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1 s2.0 S2589299119300618 Main PDF
1 s2.0 S2589299119300618 Main PDF
Utilization and recycling of end of life plastics for sustainable and clean
industrial processes including the iron and steel industry
Sheila Devasahayam a,⇑, Guntamadugu Bhaskar Raju b, Chaudhery Mustansar Hussain c
a
Monash University, Clayton, Melbourne, Australia
b
National Metallurgical Laboratory (Formerly), CSIR Madras Complex, Chennai, India
c
Department of Chemistry and Environmental Sciences, New Jersey Institute of Technology, Newark 07102, NJ, USA
a r t i c l e i n f o a b s t r a c t
Article history: About 400 million tonnes of plastics are produced per annum worldwide. End-of-life of plastics disposal
Received 21 April 2019 contaminates the waterways, aquifers and limits the landfill areas. Options for recycling plastic wastes
Revised 16 August 2019 include, feedstock recycling, mechanical /material recycling, industrial energy recovery, municipal solid
Accepted 16 August 2019
waste incineration. Incineration of plastics containing E-Wastes releases noxious odours, harmful gases,
Available online 19 August 2019
dioxins, HBr, polybrominated diphenylethers and other hydrocarbons. This study focusses on recycling
options, in particular, feedstock recycling of plastics in high-temperature materials processing, for a sus-
Keywords:
tainable solution to the plastic wastes not suitable for recycling. Of the 7% CO2 emissions attributed to the
Waste plastics
Thermo and thermoset plastics
iron and steel industry worldwide, 30% of the carbon footprint is reduced using the waste plastics com-
Iron and steel industry pared to other carbon sources, in addition to energy savings. Plastics have higher H2 content, than the
Feedstock recycling coal. Hydrogen evolved from the plastics acts as the reductant alongside the carbon monoxide.
Carbon sequestration Hydrogen reduction of iron ore in presence of plastics increases the reaction rates due to higher diffusion
Energy and emissions savings of H2 compared to CO. Plastic replacement reduces the process temperature by at least 100–200 °C due to
the reducing gases (hydrogen) which enhance the energy efficiency of the process. Similarly, plastics
greatly reduce the emissions in other high carbon footprint process such as magnesia production while
contributing to energy.
Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
2. Options for end of life plastic wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
2.1. Land filling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
2.2. Industrial energy recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
2.2.1. Incineration of municipal solid waste (MSWI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
2.2.2. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
2.3. Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
2.3.1. Biological recycling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
3. Plastics for carbon sequestration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
4. Advantages/disadvantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
⇑ Corresponding author.
E-mail addresses: sheiladevasahayam@gmail.com (S. Devasahayam), chaudhery.m.hussain@njit.edu (C. Mustansar Hussain).
Peer review under responsibility of KeAi Communications Co., Ltd.
https://doi.org/10.1016/j.mset.2019.08.002
2589-2991/Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646 635
1. Introduction recycling rate of 11.8% [5]. According to Plastics Europe, for the first
time, recycling (31.1%) overcame landfill (27.3%) in 2016, [6]
About 400 million tonnes of plastics are produced per annum (Fig. 1). From 2006 to 2016, the volumes of plastic waste collected
worldwide. End-of-life of plastics disposal contaminates water- for recycling increased by 79%, energy recovery increased by 61%
ways and aquifers, limits the landfill areas and generating noxious and landfill decreased by 43%.
