QUESTIONS

Lecture 1+ Reading intro and chapters 1 and 2

1. Why recycling?
 Recycling contributes to circular economy and materials sustainability. Through recycling it is
possible to process materials to obtain the same or lower quality/grade.
 Over-use and compromised materials usage (increased diversity and complexity of elements in
common products), material scarcity and dependence.
 Benefits: extension of resource life, great energy savings, less pollutions & CO2 emissions,
reducing landfill space, increasing employment opportunities.
2. What happens if we don’t recycle (properly)?
 There can be a material scarcity
 Determines the quality and grade of the recovered product
3. How to recycle?
Recycling involves interconnected multi-stage operations:
*Should already start during the design and manufacturing phases.
 Collection, transport
 Pre-processing: dismantling, size reduction, sorting and separation
 Generation of scrap
 End-processing: chemical or metallurgical recovery and refining
4. What is the cost for recycling?
Recycling is governed by policies, environmental regulations, and more and more by the economics:
 Recycling does help to conserve resources and reduce wastes; it is important to remember that
there are economic and environmental costs associated with waste collection and recycling. For
this reason, recycling should only be considered for the waste which cannot be reduced or reused,
and recycling operation is environmentally sound & economically viable.
5. Can recycling be economical?
Depends on the processing needed for the recovery of the materials, as well as the available technology.
6. How much have been done with recycling?
There has been an increasing trend to recycling materials, due to the challenges that us as modern societies
are facing (consumption of resources, new transitions to technological and ‘clean’ approaches). However,
the recycling rates could be much higher.
7. What are the limitations?
Available technology, costs, opportunities among the countries.
8. Is recycling always the best option?
No, recycling is the third option (after reduce and reuse). Recycling should only be considered for the waste
which cannot be reduced or reused, and recycling operation is environmentally sound & economically
viable.
9. What are the remaining problems and challenges?
Available technology, costs, opportunities among the countries.

10. What should we do to improve recycling?

Implement and improve available recycling technologies, develop new technologies for recycling, identify
the groupsof materials that can be recycled (ceramics, polymers and plastics, glass, metals), have a look in
the materials that are ‘lost’ in landfills, tailings and other residues, improve the collection and pre-
processing, explore the collection of different groups of materials (i.e. scarce metals), social programmes
for commitment.

Lecture 2
Recyclability of materials: How easy or difficulty to be recycled and what is the final product quality. Quantity,
Quality, Timing/Life time, Efficiency, (Cost, Market)
1. What is the recycling value chain?
a. Collection: regional recycling programs, collection and transportation (recyclers)
 b. Physical separation: pre-processing: pre-sorting, liberation and separation (recyclers)
c. Materials refining: end-processing: final chemical/metallurgical separation (refining), paper mills, steel
plants, Al remelters and refiners, glass manufactures, plastics re-processors
d. Markets of the recyclates: volatile and dynamic, competition with virgin materials (quality and prices)

2. How metals flow from the primary production (after mining) to their end of life and come back to the raw
materials supply again?

3. Where are the losses?

Sources: MSW (Municipal Solid Waste), industrial waste (ashes, slags, residues, sludge, etc.), failed
processes, users’ homes.
4. Definition of various recycling rates: (1) EoL Recycling Rate; (2) Recycled Content; (3) EoL collection
rate; (4) EoL processing rate; EoL recovery/refining rate; (5) Old Scrap Ratio; (6) Overall Recycling
efficiency (rate).
 EOL Recycling Rate (EOL-RR, %)
o How much available EOL material has been recycled
o How well a material is recycled
o Eg: fraction of zn recycled relative to the amount of zn available at EoL

EoLmetal collected for recycling

EoL products (metal content )

 Recycled Content (RC, %) = Recycling Input Rate (RIR)

o Fraction of recycled material contained in the total material input in the flow metal
production
o Relative to primary production
o Eg: fraction of zn scrap (new and old) in the total metal use in fabrication and
manufacturing
Scrap ¿ manufacturing ( new scrap ) + Scrap used ∈production(new∧old ) ¿
Primary metalinpu
 Old Scrap Ratio (OSR, %)
o Ratio of the old scrap to the total (old + new)
o More old scrap, more true recycling!
o Information on the composition of the scrap used in the metal production
o Eg: fraction of zn from old crap in the overall recycling flow
 EoL metal collected for recycling
( EoL metal collected for recycling+ Recycled EoL metal(old scrap))

 EoL Collection rate: (X, %)

o How much of the EoL metal (in products) is collected and enters the recycling chain (as
opposed to metal that is landfilled) with respect to the total available
EoLmetal collected for downcycling
EoL products (metal content )

 EoL processing rate: (physical) pre-processing (Y,%)

o Percentage of secondary materials (scrap) physically separated from the collected EoL
products

 EoL Recovery/Refining Rate: (metallurgical) end-processing (Z,%)

o Percentage of end-use material recovered with respect to the material content feeding to
the refining plant (smelters/refineries).

