Welcome to Sustainable Resources and Processing

CHEN 44461/64491 – Professor Arthur Garforth

The Chemist makes the substance in the best way and then the Chemical Engineer
transforms the substance into materials on a scale which is useful to society.
Safely Sustainably Ethically
L1. Linear and Circular Economy of Chemicals and Products
Sustainable Resources and Processing , CHEN 44491 & 64491

Intended Learning Outcomes:

• Introduce Green Chemistry and Chemical Engineering

• Understand the concept of linear and circular economy -

Identify, describe, evaluate the benefits and drawbacks

• Waste disposal and implications, monitoring and

analysis (e.g. chemical and biological oxygen demand)

• Case study: Improving the circularity of Polymer

waste and assessment of methodologies (LCA)

Arthur Garforth – Chemical Engineering, Engineering A, 4W, Office 22

arthur.garforth@manchester.ac.uk
Principles of Green Chemistry and Engineering
• 12 Principles of Green Chemistry based on UN Sustainability Goals
• Efficiently utilises (preferably renewable) raw materials, eliminates waste and
avoids the use of toxic and/or hazardous reagents and solvents in the
manufacture and application of chemical products.
• According to this definition ‘raw materials’ includes the source of energy.

• 12 Principles of Green Chemical Engineering

• Conserve energy and resources and avoid waste and hazardous materials—as
those of green chemistry, but from an engineering viewpoint.

• Sustainable Development “meeting the needs of the present generation

without compromising the ability of future generations to meet their own needs”

• Sustainability is our ultimate common goal

UN Sustainable Development Goals
(Video 1.25 mins) https://youtu.be/0XTBYMfZyrM
UN Sustainable Development Goals – Chemical Engineers contribution
– IChemE (President Nigel Hirst) – My research goals (AG)
What is a linear economy?
A linear economy traditionally follows the “take-make-dispose” step-by-step
plan. This means that raw materials are collected, then transformed into
products that are used until they are finally discarded as waste.
5000 years of Landfill
3000 – 1000 BC in Knossos, Crete (large pits) 1874 Incineration attempted in Birmingham, UK
500 BC - Municipal tips one mile out of Athens 1885 large scale incineration in USA

1908 102/180 incinerators abandoned = cost,

1354 House rubbish to be removed weekly poor maintenance and poor air quality
1388 Act banned throwing rubbish into ditches/rivers
1414 Beadles of London – willing to pay informers! 1924 NY citizens revolt over land + ocean dumping

Middle Ages it all went from bad to worse 1935 Incineration of over 40% of waste BUT air
pollution and cost prevented wide-scale adoption
1741 “London abounded with such heaps of filth”
Same was true for much of Europe up to 19th C

late 1800s, urban centres had sanitation departments,

garbage was collected and transported out of town for
disposal in open pits and later in excavated pits.
1881 New York created Dept for Street Cleaning
1990 82% of solid waste was buried !!
duties previously carried out by the Police Dept!!
(note: 25% NY waste dumped into the sea until 1934)
Disadvantages of Landfill sites:
• Occupation of Land • Leachate Hazard and Groundwater pollution:
• Vermin/Scavengers • Expensive and variable effectiveness (e.g. heavy metals)
• Pathogen content • Inorganic (e.g. metals, salts)
• Organic chemicals (in household cleaning products)
• Aesthetics
• Other organic compounds found include chlorinated
• Economics organic pesticides (Aldrin, dialdrin, DDT now all
banned), PAHs and halogenated aromatic compounds.
• Gaseous emissions:
Metal g/ton (~ppm)
Odour, Fire and Explosion Vaping?!
Cd 4.7
CO2, CH4, N2, Mercaptans, H2S,
Pb 424 Compound mg/ton
H2 and organic acids
Cr 90 PCDD (…dioxins) 29
Ni 24 PCDF (…furans) 2
CH4 CO2
Hg 0.71
Tons of gas/ton MSW 0.085 0.193 PCB 73
Sn 12.5
(CO2 equivalent) 5.830 PAH 426
Ar 1.14
Chlorobenzene 47
Cu 266
Zn 242
Chlorophenol 137
Aqueous Emissions are assessed prior to discharge
• When discharged bacteria feed on it →oxidising it: Examples of Theoretical Oxygen Demand
C → CO2 N → NO3- S → SO42-
• O2 required depletes the water resulting in death of CO(NH2)2 + 9/2 O2 → CO2 + 2H2O + 2NO3-
aquatic life and the amount used is the biochemical
oxygen demand (BOD) CH2OHCH2OH + 5/2 O2 → 2CO2 + 3H2O
• BOD5 determined using standard test (5 days at 20oC)
→ a good indication of effluent on environment
Other contaminants may be specified on toxicity
and include:
• A faster test using acidic K2CrO7 (strong chemical
• Nominated compounds (e.g. phenol, benzene)
oxidant) = Chemical oxygen demand (COD)
• Heavy metals (Cr, Co, V and so on)
• COD is usually higher than BOD5
• Halogenated organic compounds
• Domestic sewage for example, BOD5/COD = 0.37
• Organic N2 and S
• An average value across all contaminants = 0.35
• Nitrates, Phosphate
Effluent treatment regulations might specify a • Suspended solids
level of BOD5 or COD or both. • Acidity/alkalinity (pH)
(Wang& Smith)
 Eutrophication and Nitrate level standard
• WHO drinking water .