odours, harmful gases and other hydrocarbons during incinera- Waste plastics are classified into the hydrocarbons containing
tions [1]. The image of a dead sperm whale with 29 kg of plastic no heteroatoms e.g. polyethylene, polypropylene and polystyrene;
inside its digestive system from ingestion of plastics highlights and, hydrocarbons containing heteroatoms, e.g. polyvinylchloride,
the gravity of the plastic pollution [2]. Plastics disintegrate into acrylonitrilestyrene-butadiene resin (ABS) and polyethylene
smaller particles to <0.1 mm. Depending on the size, disintegrated terephthalate. One of the major components of E-Waste is ABS,
plastics are classified as macroplastics (>5 cm); mesoplastics containing brominated flame retardants (BFRs), tetrabromobisphe-
(5 mm to 5 cm); microplastics (100 nm to 5 mm); and nanoplastics nol A (TBBPA) and brominated epoxy oligomers. Plastics that con-
(<100 nm). Microplastics convey pollutants via food to the users tain BFRs include epoxy and polycarbonate resins, ABS, brominated
affecting the ecosystems [3]. The nano- and microplastics are ABS (Br-ABS), high impact polystyrene, brominated polystyrene
ingested by most marine and terrestrial organisms. and phenolic resins [7]. The presence of bromine in ABS results
The Leibniz-Institute of Freshwater Ecology and Inland Fisheries in dioxin and/or benzofuran formation during pyrolysis because
(IGB) reports of tiny pieces of plastic surfaces carrying pathogens of the reactions of organic halogen compounds in the pyrolysis
facilitating the spread of maladies in the environment. Microplas- oil [8,9].
tics can interact with soil fauna, impacting their wellbeing and soil Polymeric matrices are divided into thermoplastics and ther-
functions. Earthworms, make their tunnels in a different way in the mosets. Thermoplastics undergo chemical [10,11], thermal,
presence of microplastics in the soil, affecting their fitness and the photo-, or biodegradation [12]. They can be transformed or repoly-
soil condition. Phthalates and Bisphenol A seeping out of plastics merized into new products. However, the challenge is to ensure
interrupt the hormone scheme of vertebrates and invertebrates material performance during its useful lifetime is not compro-
[1]. Nanoplastics cause inflammation of the cells; pass through or mised during the end-of-life degradation and/or reprocessing [13].
change cellular obstacles, traverse selective membranes such as Opportunities for the waste plastics and their impact on the
the blood-brain wall or the placenta, elicit deviations in gene environment are discussed in the following section.
expression and biochemical responses inside cells, e.g. behavioural
patterns of fish change as the blood-brain barrier is crossed [1].
Hence it is important to dispose of end of life plastics sensibly. 2. Options for end of life plastic wastes
Despite plastics being the source of energy, replacing the non-
renewable resources and diminishing carbon foot print, only 9% Figs. 2 and 3 and Table 1 illustrates the relative Net-energy/
of the plastic wastes have been recycled, 12% incinerated and GHG-effects of different disposal/ repurposing options [14]. Incin-
79% still in the landfills as of 2015 [4]. In 2015, around 55% of glo- eration and gasification show the highest net emissions. Pyrolysis
bal plastic waste was discarded, 25% incinerated, and 20% recycled. and the catalytic depolymerisation show negative net emissions
Annual Australian plastics recycling in 2016–17 is 415200 t at [15].
Fig. 1. In 2016, for the first time, more plastic waste recycled compared to the landfilled [6], reproduced in accordance with the copyright policy of PlasticsEurope: https://
www.plasticseurope.org/en/privacy-policy.
636 S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646
Fig. 2. Net-energy/GHG- effects of recycling, recovery and disposal processes for LDPE [14] (Harald Pilz, 2014).
Fig. 3. Saved energy resources using different recycling processes [14] (Harald Pilz, 2014).
Table 1
GHG emissions for different disposal options [15] reproduced under open Government license (https://www.zerowastescotland.org.uk/OpenGovernmentLicence).
2.1. Land filling ination. Offensive smells, high temperatures constrain the recycla-
bility of silicones [18,19].
Land filling EOL plastics wastes are valuable resources with no
net Green House Gas (GHG productions or benefit. Degradation 2.2. Industrial energy recovery
of polyethylene (PE), polyethylene terephthalate (PET) and
polyvinylchloride (PVC) generate organic pollutants such as poly Energy recovery processes convert solid waste in to energy or
chlorobiphenyl and polycyclic aromatic hydrocarbons. Thermosets feed stocks. Plastics have heating values in excess of 40 MJ/kg,
and composites such as epoxy cannot be re-formed and need to be due to high carbon, hydrogen and low ash content. One kg plastic
landfilled or incinerated [16,17]. Disposal of silicone (mixed waste has the same heating value as 1 liter fuel oil. Energy claimed
inorganic-organic polymers) wastes from electrical, electronic, from EOL plastics is converted as heat, steam or electricity. Indus-
medical and other industries in landfill results in methane contam- tries such as cement kilns, fluidised bed combustion processes
S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646 637
Table 2
Pyrolysis yield of LDPE and HDPE with HZSM-5 (nanocrystalline zeolites) [36] (Data Incineration of chlorine containing plastics like polyvinyl chloride,
sourced with permission).