EoL Recycling Rate (EOL-RR)  X*Y*Z

**** Recycling into new products, regardless of quality

 Overall Recycling process efficiency rate (%):

o The efficiency in any given recycling process
EoLmetal collected for recycling
EoLmetal collected for downcycling

5. Two types of recycling:

 Up-cycling: recycling back to virgin materials quality (high value-
added recycling) – “functional recycling”
 Down-cycling: recycling to lesser quality materials
6. Why does the collection rate highly influence the EoL recycling rate?
Because it is the first step for recycling, and it dictates the quantity and quality of the materials that will be
recovered. Improve by: design for recycling and technology
7. Please explain grade and recovery (rate) in recycling, and the relationship between the two. How they
influence the recycling cost?
 Grade: the purity of a material in the product fraction
o A measure of the product quality
 Recovery (rate): % of marketable materials compared to the same materials in the feed (waste) (=
processing rate)
o A measure of separation efficiency (quantity)
There should be a decision on whether to focus on achieving a higher grade or recovery rate, depending on the
material that is to be recycled, the sector, and the economics. It is a challenge, as: Higher grade → lower recovery
rate; Higher grade → higher processing cost

Both influence the recycling cost, as this highly depends and is determined by the recovery rate, grade, and efforts
(consumption, labour, applied technology etc.)

o Feed: feed (mass) = product (mass) + tailing or waste for reject (mass)
o Recovery of the material:
Product ( mass )∗concentration p conc p∗( conc f −conc t )
R= ∗100 %= ∗100 %
Feed ( mass )∗concentration f conc f∗( conc p−conc t )

Regulations & recyclers: + recovery rate

Manufacturing industry: + grade/purity

8. What is the cut-off grade? How does it affect the recycling operation?
The minimum concentration of valuable components. It involves, setting the quality of recycled (final)
materials (determined by the way recycled materials are used by end-users), and sometimes could be lower
than those of virgin materials.
9. Exercise slide 18

Lecture 3
1. What are the various components of recycling cost?
 CAPEX (Capital): long term investment (buildings, equipment, machinery) + OPEX
(Operational costs): continuo investment (labour costs, consumable, maintenance, energy
consumption, logistics, etc.)
2. What is “Economy of Scale” and “Diseconomy of Scale”? What are their implications for recycling
industry?
 Economy of scale: manufacturing/ recycling of a product where price decreases with the
increase of volume production. Reduction in product cost
o 0.6 rule: capital costs increase with 0.6 power of capacity increase
 Eg. 4X increase of production volume – capital cost 4 0.6

 Diseconomy of scale: situation in which economies of scale no longer function for a

company. The company sees an increase in marginal cost per unit volume when output is
increased. ☹

Implications: in EofS there could be a technological advancement: higher investment and processing costs; larger
recycling capacity; increased collection and transportation cost. In DofS, higher processing and separation cost (per
unit); compromised recycling rates; not compelling to law.

3. You have been assigned to lead a project to establish a recycling plant for precious metals from printed
circuit boards (PCBs). Discuss the key considerations you must address to ensure the project's
technical, economic, and environmental viability.
  Costs (CAPEX & OPEX), regulation, viability of the recycling process, available supply,
profit, design for recycling, time, labour opportunities.

4. Calculate the expected increase in production volume by three times, applying the 0.6 rule.
0.6
3 =1.93
5. What are the characteristics of a complex product? How product complexity affects the recycling cost
and operation? Please use examples to explain.
 A complex product is one that has been made of a considerable amount of different materials,
and/or its assembly level is difficult. High degree of elemental mixing.

A complex product can affect its recycling cost and operation due to the processing that has to be carried out in
order to dismantle it and recover the different materials from it. Diluted streams of materials (= more reject streams
with conc. Lower than the cut-off-grade). However, more complex = more recycling cost/tonne.

6. What is a critical raw material? Discuss about the critical raw material act (CRMA). Critical raw
materials (CRMs) are raw materials of high economic importance for the EU, with a high risk of
supply disruption due to their concentration of sources and lack of good, affordable substitutes.

The CRMA Act: increase and diversify the EU’s critical raw materials supply; strengthen circularity
(including recycling); support research and innovation on resource efficiency and the development of
substitutes

7. What is the importance of recycling in the supply of CRMs?

Enhance circular economy, and compile with the goal of: at least 25% of the EU’s annual
consumption from domestic recycling. Cut dependency on foreign sources.

Lecture 4

1. What is the recycling value chain? Pre-processing consists of three main steps, explain them.
2. Collection: regional recycling programs, collection and transportation (recyclers)
3. Physical separation: pre-processing: pre-sorting, liberation and separation (recyclers)
a. Pre-sorting: dismantling (removal of useful parts for reuse) and depollution (removal of
substances posing health or environmental risks and/or those whose presence could adversely
affect (contaminate) the quality of the secondary raw, reducing volatile organic compounds
emissions (VOCs) and in
preventing fires and explosions)
b. Liberation: leads to volume or size reduction
c. Separation: segregation based on different physical/chemical properties (size, shape, density,
surface friction, magnetism, colour, conductivity)
4. Materials refining: end-processing: final chemical/metallurgical separation (refining), paper mills, steel
plants, Al remelters and refiners, glass manufactures, plastics re-processors
5. Markets of the recyclates: volatile and dynamic, competition with virgin materials (quality and prices)

6. What is “liberation”? What types of liberation tools and machines are available and how do they work?
Liberation refers to the action in which mechanically connected materials are disjoined from each
other, and can be very complex. Leads to a size and volume reduction.