< 50 mg/l NO3- (<50 ppm)

• Global concern over harmful algal

blooms and effects on humans
J. Water & Health (2019) 17(5), 826

• Nitrates cause neonatal birth

defects and blue baby syndrome.
Also colorectal, bladder and breast
cancer, and thyroid disease.
Int. J. Environ. Res. Pub. Health (2018), 15, 1557

https://water.jrc.ec.europa.eu/portal/apps/opsdashboard/index.html#/cb6034c2a75e4df282f8a62f90c16caa
https://ec.europa.eu/environment/water/water-nitrates/index_en.html (10th May 2018)
Plastic Pollution - Plastic Waste & Microplastics
Plastic waste

Video (3.20 mins)

https://news.sky.com/story/viewers-
clean-norway-beach-following-sky-news-
whale-death-documentary-11346575

Microplastics
What are they? Video (2 mins) https://youtu.be/aiEBEGKQp_I Yummy
Video (50 secs)
In the air : Each person inhales 16.2 bits of plastic fibre per hr https://abcnews.go.com/US/humans-
consume-equivalent-credit-card-worth-
~ equivalent to size of credit card per week (260 g p.a.) plastic-week/story?id=63687144

In the ocean : Emerging evidence that particles from the wearing of tyres and Video (3.40 mins)
road materials are a major source of micro-polymers ending up in the ocean. https://youtu.be/ZFreX8pJiG4
16
 Plastics in the Food-chain ! Should we be worried?
Only one report has examined 8 healthy human
volunteers faeces from around the world
Microplastics from
1o and 2o packaging
enter Food Chain

Baechler et al, Limnology and Oceanography letters

5 (2020) 113 -136
Ann Intern Med. 2019;171:453-457. doi:10.7326/M19-0618

WHO has called for more research on

the effect of microplastics in humans
 What is a “Circular Economy” ?

• An economic model built on the concept

of cycles where the earth is considered to
be as a closed system and circular system
with limited capacity to assimilate waste or
pollutants.

• Wastes are a resource and manufacturing

loops should be as small as possible, i.e.
should require the least energy input and
retain the highest value.

• A circular economy follows the 3R approach:

reduce, reuse and recycle
Sources: Hong, M. and E. Y. Chen. 2019. Future Directions for
Sustainable Polymers. Trends in Chemistry 1(2):148-151, and
https://carbios.fr/en/technology/biorecycling/
 Recycling Landscape Generation and recovery of material in MSW in 2000 (US EPA 2010)

Material Generated Recovered Recycled

200
MSW in USA (population 328 M) (2000) (M tonnes) (M tonnes)

150 Paper 76.42 42.94 56 %

Mass (M tons)

Glass 12.15 2.81 23 %

100
Steel 15.68 5.29 34 %
50 Other non-Fe 1.76 1.21 69 %
metals
0
Plastics 30.05 2.12 7%
2000 2010 2018
Rubber/Leather 7.41 1.06 14 %
200 Textiles 12.37 1.89 15 %