(PVC) reduces landfilled wastes, but leads to dioxins generation.
Yield (% wt) LDPE HDPE LDPE-HZSM-5 HDPE-HZSM-5
Gas Fraction 14.6 16.3 70.7 72.6
Liquid Fraction/wax 93.1 84.7 18.3 17.3 2.2.2. Pyrolysis
Solid Fraction – – 0.5 0.7 Pyrolysis can treat mixed and dirty plastics. It results in dechlo-
rination, breaking of C–C and C–H bonds (scission) or recombina-
tion of gases, liquids and solids to provide new crosslinked
structures similar to high energy radiolysis products [22–27]. Thus,
high energy radiolysis is recommended as a recycling option for
(paper industry) and coal fired power stations utilise the energy
waste plastics [28].
recovered from the mixed plastic waste directly substituting fossil
Pyrolysis of organic materials lead to formation of gases, liquids
fuels.
and solids (char). Pyrolysis products include carbon, HCl, H2, ben-
Energy recovery remains a suitable option for the mixed and
zene and toluene in the absence of oxygen between 300 °C and
soiled plastic wastes that are technically and economically difficult
500 °C (Table 2) [29]. Biofuel produced during pyrolysis can substi-
to recycle [20]. ‘‘Refuse Paper and Plastic Fuel (RPF), generated
tute fossil fuel with no toxic or harmful emissions. The dioxins pro-
from difficult-to-recycle wastes such as laminated paper coated
duction is controlled in pyrolysis unlike in incineration. Various
with plastics and waste plastics is cheaper and emits 2/3rd CO2
pyrolysis processes for processing plastics containing BFRs include,
for the same calorific value compared to coal [21] (Fig. 4).
fluidized bed pyrolysis [30], two-stage pyrolysis [31], long resi-
dence time pyrolysis [32], and pyrolysis in the presence of iron
2.2.1. Incineration of municipal solid waste (MSWI) and calcium based catalysts [33].
Energy efficiency of MSWI plants using mixed plastic waste, is Waste plastics carbonization yields roughly about 20% coke,
less than the industrial energy recovery process. Incineration 40% tar and light oil, and 40% gases [34], in addition to energy
results in net positive CO2 generation [14], steam and cinders. and other materials [35] with net emissions of –160 kg CO2. The
Table 3
Cradle-to-gate life cycle inventory data of commodity plastics [38].
Resin type Energy (GJ tonne1) Water (kL tonne1) CO2-ea (–) Usageb (ktonne)
PET 82.7 66 3.4 2160
HDPE 76.7 32 1.9 5468
PVC 56.7 46 1.9 6509
LDPE 78.1 47 2.1 7899
PP 73.4 43 2.0 7779
PS 87.4 140 3.4 2600
Recycled plastics 8–55 Typical 3.5c Typical 1.4 3130
a
CO2-e is global-warming potential (GWP), calculated as 100-yr equivalent to CO2 emissions (M. Patel, N. von Thienen, E. Jochem, E. Worrel, Res. Cons. Recycl. 2000, 29, 65–
90).
b
2002 Usage for the aggregate EU-15 countries across all market sectors.
c
Typical water and GHG emissions values for recycling 1 kg PET from waste plastics (Hopewell, J., Dvorak, R., Kosior, E. Phil. Trans. R. Soc. B. 2009, 364, 2115–2126).
638 S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646
2.3. Recycling
Table 4
Chemical make-up of plastics, coal and fuel oil [56–58].