Mechanisms (tools):
 Manual: traditional, time consuming and costly, still required (hazards)
 Mechanical size reduction: machines (cutting, grinding, milling, etc.)
o Comminution: crushing and grinding
 Crusher (jaw crusher): reciprocating movement of the swinging jaw
compresses and crushes the material as it enters the zone between the jaws.
The type, feed rate and the crusher speed determine the type of the
 processed material and the size of the produced particles. Mat (mainly glass,
rocks and Fe metals)
 Shears, shredder: 1) material fed into the rotating cutters, 2) Cutters grab
and pull the material through the blades for cutting 3) the type and size of
the produced particles depend on the type of blades used, the rotational
speed and the openings of the screen. Mat (tires, metals, plastic, wood,
leather, paper).
 Mills (hammer and ball mills): specially designed blades located on the wall
of the rotating shell, the balls (made of steel, rubber or ceramics) are lifted
up on the rising side of the shell and are left to fall on the feed material from
near the top of the shell. The degree of milling is influenced by the type of
balls, the rotational speed and the residence time. Mat (ores, glass, slag,
refractory materials)
 Cryogenic: immersion in N2 liquid and crushing
 Robot assisted: faster, safe handling of hazards, suitable for repeating actions

7. How will “liberation” affect the quality of the recycled materials (recyclate)?
Liberation can improve the quality of recycled materials, as it will make the separation steps easier by
size or volume reduction.

8. What are “identification and sorting”? What identification and sorting technologies are available for
recycling? How do they work?
Identification and sorting are both physical separation technologies.
 Identification: manual sorting, separation equipment, sensor-based sorting.
o Manual sorting
o Separation equipment: density separation, wet or dry cyclones, centrifuges, Magnetic
separator, Eddy current, floatation, screening
o Sensor-based sorting: visual and instrumental identification
 Visual: optical (cameras, manual)
 Instrumental: portable optical emission spectrometer, portable X-ray
Fluorescence (XRF) spectrometer, radiation detector, XR scanner, Infra-red
cameras

9. What are the main physical separation technologies? What are the principles?
 Density separation: based on the principle that different materials in the waste may have
different densities. If multiple materials with different densities are placed in a flow with an
intermediate density, it is possible to separate materials based on their specific gravity.
o Gravity air separation: air flows in a particular direction; material with higher density
than that of air is disengaged at the bottom, material with lower density is carried by
the ascending vortex out of the top.
o Cyclone separator: high speed rotating flow in a helical pattern; denser particles have
too much inertia to follow the tight curve of the stream, they strike the outer wall and
are collected at the bottom, and lighter particles leave the cyclone out of the top of
the container. Good for fine particles.
o Dense medium separation: bath of fluid with heavy media and feed material to be
classified is immersed in the bath; material with lower density will float and with
higher will sink.
o Jigging: Water is pulsated up and down and it’s created an alternating direction
vertical force; material is re-layered; high density particles are settling down to the
bottom layer quickly, and low density settle slowly in the top layer.
o Shaking table: inclined deck with riffles is washed with water. the direction of the
water on the table is perpendicular to that of the riffles and the table shakes in the
long axis. This movement helps the denser
concentrates to ascend and move towards the concentrate end, the lower density
 particles will not be able to ascend, and they will flow over the riffles towards the
tailings end.
 Magnetic separation:
o Magnetic separation: picking up ferrous scrap from a mix using a magnetic force.
Permanent or electrical magnets, applying/generating fields of low magnetic
intensity.
 Ferromagnetic: materials are strongly affected by m. fields
 Paramagnetic: materials are only slightly (but still notably) affected by
magnetic fields
o ECS: separation of non-ferrous metals from non-metals, Separation of different non-
ferrous metals (incl. stainless steel)
 When a conducting object is passing across an alternating magnetic field,
(eddy) currents will arise in the object, generating a (Lorentz) force
perpendicular to the field applied.
 An electric current is induced within a conductor when it is exposed to a
changing magnetic flux, and the induced electric current generates a
secondary magnetic field around the conductive particle/material, which
opposes the original magnetic field
 The interaction between the secondary magnetic field and the external
magnetic field creates a repelling force, which propels the conductive
particle out of the product stream,
effectively separating it. The irregular shape of conductive particles causes
the induced current to flow in swirling paths within the material (Eddy
Current).
 Are not designed to sort ferrous metals/steel which
become hot inside and lead to damage; must be removed beforehand

10. What factors affect the efficiency of an eddy-current separator?

Shape and size of the particles, speed of the belt, intensity of the magnetic fields, rotating drum speed,
distance to the magnets.

Lecture 5
General 1
1. What are the roles of recycling metallurgy in the end-processing of metals recycling?
Transforming metal scrap to pure metal or alloys.