150 Wood 16.39 1.58 10 %

Mass (M tonnes)

MSW in EU (population 514 M) Other mat.s 4.5 1.15 26 %

100
Food and … 31.79 0.8 3%
50 Yard trimmings 32.9 21.3 65%
Misc inorganics 3.78 - -
0
1999 2009 2019 total 249.61 82.87 33 %
Individual Country Recycling Rates - 2016
Methods used for recycling polymers

Polymer
Recycling

1o 2o 3o 4o
Re-extrusion Mechanical Chemical Incineration
• Waste from product • Open Loop • Closed Loop • Waste to energy
manufacturing reused • “lower quality” • Keeps chemical value • Decline in use in EU
back into process • Limited on no. of recycles → GHG emissions
• No new planning
permission (UK)
Fate of Plastic across Europe - 2021

“Reshaping Plastics – Pathways to a circular, climate change

neutral plastics system in Europe” (Apr 2022, SYSTEMIQ)
“Pathways to a circular, climate change neutral plastics system in EU”
Focus on important plastic (2021) = LINEAR
sectors: Incineration, Landfill,
Energy Recovery, Export
1. Packaging or Littered
2. Household goods
Reduce
3. Automotive
Reuse
4. Construction (by 2030)
Recycle

Covers 75% of total EU

Elimination, Reuse,
plastic demand and 83% New delivery models,
post-consumer waste Substitution
generation
Ambitious expansion,
£££ collection, sorting,
mechanical, chemical
recycling infrastructure

“Reshaping Plastics” (April 2022, All circularity levers

SYSTEMIQ for Plastics Europe, applied upstream
developed Circularity Scenarios as (by 2030, 46% (reduction /substitution)
GHG saving) and downstream
shown here) (recycling scenario)
ANOTHER WAY TO MOTIVATE = LEGLISLATION

(EU) 2019/904 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL

5 June 2019 on the reduction of the impact of certain plastic products

on the environment – e.g. tethered plastic tops on bottles!

1st International Global Plastic Pollution Treaty (GPPT) in Kenya Nov 2023

More than 170 Countries gathering in to draft the 1st GPPT.

Final report will be out in 2024.

28
 Recycling of Polymers – where to start?
Municipal Packaging Waste

= 73.2% of plastic packaging waste

o UK processed 4.0 Mt of virgin & recyclate (2018)

o Food and non-food packaging (1.6 Mt)
o Flexible packaging accounts for 320,000 t
o Multi-laminated accounts for 80,000 t
o Flexible packaging difficult to collect, sort, recycle
o New technology to divert from landfill or incineration
Sources: Hong, M. and E. Y. Chen. 2019. Future Directions for Sustainable Polymers. Trends in
Chemistry 1(2):148-151, and https://carbios.fr/en/technology/biorecycling/ 29
 Improving the circularity of used polymers
CCUS
CO2, CH4
Crude Oil

Petrochemical
Intermediates
?
(C2= C3= p-xylene)

Waste to
monomer
(iso 22095)

Recyclate
Intermediates
• LPG
• Naphtha Cat Cracking
Ind. Eng. Chem. Res., 58 (45), 20601-20609 EP2437886 ; EP 2649121
• Jet (SAF) Hydrocracking
Circular economy – Industrial example
• (2018) SABIC working with UK based Plastic • (2021) SABIC (www.sabic.com) cooperate
Energy on using chemically recycled plastics with BP (www.bp.com) on creating a circular
waste as feedstock at its production facilities economy at Gelsenkirchen, Germany, where
in Spain. (https://plasticenergy.com/ ) both play a prominent role as producers
Chemical recycling Plastic Energy
, Gelsenkirchenl site (Photo: Sabic)
operates two plants in Spain
(Photo: Plastic Energy)

https://www.plasteurope.com/news/detail.asp?id=241332
https://youtu.be/XLtvPuzzFhw • https://www.plasteurope.com/news/SABIC_t247164/mmm
The Times: 11/07/2022
Methods of recycling polymers