Wt% PE PP PS PET PVC Waste plastics (packaging) Pulverised coal Fuel oil
C 85.6 85.75 92.16 64.71 41.4 77.81 79.6 85.9
H2 14.21 14.15 7.63 3.89 5.3 11.99 4.32 10.5
S – – – – 0.03 0.9 0.97 2.23
Ash 0.19 0.1 0.21 0.17 0.4 4.9 9.03 0.05
Cl – – – – 47.7 1.4 0.2 0.04
K – – – – – 0.05 0.27 0.001
Na – – – – – 0.09 0.08 0.001
S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646 639
Table 5
Properties of resins [59,13,61,62].
Sustainable iron making is classified as direct smelting (liquid productivity improved by 40%
product) and direct reduction (solid product) processes. Corex, reduction in dust emissions by 40%
Finex and Hismelt are categorized under direct smelting. FASTMET elimination of odour or white smoke from scrap preheating
and MIDREX (gas based) are classified as direct reduction pro- Dioxin emissions regulatory requirement met.
cesses. Waste plastics can be fed directly into the Corex and the
other smelting reduction processes to reduce the fuel rate, elimi- In the EAF steel making, 30% of the coke and coal can be
nating the need for expensive injection systems needed in conven- replaced by PE wastes. Energy savings up to 12 kWh/t of plastic
tional iron making [67]. charge can be realised [74]. About 1.7 kg of tyres can replace 1 kg
In a Hydrogen flash smelting process, iron ore concentrates can of anthracite [75]. Carbon neutral natural rubber in tyres con-
be sprayed directly into a suspension or flash-type furnace cham- tribute to lower CO2 emissions [76]. Tyre injection trials at OneS-
ber and the reductant used can be synthetic gas produced from teel’s Sydney steel mill, Australia, reduced electrical energy
partial combustion of coal and/or waste plastics [55]. This process consumption from 1.526 MJ/kg to 1.483 MJ/kg billet (0.043 MJ/
could use approximately 38 percent less energy than a BF. When kg savings in energy), reduced the amount of carbon injected from
using Hydrogen, this new technology will produce only 4% of the 464 kg/heat to 406 kg/heat, and improved number of liquid tonnes
CO2 produced in the BF process, and 90% to 99% reduction achieved per power-on time minute from 2.12 to 2.2 t/min [77].
in a few seconds at temperatures 1300 °C. This is attributed to the The chemical composition and physical characteristics of waste
smaller hydrogen molecules as reductant are capable of diffusing 5 plastics and their char determine the reduction characteristics in
times faster than the CO. BFs and EAFS. Plastics contain lower sulfur and alkaline amounts
Benefits of this process: compared to BF include [68]: compared to coal, heavy oil or coke. Plastics reduce sulfur content
in the hot metal due to their lower sulfur content [78]. The low ash
Mitigation of CO2 production and sulfur content of the plastic can reduce the amount of lime
Reduction in energy consumption and energy savings up to 7.4 (flux) in the blast furnace, and thus reduce the slag ratio and iron-
GJ/t hot metal (>50% BF energy use) making cost of the blast furnace. Because waste plastics show
Reduced iron oxide waste lower thermal ignition temperature, shorter burning time, higher
burning rate, lower ash ratio and higher calorific values when com-
Application of waste plastics in direct reduction process is pared to pulverized coal, they are more beneficial for blast furnace
demonstrated by Sinha (2015) [69]. Reduction of iron ore pellets injection and as a suitable secondary fuel [79,80]. HDPE char from
using coke-plastic showed improved reduction for all the PET com- fast pyrolysis contain, Carbon, 42.62%; Hydrogen, 3.06%; Nitrogen,
positions when compared to 100% coke composition, with 5% PET 0.43%; and Sulfur, 1.8%. The calorific value is 18.82 MJ/kg [81].
and coke mixture offering a high degree of reduction. Higher per- Hydrogen in polymers leads to high H2O and a low CO2 emission,
centage (10%, 20%) of PET-coke lead to reduction in permeability and aid the reduction reaction [according to reactions (1) and
when the accumulated PET char in the reaction vessel are fused (2)] [82]:
to huge hive like configurations.