2. What metallurgical technologies are available for refining metals from metal scrap? How they differ from
normal or primary metals extraction (extractive metallurgy)?
 Melting, smelting and refining
 Alloying and casting
 Alternative hydrometallurgical refining

3. What are 3 types of metallurgical processes? Please give an example how they are used in metals recycling.
 Pyrometallurgy: chemical reactions at high temperatures.T o extract metals from
minerals (or secondary waste) and refine metals from crude metals or metal scrap
o Iron and steel, lead and tin, cu (85%), titanium, ni, co, zn (20%)
 Hydrometallurgy: chemical reactions in aqueous environments, normally below 100°C by
dissolving minerals or metal scrap
o Zn (80%), Cu (15%), Ni, Co
 Electrometallurgy (electrolysis): chemical reactions through charge transfer to precipitate or refine
metals
o Cu electro-refining and electrowinning, zinc electrowinning

Eg. Melting instead of smelting is mostly performed for new scrap (instead of from a mineral).
 4. Please explain why recycled metals may have lower quality compared to the virgin metals produced from
primary ore.
Because of their source, due to the complexity of the scrap (in particular EoL scrap), or the processes (and
number of them) they have to go through to achieve the desired final product.

General 2
1. Please give your explanations what kind of metal scraps are recycled more efficiently with:
– (1) Pyrometallurgy: direct melting
EoL scrap from metal scrap,
– (2) Pyrometallurgy: smelting and refining
Residues compounds (oxides, salts)
– (3) Hydrometallurgy with or without electro-winning or electro-refining (Refer to lecture on
“Hydrometallurgy”)
Residues compounds (oxides, salts) and EoL scrap from metal scrap
2. What are potential different types of impurities in crude metals or in metal scrap?
 Non-metallic elements: S, O, C, N, H (gas dissolution to metals)
 Metallic impurities: from ores
 Non-metallic inclusions: slag entrainment or reactions
 Impurities brought by scrap: tramp elements
 Trace metals: Ag, Au, PGM – economics! (e.g. Cu-, Ni- ores)

3. What are the “harmful” and “valuable” impurities? Please try to find some examples in different metals
refining.
 S and P in steel reduces ductility and toughness
 As, Sb, Sn in copper reduces electrical conductivity

Pyrometallurgy
1. What are different unit operations in pyrometallurgy?
Thermal chemistry (Energy aspects of heating and melting of metals, Calculation of reaction heat: refining energy +
or -), and metallurgical thermodynamics (Reaction equilibrium (equilibrium constant), reaction temperature and
reaction order (Ellingham diagram)).

2. What are the general working principles of the following pyrometallurgical technologies? Please give at
least one example of the above unit operation
 Calcination: thermal decomposition of carbonates/hydrates to oxides
CaCO 3=CaO+CO 2¿ )
 Roasting*: of complex metal scrap for selective hydrometallurgical leaching (from metals to

Nd(s, NdFeB) + O2 → Nd2O3(s)

oxides or salts)

 Sintering*: treatment of solid residues and flue dust

 Smelting*: chemical extraction process: smelting of secondary feed (oxide residues, EAF dust)
 Converting: selective oxidation of (large amount) impurities via air/O2 blowing, Metal or alloy

Cu2S + O2(g) = 2Cu + SO2(g)

production (steel, Cu)

 Fire (pyro) refining*: impurity removing at high T; Widely used for primary metals production
and for refining of scrap metals

3. What types of pyro-refining (fire-refining) technologies are available? Please explain how do they work (by
using an example).
 Metal-to-slag:
o Fire refining: selective oxidation of metal impurities (forming slag)
o Electro-slag refining: for special steel refining, metal droplets through refining slag
(CaF2 based, low melting, less viscous)
 Metal-to-metal:
o Liquid – liquid separation: decreasing solubility of A in B upon cooling (separation of Zn
and Pb: Zn condensation by Pb splashing)
o Liquation: (metal precipitation) impurity solidifying upon cooling, separation from purer
liquid metal (removal of Fe from Sn)
o Zone refining: melting and re-solidification → extra purity (Si, Ge for electronics
industry), repeating operation (=expensive!)
 Metal-to-gas:
o Vacuum refining: reducing partial pressure of product gas
Steel converting: e.g. [C]metal + [O]metal = COgas
o Inert gas purging: removal gas product (e.g. CO) by diluting the partial pressure with
inert gas (Ar or N2).

4. What are the principles of oxidative fire refining? How is it used in refining of metal scrap for removing
harmful impurities?
Bulk metal (Me) is always first oxidized, then the formed oxide (MeO) will oxidize the impurities (Me’). Me’O
forms a slag or dross floating on melt top:
 Applying O2 into melt to selectively oxidize the impurities
[Me’]metal + O2 = (Me’O)slag
 The impurities must have higher affinity with O2 than the bulk metal
 The formed metal oxides must be able to separate from the main (slag formation)
To remove harmful impurities: For high volatile formed impurity oxides ---- Metal to gas refining!
Example: removal of As and Sb from Pb, the formed As2O3 & Sb2O3 with high volatility to gas phase!

