, applications. Nanotechnology and nanomaterials, Intech, 2011
Multi-walled carbon nanotube
Source: Kumar M. in Yellampalli S., Carbon nanotubes,- Synthesis, characterisation, applications. Nanotechnology and nanomaterials, Intech, 2011
Widely-accepted growth mechanisms for CNTs: (a) tip-growth model, (b) base-growth model.
Tip Growth;
Base Growth
carbon precipitation on the surface
Source: Liu, J., et al., (2011) Polymer Degradation and Stability, 96(10), 1711-1719.
Two-stage screw kiln pyrolysis-moving bed catalytic reactor (polypropylene) 1st stage – Pyrolysis with Zeolite ZSM-5 2nd Stage – Chemical Vapour Deposition with nano- sized NiO Catalyst
Catalyst temperature Pyrolysis temperature
Fluidised bed-catalytic gasification of waste plastics for carbon nanotube production.
Source: Yang et al, (2015), Energy & Fuels, 29, 8178-8187
Polyethylene & polypropylene
gasification in a fluidised bed
Air, N2 or H2/He
(H2 calcination) optimised product yield and quality.
temperature
Acomb J.C., Wu, C., Williams P.T. (2014), Applied Catalysis B: Environmental, 147, 571-584.
Low density polypropylene
Two-stage pyrolysis- catalysis of plastics
Ni-Al2O3 Fe-Al2O3 Co-Al2O3 Cu-Al2O3
Acomb J.C., et al. (2014), Applied Catalysis B: Environmental, 147, 571-584. Acomb J.C., et al. (2015), Journal of Analytical and Applied Pyrolysis, 113, 231-238
Influence of steam
Ni-Al2O3 catalyst; Polypropylene
carbons
distort carbon nanotubes
b d f h
Influence of catalyst temperature
Fe-Al2O3 catalyst; Polyethylene
0 steam 0.25 g h-1 steam 1.9 g h-1 steam 4.74 g h-1 steam
900 °C 800 °C 700 °C
Laboratory scale fluidised bed with polystyrene and FCC catalyst
Source: Kaminsky et al., J. Anal. Appl. Pyrol. 79, 368-374, 2007.
Laboratory scale fluidised bed with polypropylene and AlCl3
Source: http://www.chm.bris.ac.uk/motm/mcm41/mcm41.htm; http://cinabrio.over-blog.es/ Ennaert T, et al, Chem Soc Rev. 2016, 45, 584-611
MCM-41
channels
width
amorphous SiO2
Solid acid catalysts
ZSM-5
AlO4
membered rings
Hierarchical
mesopores
Important influences of;
Source: Aguado, J. et al. (2007) J. Anal. Appl. Pyrol., 79, 415-423.
Thermal pyrolysis ZSM-5 pyrolysis- catalysis MCM-41 pyrolysis- catalysis
C5 - C12
aromatic content
Fluidised bed pyrolysis-catalysis of waste plastics fuels production
Schematic diagram of a catalytic fluidised-bed reactor system: 1. feeder, 2. furnace, 3. sintered distributor, 4. fluidised catalyst, 5. reactor, 6. condenser, 7. flow meter, 8. 16-loop automated sample system, 9. gas bag, 10. GC, 11. digital control..
Lin Y.H., et al (2004) Polymer Degradation, 86, 121-128.
Type of catalyst influences yield and composition
Comparison of alkenes Comparison of alkanes
Lopez, A.; et al (2011). Appl. Catal. B-Environ., 104, 211-219.
ZSM-5 pyrolysis-catalysis Oil Composition (ZSM-5, 500 °C
Simulated mixture of plastics
Muhammad C., et al. (2015), Energy and Fuels, 29, 2601-2609.
Furnace Furnace Thermocouple Plastic Nitrogen Catalyst Condenser System Gas Sample Bag Thermocouple
Oil Composition
ZSM-5 pyrolysis-catalysis ZSM-5 pyrolysis-catalysis Thermal pyrolysis Thermal pyrolysis
Hierarchical nanocrystalline ZSM-5 zeolites prepared by different methods Batch single stage reactor
zeolites; high acidity
and surface area
Hierarchical nanocrystalline HZSM-5 (PHAPTMS)
Serrano, D.P., et al. (2010), Journal of Catalysis, 276, 152-160.
established, e.g. MSW plastics, WEEE plastics
exported – mainly to China
recycling or energy recovery
production of higher value products.