Ironmaking in the rotary hearth furnace (RHF), a direct reduc- Fe2 O3 + 3CO = 2Fe + 3CO2 (coke, pulverized coal) ð1Þ
tion process can utilise non coking coal and low-grade carbona-
ceous materials such as waste plastic as reductant, for the Fe2 O3 + 2CO + H2 = 2Fe + 2CO2 + H2 O (using plastic) ð2Þ
reduction of iron ore e.g. Commercially operating Fastmet’
The pyrolysis reactions of plastics include conversion of poly-
process/‘Fastmelt’ process, and ITmk3 process, ‘Redsmelt’ process,
mers into hydrocarbons (mainly CH4):
‘Inmetco’ process, ‘Iron Dynamics’ process, ‘DRyIron’ process,
‘Comet’ and ‘SidComet’ processes and Hi-QIP process. Higher per- Polymers ! Cn Hm (g) ð3Þ
centage of volatile matter of the carbonaceous reductant can cause
rapid evolution of gas to increase the internal pressure within the Decomposition of hydrocarbons into carbon and H2;
pellets or briquettes leading to break-down of the same [70]. Cn Hm (g) ! nC (s) + m/2 H2 (g); DH = hydrocarbon dependent
MIDREX NGTM, the natural gas-based configuration of the
MIDREXÒProcess, produces direct reduced iron (DRI). The high ð4Þ
temperature MIDREXÒ Reformer converts natural gas into reducing (e.g. CH4 ? C (s) + 2H2 (g); DH° = 75.6 kJ/mol);
gas rich in H2 and CO (methane dry forming reaction), reducing the The hydrocarbon could also act as a sink for CO2 gas, producing
iron ore to iron. The reaction also produces CO2 and H2O. CO2 from CO and H2 (reaction (5))
the reduction furnace is used in the reforming reaction of CH4 + -
CO2 to produce more reducing gases 2H2 and 2CO, used in DRI Cn Hm (g) + nCO2 (g) ! 2nCO (g) + H2 (g) ð5Þ
production. Water vapour reacts with C produced from the cracking reac-
tion of CnHm:
MIDREXÒ Reformer facilitates the reaction between both CO2
and H2O with natural gas and does not require any CO2 removal H2 O + CðsÞ ! H2ðgÞ + COðg ); DG = 133.72—0.1419 T kJ/mol ð6Þ
system [71]. The syngas produced from plastics can be used in a
The reduction of H2O to H2 and CO through Eq. (6) occurs
Midrex DR plant and it is estimated that this alternative route
between 2 and 6% in the temperature range 1000–1200 °C [83].
results in 5% CO2 mitigation [72].
JFE Engineering, developed electric arc melting furnace ECOARC. CH4 + CO2 ! 2CO + 2H2 ; DH = 247.3 kJ/mol (methane dry reforming)
Which can process press scraps from scrapped automobiles, ð7Þ
with high plastics and other combustible content. Benefits of
and the Boudouard reaction (reaction (8)).
ECOARC compared to conventional EAFs include [73]:
electrode consumption reduced by 50% C + CO2 ! 2 CO; DH = 172 kJ/mol ð8Þ
reduced electricity consumption: 196 kWh/ton at an oxygen
consumption of 40 m3 /ton oxygen CO + H2 O (g) ! CO2 + H2 ; DH = 41 kJ/mol; (water gas shift reaction)
improvement in yield by 1.5% ð9Þ
flicker level reduced by 40%
S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646 641
CO + 3 H2 ! CH4 + H2 O (g); DH = 205 kJ/mol; (reverse steam reforming reaction) Embodied energy is the amount of energy consumed to extract,
ð10Þ refine, process, transport and fabricate a material or product
Secondary reactions increase the CO content. CO content is (including buildings). It is often measured from cradle to (factory)
greater than the CO2 at a high heating rates and depends on the gate, cradle to site (of use), or cradle to grave (end of life). Likewise,
Boudouard reaction (reaction (8)) [84]. As the hydrogen content embodied carbon footprint is the amount of carbon (CO2 or CO2e
in the bosh gas increases, the water–gas shift (reaction (9)) gains emission) to produce a material. The calculated embodied energy
prominence in the reduction process. and the embodied carbon values from cradle to gate are given in
Reduction by H2 needs less energy compared to the direct the Table 6. The calculation is based on the data sourced from Geoff
reduction as the process is less endothermic, needing less energy. and Craig 2008, Dong 2018 and O’Farrell, 2018, [5,87,88].