5. Exercises from slide 29 and 31.

6. What is Ellingham diagram? How is it used in (oxidative) pyro-refining of metals in recycling or primary
metals production?
Diagram for thermodynamic prediction; it is based on Standard Gibbs energy of metal oxidation reactions
as function of temperature, and serves as comparison of Gibbs energy levels of different metals.
7. How will temperature affect the oxidation of metals for removing impurities? Please find examples.
It can determine whether impurities (metals) can be removed or not. Everything below the base of the
 process can be removed. The lower DeltaG, the easier to remove from the slag.
8. Is it possible to remove Cu (no), Ni (no), Mn (yes), Si (yes), Cr (yes), and C (yes), from steel melt (Fe) with
O2 at 1600°C?
9. Is it possible to remove Fe (yes), and Ni (yes) from Cu scrap melt with O2 at 1200°C?
10. If Al scrap is contaminated with steel, is it possible to refine Al with O2 to remove the Fe at high
temperatures?
No, the highest temperature would not be enough to remove Fe, also Fe has a higher deltaG

Hydrometallurgy
1. What is hydrometallurgy and hydrometallurgical unit operations related to metals recycling? How are they
used for metal recovery in metals recycling loop?
Hydrometallurgy: chemical reactions in aqueous environments, normally below 100°C by dissolving
minerals or metal scrap. Unit operations:
 Leaching/ dissolution -- Purification & separation – Metal precipitation
1. Raw materials (ore, waste, scrap)
2. Dissolution of minerals or metals in aqueous solutions (acid, alkaline, salt, or water)
3. Separation & removal of impurities (precipitation, cementation, solvent extraction, ion-
exchange, ionic liquid, etc.)
4. Metal production (Cementation, gas reduction, electrowinning)
5. Metal product (pure, metal alloy)

Reasons to use hydrometallurgy instead of pyrometallurgy?

– For low quality and complex scrap; Pyrometallurgy may be too expensive!; Hydrometallurgy could be
very selective and flexible!

2. Hydrometallurgical unit operations related to metals recycling:

For recycling: refining of crude metals to pure metals: similar primary production after leaching in later
stage.

3. What is the Pourbaix (Eh-pH) diagram and its applications for leaching or precipitation of metals
in hydrometallurgy?
Diagram in which the thermodynamic equilibrium of metals, ions, hydroxides (or, oxides) in aqueous
solution is shown; Isothermal conditions; the boundary of stability regions of metal, ion, hydroxides (or
oxides) are equilibrium lines; water stability zone is included; does not reflect reaction kinetics.

4. Please explain principles of leaching, reagents used in leaching and factors affecting leaching rate and
leaching selectivity.

Lixiviants:
 Acid
o Mineral acids (strong): H2SO4 HCl, HNO3, HF, their mixtures (aqua regia)
o Organic acids (weak): acetic-, tartaric, formic, citric-, etc.
 Alkaline or base: NaOH, NaCN, NH4OH
 Salt: FeCl3, Na2CO3, NaCl
 Water
 Bacteria assisted (bioleaching)
 Electrochemical/ electroleaching (no leaching agent, but electrolyte needed)
 Anodic dissolution (under electrical potential)

Better dissolution in those metals that have a lower E0, V. Factors affecting leaching: Thermodynamics (T,
concentration of lixiviant (acidity or alkalinity), liquid to solid ratio; Solubility of the solid (mineral) in the lixiviant
must be high); Kinetics (slow process: surface reaction, diffusion of lixiviant in l and s particles, product diffusion;
Mixing; Parameters: Particle size, mineralogy, T, P mixing, liquid/solid ratio, time)
5. What are the typical leaching reactions? Please use examples to illustrate.
Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(g)
Cu(s) + O2(g) + H2SO4(aq) → CuSO4(aq) + H2O(l)
2Al(s) + 2NaOH(aq) → 2NaAlO2 (aq) + H2 (g)
Cu(s)+ ½ O2(g) + 2NH4+(aq) + 2NH3(aq)→ Cu(NH3)42+(aq) + H2O(l)

6. What is the bacteria (assisted) leaching? Where it could be used for metal recovery or recycling?
It is a bioleaching, environmentally friendly way to extract metals like with microorganisms. Can be
applied in sulfidic ores, tailings and metallurgical side streams.