Polymer
Recycling

1o 2o 3o 4o
Re-extrusion Mechanical Chemical Incineration
Open Loop Closed Loop
Waste from product Decline in use in EU
Downstream Upstream
manufacturing reused GHG emissions
“lower quality”
back into process

How do we choose ?
Life Cycle Assessment (LCA)
• An inventory – based technique for assessing the potential environmental
impacts associated with a product, with scope depending on which stages of life
of the product are included, e.g. gate-to-gate, cradle-to-gate and cradle-to-grave.
• Abiotic Resource Depletion (reference, Sb)
• Abiotic Resource Depletion of Energy (reference, Fossil fuels)
• Primary Energy Demand (Total use of energy in LC renewable and non-renewable)
• Global Warming Potential (CO2, CH4 and N2O) - (reference is CO2)
• Stratospheric Ozone layer depletion potential (CFC-11)
• Human Toxicity potential (air, water and soil) (1,4 dichlorobenzene)
• Eco-toxicity potential (freshwater + marine aquatic, sediment and terrestrial toxicity)
• Photochemical oxidant creation potential (VOCs, NOx – photochemical smog) (ref C2H4)
• Acidification Potential (SOx, NOx and NH3) (ref species SO2)
• Eutrophication potential (nutrients to over fertilise, NOx, NO3-, NH4+, PO4 3- )
Note: ISO 14040 is an overarching standard encompassing all four phases of LCA.
ISO 14041 deals with goal and scope definition and life cycle inventory methods.
ISO 14042 deals with life cycle impact assessment methods and,
ISO 14043 life cycle interpretation methods.
LCA of polymer recycling routes – CO2 emissions

Multiple solutions will be needed.

• Mechanical 1st where possible

• Chemical to preserve valuable chemicals
“The times they are a changing”
No planning permission for Incineration.
Export of plastic to be banned.

https://www.youtube.com/watch?v=s138S0keHSM
Further Reading
General Sorting, Mechanical and Chemical Recycling links
• Recycling PET, Polygenta Technologies Limited is a leading producer of recycled Polyester Filament
yarn from 100% post-consumer PET bottle in Indian Subcontinent. The plant is located in Nasik, India
and has a production capacity of 10,000 MT per annum. https://youtu.be/cpGr22a1_BE

• Recycling Nylon - Sedna® carpet is soft, luxurious and durable. It is made with ECONYL® regenerated
nylon, a yarn made from recycled waste material such as old carpets and abandoned fishing nets
collected from the bottom of the sea. Sedna (https://www.youtube.com/watch?v=cMGOZHakdTI)

• WRAP and recycling and collections points:

https://wrap.org.uk/resources?type=1499&field_initiatives_target_id=All&sectors=All#

• Collection and mechanical recycling: https://www.terracycle.com/en-GB/pages/tools-and-resources

• Automated sorting technology: https://zenrobotics.com/

• Recycling codes for polymers: https://en.wikipedia.org/wiki/Recycling_codes

• Entrepreneur alert: https://earthshotprize.org/ ; https://youtu.be/bymiMNa6QJk

L2. Conventional and alternative routes for fuels and chemicals
Coal Natural Gas Biomass Natural Gas
Contents and Learning Outcomes
Gasification Steam
• Gasification Technology to Synthesis Gas >1100oC Reforming
• Detail routes to chemical production from synthesis gas ≤ 150 bar 750 - 870 oC
Part. Ox 15 – 30 bar
• Strategies for the control of emissions from gasification
• Alternative feedstocks (waste and renewable)
Shift reactor HTS/LTS
• Steam reforming (Autothermal reforming)
• Concept of “grey”, “blue” and “green” H2 production Synthesis gas Synthesis gas
(CO + H2) (CO + H2)
• Conversion of synthesis gas into fuels and chemicals
• Biomass conversion processes (1o and 2o sources)
MeOH FTS
• Highlight status of CO2 utilisation (TRL) 40 - 100 bar 15 – 40 bar
200 – 320oC 200 – 350oC

Refining Refining
CEAS, Engineering A, 4W Office 22,
Chemicals Liquid fuels
arthur.garforth@manchester.ac.uk