Diffusivities of H2 and H2O are higher compared to CO and CO2 The embodied energy coefficients can be obtained by compar-
resulting in faster reduction rates especially at lower temperatures. ing the calorific value of plastics with that of the coke or coal its
High H2 content in the raceway reduces the optimum raceway adi- replacing [87] in blast furnace or EAF. Accordingly, since both plas-
abatic flame temperature (RAFT) [85]. A higher H2 content in the tics and coal have similar calorific values (Table 7), The energy sav-
shaft increases amounts of coke fines in the furnace shaft, ing coefficient of plastic (fplas) is equivalent to one [87].
decreases permeability and offers a higher calorific value (CV) than Japan Iron & Steel Federation aims to recycle 60% of its waste
coal. plastics (600,000 tons) every year in order to save energy [89].
Production of 1 ton of hot metal requires 370 kg of coke and In 2000, Nippon Steel & Sumitomo Metal Corporation used a coke
90 kg of heavy oil depending on the iron ore quality and the pro- oven to commercially recycle large amount of waste plastics [90].
cess. The 90 kg of heavy oil can be partly replaced by up to 70 kg About 200,000 tons per year of waste plastics are thermally
plastics waste. A 220000 t of mixed plastic waste in a BF, achieves decomposed into approximately 20 mass% coke, 40 mass% hydro-
the following [20,86]: carbon oil (tar and light oil) and 40 mass% coke oven gas, which
880,000 m3 of saved landfill, are utilized as iron ore-reducing agents in blast furnaces, raw
>10 millions GJ of saved energy, materials for the chemical industry, and a fuel for power plants,
> 400,000 t CO2 saved per annum, as well as decreased SO2 respectively.
and dust into the air. Table 8. shows the Energy and emission saving in Nippon’s
Plastic waste feedstock recycling in BF saves 47 MJ/kg of waste plastics recycling process (1,200,000 t/yr.) in coke ovens
resources as shown in Figs. 2 and 3 [14]. for various plastics calculated from data in Table 6. PET feedstock
Energy saving and carbon emission reduction (DE) of recyclable energy (chemical energy stored in a material when not used as a
wastes recycling can be calculated using embodied energy/carbon fuel) is assumed to be 40 MJ/kg [61,91].
method as follows [87]: Carbon dissolution into liquid iron is a significant part of the
carburizing process in iron and steelmaking, as the metal carbon
Eraw ¼ Mraw f raw ð11Þ content dictates the melting point of the iron. Up to 5.28 wt% car-
Table 7
Erecy ¼ Mrecy f recy ð12Þ Calorific values of conventional fuels [39], reproduced
with permission.
Table 6
Embodied coefficients for raw materials and recyclable wastes.
Material Embodied Embodied DE = (Eraw Erec), Embodied Embodied Carbon emission Feedstock
energy, Raw, energy, Energy reduction carbon in raw, carbon in reduction by recycling, energy
ERaw MJ/kg, Recyclable, by recycling Craw, kg CO2/kg recyclable,Crec, kg CO2/kg included,
ERec MJ/kg kg CO2/kg DC = Craw Crec MJ/kg
General 89.84 17.97 71.87 2.82 0.57 2.26 35.6
ABS 114.2 7.19 107.01 3.715 0.23 3.48 48.6
High density polyethylene 62.9 18.6 44.3 1.31 0.39 0.92 54.3
(HDPE)
Low density Polyethylene (LDPE) 64.5 11.29 53.21 1.40 0.25 1.16 51.6
Nylon 6 365 1.10 363.91 16.66 0.05 16.61 38.6
Polypropylene 107.44 11.17 96.26 5.66 0.59 5.08 55.7
Expanded polystyrene 104.03 90.25 13.78 2.93 2.55 0.39 46.2
General Purpose Polystyrene 104.03 90.25 13.78 3.25 2.82 0.43 46.3
Polyurethane 104.6 11 93.6 5.45 0.57 4.88 34.67
Polyethylene terephalate (PET) 109.5 21.9 87.6 5.70 0.46 5.24 40
PVC General 71.53 15.1 56.43 2.23 0.47 1.76 28.1
PVC pipe 67.5 0.95 66.56 2.5 0.04 2.46 24.4
Rubber (General) 57.24 12.08 45.16 1.79 0.38 1.41 41.1
Synthetic rubber 120 4.02 42
Natural latex rubber 67.6 1.63 39.43
Epoxide resin 139.3 5.91 42.6
642 S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646
Table 8
Saved Embodied Energy and Carbon in coke oven from recycled plastic streams.
bon dissolve in liquid steel, influenced by methane, hydrogen, ash ing high strength, e.g. car bodies, ships, fittings of overhead electric
content, Si, S and microporosity. Carbon pick-up for metallurgical transmission lines and greatly in construction [107].
coke in liquid steel is 0.8%; for raw HDPE it is 2.48 wt%, and for
PET it is 2.3 wt% [92]. Carbon pick up for graphite is 3%, for
3. Plastics for carbon sequestration
pet coke 4.2%, for charcoal 2%, and for coal and nut coke
1.5% [93].
High carbon foot-print processes, e.g. calcination of magnesium
Even though, the use of thermoplastics has been extensive in
carbonate, carried out in presence of waste plastics and biomass
iron and steel industries, the thermoset plastics have not been used
show 99% and 98% reduction in reduction in CO2 and methane
to the same extent. Only options for EOL thermoset composite
emissions respectively [108,109]. One ton of magnesia (MgO) pro-
materials are: mechanical recycling, chemical degradation and
duction releases 1.1 t CO2 from the magnesium carbonate
thermal degradation towards materials and energy recovery [94].
endothermic thermal decomposition according to the reaction
Thermosets once formed cannot be reformed. Thermoset polymers
(14) [110].
with cross-links that reverse [95] or exchange [96] at high temper-
atures are being developed, making it possible to reworking these MgCO3 ! MgO + CO2 ð14Þ
materials before reuse. Connora Technologies profess commercial-
ization and recyclability of thermosetting composites for re-use or The energy demand for MgO production is up to 12 GJ/t MgO
repurposing [16,17]. Fully recyclable bio epoxy resins are being [111]. MgCO3 calcination results in excessive amounts of CO2
used in composite formation [97]. (1:1 MgO:CO2), consequently the Carbon Avoidance Potential is
Raw thermoset resins aid iron alloy formation, e.g. nano scale very negligible. Biomass and thermoset plastics (epoxy resin)
iron carbide (<2 nm), SiC and ferro silicon at much lower temper- together greatly decrease CO2 and CH4, increase H2 and hydrocar-
atures (1500 °C) than the conventional temperatures above bons production. Addition of epoxy resin causes 99% reduction in
1800 °C, greatly reducing energy and emission [98,82]. Carbon emission. Net Calorific Value, LHV of 0.26 MJ/kg organic
Commercial epoxy resin, epiglue and silicones replace nonre- matter and 16.86 MJ/kg organic matter are realized in presence
newable resources such as coke and pure quartz. The feedstock of epoxy and bio mass and epoxy together respectively, contribut-
recycling of silicones allows maximum resource recovery in iron ing to hydrogen economy [108]. Plastics also greatly reduced CH4,
alloy production while lessening the landfill/depolymerization of generated in presence of biomass using MgCO3/MgO as catalyst
silicones. Silicon, carbon and hydrogen in waste silicones, can sub- [109].