7. What are the leaching reactors/systems available for industrial use?

Cylindrical jacketed stainless steel

8. What are the main differences for leaching of metals in comparison with leaching of minerals, e.g. oxide
ore?
Main differences: “leaching process”:
 Primary hydrometallurgy: dissolution of “natural minerals/ore” vs. recycling hydrometallurgy:
dissolution of “metal scrap”
o Not all metals could be dissolved with acid or alkaline: “selectivity” (☺)!, but some can
be dissolved in both.
o Quite often oxidant is needed, depending on the redox potential of the metals relative to
H2
 Hydrometallurgical recycling of residues/waste: dissolution of “artificial minerals”

9. What are the solution purification techniques? How are they used to remove unwanted metal impurities?
– Hydrolysis: Hydroxide precipitation through ph control of solution.
Fe(OH)3 can be precipitated from Fe3+ at lower pH than the precipitation of Zn2+ to Zn(OH)2. Fe2+ has
to be oxidized to Fe3+ to for Fe(OH)3 precipitation at lower pH
– Cementation: selective removal of metal impurities or selective precipitation of metals; Based on
electrochemical reactions, Difference in electrochemical potentials - displacement reaction, Standard half-
cell potential (Tables)
▪ For metal recovery (Au, Cu), or purification (ZnSO4)

10. What are the standard redox potentials of metals?:

The standard reduction potential is the likelihood that a species will be reduced. It is written in the form of
a reduction half reaction.

11. How redox potential difference could be used in:

– Cementation: The lower the E0, the more reductant not oxidant (taking into reference H2).
- Leaching of metals;
– Purification or cleaning of leached metal solutions:
– Precipitation of metals from a mixture of multi-metal solutions

12. What are different electrochemical techniques used for metal recovery or refining, and their working
principles?
ELECTROLYSIS: As the last step for many metals deposition (from solutions), or for metals refining!
– Cementation: The lower the E0, the more reductant not oxidant (taking into reference H2).
-Electro-winning: use of electrical energy to induce a chemical transformation. Electrolytic precipitation of
metals from purified leach solutions
The higher the E0, the easiest (taking into reference H2).
– Electro-refining: use of electrical energy to induce a chemical transformation. Electrolytic production of
pure, refined metal out of crude metal
Review questions
1. Copper can be precipitated in the metallic form using iron, and it can be refined by electrowinning.
a) Write the reactions for both processes.
b) Calculate the ΔG0 for each process and discuss their feasibility.

2. Consider the recycling of zinc from galvanizing plant waste, zinc oxide is reduced to zinc metal using
aluminum in a cementation process. Zinc metal is also recovered by electrowinning from zinc sulphate
solution.
a) Write the reactions for both processes.
b) Calculate the energy required for the electrowinning process at 100% efficiency if 100 kg of zinc is
recovered. Discuss the economic and environmental trade-offs of each method.

3. In an electrowinning process, 5.0 kg of Zn is deposited over 8 h using a constant current of 120A.

a. Calculate the theoretical amount of zinc that should be deposited.
b. Determine the current efficiency (η).
c. Calculate the power consumed during the 8 h electrowinning process.
d. Determine the total energy consumption.
Lecture 7:

1. What are the sources of polymer for recycling?

 Polymer = a macro molecule produced by linking small repeat units called monomers
o Source: natural (e.g. cellulose, proteins, rubber), synthetic (made from petroleum: e.g.
nylon, PET, epoxy)
 Plastics = Polymers combined with various additives (e.g. plasticizers, stabilizers, pigments, dyes,
fillers, fire retardants) used to enhance or alter material properties (e.g. color, flexibility).
Thermoplastics (butter), Thermosets (irreversible)

Sources: Post‐industrial waste (clean known composition: packs, production waste); Post‐
consumer waste (unknown, mixed, contaminated)

2. What are the driving forces for recycling of plastics?

Regulation, job opportunities, reduction on the consumption of fossil fuels
3. Can all types of polymers be recycled: what can and what cannot? If not, why?
No, thermoset plastics contain polymers that form irreversible chemical bonds and cannot be recycled.
However, thermoplastics can.
4. What are the differences between mechanical recycling, feedstock recycling and energy recovery for
plastics?
 Mechanical recyc: primary (closed loop uprecycling) and secondary (downgrading) recycling; low
cost, only for thermoplastics, sensitive to impurities, mixed w/virgin resins, best time to market.
 Feedstock recycling: teritary recycling (chemical recycling); higher quality of products also used
for thermosets.
 Energy recovery: quatary recycling (valorization)
5. What is a biobased and a biodegradable plastic? Search about one example of each.
Biobased: fully or partially made from biological resources, rather than fossil raw materials; not necessarily
biodegradable (cuttery made of wheat)
 Biodegradable: plastics that biodegrade in certain conditions at their end of life (mushroom pack)
6. What is the recyclability of plastics? What is the compatibility issue in plastics recycling?
Recyclability basic depends on how the plastics were made. Compatibility of plastics depends on whether
or not the use of a secondary material within a component or sub-assembly will cause impurities that will
disrupt the recycling of the primary material. Incompatibility: when different types of plastics are melted
together, they tend to phase-separate, and set in these layers. The phase boundaries cause structural
weakness in the resulting material, meaning that polymer blends are useful in only limited applications.
7. What are the main processing operations (steps) in plastics recycling?
Collection of pack, first sorting, sorting of pack by polymer type (+ other materials for recycling; landfill;
energy recovery), shredding, cleaning, second sorting, input for recyclate production
8. What are the separation technology for plastics recycling?
Sorting tech (highly automated) based on physical/chemical properties:
 Size: screening
 Gravity: sink‐float separator, wind sifter
 Contact charging: electrostatic separation
 Wettability: floatation
 Colour: optical separation
 Composition: Xray fluorescence, IR
 Softening point: thermal adhesive separation

9. What are the challenges in plastics recycling?

Collection and sorting, lifespan, complexity of EoL, quantity (versatile, cheap, durable, light)
10. What are the main challenges for the mixed plastics recycling?
Compatibility, composites, use of dyes, fillers, and other additives (cost to remove this)
11. What are the options of energy recovery for waste plastics?
 Pyrolysis: heating in the absence of O2 (e.g. N2, H2)
 Gasification or combustion: deficient O2, steam
Product: raw materials & secondary fuel (gas, oil, char) and thermal energy
Restrictions: on heating temperature, particle size, moisture content, contamination level (mostly heavy metals and
halogens)

Lecture 8:

A composite material is formed by combining at least two distinct materials, which remain separate at a
macroscopic level in the final structure. This combination creates a material with better properties compared to its
individual components.

1. What are the objectives of composites recycling?

In compliance with the EU goals: Reduction of use of raw materials and CE. Most of the composite scrap are either
waiting for treatment, landfilled or incinerated. Recycling focus: carbon fibers, not the matrix (economic reasons)

2. What are the potential methods of recycling composite materials?

 Composite waste from EoL products of manufacturing scrap
 Size reduction
 Collection and transport
 Separation of EoL composites
 Size reduction
 Recycling (mechanical, thermal, chemical)
 Recyclates (fibers, matrix, fuel, gas)
 Markets (manuf. Of new composites)
3. What types of composite materials or their components are recyclable?
Fine fibres, fine carbon fibres, fluffy fibres, residual resin, secondary fuel or thermal energy, clean fibres,
char residued.
 4. What are the current status, challenges and problems for recycling composite materials?
Status: waste stream increasing but not enough EoL products. Composites are difficult and heterogeneous
waste. 1-10% composites recycled ( manufacturing scrap), 20-30% incinerated and 40-70% landfilled.

Challenges & problems: cost, high energy consumption, low economic value recyclates, scale, machine
wear, sometimes requirement of post-treatment, under research, generation of waste acid or chemicals.

5. How to improve recyclability of composite materials?

Cost-effective solutions
 Development of recycling technologices
 Development of higher quality recycling routes: for matrix, fibres and chemicals.
 Repurposing: design as other apps
 Material design for reuse and recycling: transition to thermoplastic-based composites

Lecture 10:
1. Please describe briefly the life cycle of carbon steel and stainless steel

2. Why availability of steel and stainless steel is important for steel recycling?
More availability can lead to more recycling; Globally about 40% of steelmaking (ferrous) input is from
steel scrap. Cornerstone of the CE

What are the main impurities in steelmaking (and steel recycling)? How these impurities are removed?
Alloys, O, H, N
 De-oxidation, Alloy addition, Stirring (gas or electromagnetic), de-gassing,

3. Why control of copper (and tin) in steel scrap is important? How Cu could be kept low in final steel
product?
Copper is the key element related to surface defects of steel caused by a loss of ductility (T 1050-1200 °C).
Tin increases the negative effect of copper. Vacuum arc re-melting could reliably remove copper

4. Please describe briefly recycling of stainless steel? (EAF-AOD)

Electric arc furnace (EAF) steelmaking (~30% share)
 Making use of up to 100% steel scrap/solid iron as raw material
  Scrap melting and refining

AOD- Argon-oxygen decarburization: decarburization, reduction, desulfurization

5. What are the main impurities in AOD stainless steel making process? What is the main challenge to
effectively remove it?
Tramp elements: Cu, Sn, Zn, Pb, Sb, As, Cr, Ni, Mo.
6. What are the limitations for increasing the recycling rates (EOL-RR, RC, OSR) for carbon and stainless
steel?
Availability still increasing but not enough, not recovered, recognizing the complex use in final products,
Metallurgical recyclability (Thermodynamics and losses)
7. Please describe at least 2 challenges (technical and scientific) for recycling of steel and stainless steel? How
these challenges could be tackled in practice?
 Technical: separation & collection = different shapes and sizes
 Scientific: quality = chemical composition- impurities (alloys, tramp elements)

Lecture 11:
1. What is the difference between a precious, scarce and critical metals?
 Precious: expensive and are superior or noble in properties - i.e., characteristically soft, ductile,
and oxidation resistant; silver (Ag), gold (Au), platinum (Pt), palladium (Pd), rhodium (Rh),
ruthenium (Ru), iridium (Ir), and osmium (Os)
 Scarce: metals which have a lack of (future) available supply of a material due solely to its limited
geological availability and is most often a long-term issue spanning several generations (absolute,
temporary, Structural scarcity of companion metals (by products)).
 Critical: looks beyond geology to also consider factors such as geopolitics and economics and is
often more of a short-term problem (32 critical + 2 strategic* materials: Al, Co, Mg, Am, P)

2. Why does the energy transition rely on CRMs? Why is it so important?

They are used in all technological appliances, and because of the compromised goal.