stitute for metallurgical coke and quartzite as alloying elements in Plastics Waste can replace approximately 15% of normal fossil
FeSi or SiC [98]. Carbon pick up >3% was observed for the raw (not fuel in Cement Kilns, at a very high temperature of 1500 °C or
the chars) thermosets. Recyclable thermosets can contribute to more, without the risk of toxic emission due to the burning of plas-
sustainable, cleaner and cost-effective processes. tic wastes. A million-ton capacity cement plant can consume about
Earlier studies on iron ore reduction alloy formation mainly 10,000 MTs to 30,000 MTs of plastics waste annually [112]
involved a solid-gas wetting reaction and mechanism for coke/
char-metal oxide. Devasahayam, 2018, reported a wetting mecha- 4. Advantages/disadvantages
nism involving a solid–liquid-gas reaction providing a better inti-
mate contact and reaction efficiency [82,98–101]. The raw Pyrolysis of waste plastics generates CH4, H2, CO, CO2 and
epoxies and silicones form interfacial covalent bond between the hydrocarbons. They replace non-renewable resources in iron and
metal oxide and the alloying elements in the resins enabling the steel processing [35,113]. Two thermodynamically stable phases
movement of the alloying elements into iron matrix to form alloys. of polymers at 1100 °C are solid phase, carbon and the gas phase,
Plastic wastes (centrifuge tubes) aid Multi-Walled Carbon Nan- CH4 and H2 [114]. Plastics replace fossilized resources as reductant,
otubes (CNTs) formation requiring no external catalyst source, the alloying materials and binders in iron ore pelletization, contribute
iron based reactor acting as the catalyst [102,103]. Iron catalyst to reduction in process temperature, saving on energy resources,
and MgO substrate is one of most common catalyst-substrate com- contribute to energy generation and hydrogen economy and
binations used for CNT [104]. 61.5 vol% of CNTs helps increase reduce harmful emissions. Plastics are used in both direct smelting
both soft magnetic and mechanical properties in Fe–Co alloys. and direct reduction iron making processes. Both the thermo plas-
The CNTs also increase the volume fraction of the long range tics and the thermosets benefit the iron ore industry. The ther-
ordered structures in the matrix alloy [105]. mosets offer a solid-liquid-gas wetting mechanism offering a
It is reported that in Fe alloys, iron carbides form as a result of a new paradigm to the efficient iron ore pelletization and iron alloy
chemical reaction between the iron matrix and the included CNTs. production. Plastics have higher H2 content, than the coal. They
Iron carbide alloy formation enhances the microstructure-related also have high calorific value with high carbon reactivity. They
and mechanical properties of the composites due to the formation inhibit sticking of iron ore during smelting processes with high
of strong interfacial bonds in presence of CNT’s in its matrix. Refs. metallization rate. Presence of plastics increases the reduction
[106,99,100,82,98] offering broader industrial applications requir- rates due to higher diffusivity of H2 than CO. Plastics aid carbon
S. Devasahayam et al. / Materials Science for Energy Technologies 2 (2019) 634–646 643
nanotube formations offering broader industrial applications fuels are shown in Table 10 for comparison [116]. It is reported that
requiring high strength, e.g. car bodies, ships, fittings of overhead NOx, SOx and particulate emissions from German BFs due to waste
electric transmission lines and greatly in construction. Carbon dis- plastics injection met the statutory environmental regulations
solution in liquid steel alloy is enhanced in presence of plastics. [117]. BF operation results in nil dioxins from waste plastics and
Use of plastics in blast furnaces, saves resources up to 60 GJ/t. reduced CO2 (Fig. 4). Since the CO is consumed as a reductant in
Dry coke to hot metal ratio has declined to 0.45:1 in 2008 from iron and steel industry it contains the CO emissions to the atmo-
1:1 in 1950. Plastic replacement can also reduce the process tem- sphere. Adding 2 wt% waste plastics to coke in BF mitigates CO2
perature by at least 100–200 °C [115]. Tyre injection One Steel’s emissions by 2% [43,46]. Combustion of waste thermoset thermo-
Sydney steel mill, Australia, reduced the electrical energy con- plastics and e-wastes release dioxins, HBr, polybrominated diphe-
sumption by 0.043 MJ/kg, reduced the carbon injectant by 58 kg/ nylethers. When halogenated wastes are subjected to pyrolysis,
heat [77]. polybrominated diphenylethers emissions are lowered accompa-
As waste plastics contain negligible amounts of sulfur, the SO2 nied by carbon, H2, HCl, benzene and toluene generation, but no
emissions are greatly reduced (Table 4). Table 9 shows the offgases dioxins [118]. Calcium carbonate added as a flux can control the
generated from different polymers. Carbon emissions from other release of C6H6 and HBr [119].
Table 9
Off gas in the presence and in the absence of plastic resins [59] (data sourced from Sekine et al. (2009)).
Table 10
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