3. What should be the first initiative to increase the recycling rate of CRMs?Design for disassembly!

4. What are the secondary sources of CRMs?

Urban mines: WEEE, wind turbines, PV solar panels, batteries, catalysts, super alloys

5. What are the current secondary sources for REEs? Will it change in a new future? Why?
Rare earth elements; REE industrial, mine tailings, metallurgical slags, coal ash, incinerator ash and waste
water streams.
6. Describe the general recycle route of a NdFeB PM.
Neodymium iron boron (NdFeB)
  Hydrometallurgy
 Pyrometallurgy
 Electrochemical

7. What are the advantages and disadvantages of each recycling processes for NdFeB PM?

8. Why hydrogen decrepitation is a feasible method for NdFeB recycling? What are the challenges for direct
recycling?
Can be economically viable for high value magnets, maintains the microstructure and magnetic properties
of the original magnets, potentially low Env. impact

Lecture 12:
1. Please explain what are the main sources of scrap zinc and how they are recycled?
Old and new scrap (buildings, manufacturing and processing processes, dusts from steel making, discarded
products). Both are used by primary smelters, secondary metal producers, or makers.

2. What are the different steps to recycle scrap zinc or zinc containing residues to the final metallic zinc or
zinc alloys?
 Brass scrap (Cu-Zn alloys)
o New scrap: remelting to produce the same alloy
o Old scrap: as by product in Cu recycling (smelting ZnO, converting and fire-refining,
electro-refining of Cu; further recovery of zinc from flue dust
 In the galvanizing process (steel scrap from steel making+ residues): hot-dip galvanizing to coat
iron or steel with a Zn layer, that is impermeable and stops corrosion. Results in a metallurgical
bond between zinc and steel with a series of distinct iron-zinc alloys.
o Mechanical separation of zinc from steel – Impossible (Zn-Fe alloy layer)

3. What are the chemistry during the zinc recycling processes? Fe+Zn -- ZnO

4. What kind of residues are generated from steel galvanizing industry?

 Galvanizing dross: top-ash (Zn metal and ZnO, 60-85% Zn+Pb/Al/Fe/Cl (7-9% of total added
zinc)); Bottom: Fe-Zn alloy of 96% Zn (9-13% of total zinc)
 Skimmings: Zn metal, chloride, oxide (14-18% total added zinc)
 5. How to recycle zinc residues from steel galvanizing industry?
 Liquation: liquid-solid metal-metal separation: heating up impure Zn to just above melting point
of zinc, lead and iron removed; melting in various furnaces
 Zinc evaporating: 906°; Zn vapour generation, and to ZnO

6. What are the main sources of lead scrap? Acid lead batteries, plumber, plates and Pb alloys
7. How EoL lead containing products are treated mechanically for lead scrap preparation?
Crushing or shredding: lead materials, plastic scrap, sulphuric acid

8. How lead scrap is metallurgically recycled?

 Recovery of lead from acid batteries (furnaces)
 Processing in primary lead smelters, as mixed feed
 Production of lead alloys from alloy scrap
 Fire refining and electro-refining

Lecture 13:
1. What WEEE stands for? How EU classify the WEEE?
Waste electrical and electronic equipment
a. Temperature changing equipment
b. Screens and Monitors
c. Lamps
d. Large equipment
e. Small equipment
f. Small IT and telecom equipment
2. What are the issues of WEEE and why should we recycle WEEE? Can recycling solve all problems related
to WEEE?
Only 22.3 % globally documented as formally collected and recycled; E-waste is declared as hazardous
(shipped and moved uncontrolled); increasing waste generation; uncontrolled [Link]
3. From WEEE, what can be recovered and what cannot?
Metals Ferrous (steel or stainless), Nonferrous, Scarce metals and PGMs; non metals (polymers, ceramics)
4. Do we have mature processing technology for WEEE recycling? Not yet :(
5. What are the current practices in WEEE recycling?
Sorting and collection; dismantling, hazardous removal, treatment, shredding, screening, magnetic and
electrical separation or density separation
6. What are the current problems and challenges, globally speaking, in the WEEE recycling industry? What
are the social/legislative, economic and technical factors influencing the e-waste recycling?
Uncontrolled recycling practices, Economic reasons, environmental reasons and barriers, social awareness,
informal businesses but new labor opportunities, illegal trading, economics.

Lecture 15:
1. Name and explain the motivations to recycle Li-ion batteries in Europe.
Avoiding dependency on other external suppliers (CRM); clean & ethical mining (sustainable mining);
Competition with other disciplines; Legal aspects – e.g. with second-life systems
2. How are batteries collected for recycling? What is the collection rate for EV batteries?
EoL Libs: 46% in 2022 in EU; separation: manual removal from devices (mandatory by EU)
Challenging due to the large variety of battery designs, capacities, shape, size, and chemistries
3. What are the typical steps of a pre-treatment process?
Dismantling, Sorting, discharge, shredding, screening (air current), screening (sieving), grinding, heat
treatment, magnetic separation
4. Which materials are currently recycled? Which are not and why?
Cobalt, sometimes Li, but no Ni, Cu or Mn or graphite

L16: